Simple and novel synthesis of zirconia whiskers from a phosphate flux

High quality zirconia whiskers have been successfully prepared by molten salt method, using zirconium oxychloride (ZrOCl₂·8H₂O) and sodium phosphate tribasic dodecahydrate (Na₃PO₄·12H₂O) as precursor and molten salt, respectively. The effects of types of molten salt and heat treatment temperature on the formation of zirconia whiskers were characterized by XRD, Raman, DTA-TG, FE-SEM, TEM, SAED and HR-TEM. When Na₃PO₄·12H₂O is utilized as molten salt and the heat treatment temperature is 900?°C, the as-prepared zirconia whiskers with length ranging from 4?µm to 8?µm show an average aspect ratio of 25. The obtained ZrO₂ whiskers with monoclinic structure are elongated along [010] direction and exhibit a smooth surface with no distinct defects. The XRD and Raman results reveal that the phase transformation from tetragonal zirconia to monoclinic zirconia occurs with the increased crystal size and the water quenching treatment can significantly reduce the content of sodium zirconium phosphate [Na_9–4×Zr_x(PO₄)₃] in the final product. The growth mechanism of zirconia whiskers is supposed to be a dissolution-precipitation process. Since the sodium zirconium phosphate [Na_9–4×Zr_x(PO₄)₃] effectively promotes the dissolution of zirconia in liquid molten salt, zirconia can grow into zirconia whiskers according to its anisotropy.     

Importance of finding the proper ratio of alkaline earth oxide in a lithium-bismuthate-phosphate glass in order to enhance the tailoring of structural and electrical properties

Structural features of the glass family xLi₂O- yMgO (4.8 Bi₂O₃ 47.6 P₂O₅) obtained by melt quenching technique were studied taking into account the density, FTIR and UV–vis spectra and also the electrical response observed by impedance spectroscopy. In this work it becomes clarified how the alkaline earth oxides stabilize the glassy matrix and also, the fundamental importance of determining the optimal proportion in order to obtain a flabby easily polarizable matrix to enhance the electrical behavior due to a boosted cation mobility. It is evidenced that when the glass composition becomes complex it is needed to take into account a larger number of structural parameters to understand, to predict or to design the resulting physical properties.     

Co3xCu3-3x(PO4)2 microspheres,a novel non-precious metal catalyst with superior catalytic activity in hydrolysis of ammonia borane for hydrogen production

Development of robust and cheap catalyst for fast hydrogen evolution from ammonia borane (AB) aqueous solution is an interesting and important topic in the field of hydrogen energy. Herein, a novel non-precious Co_3xCu_3-3x(PO₄)₂ catalyst possessing high reactivity in AB hydrolysis has been developed for the first time. By tuning the molar ratio of Co and Cu, a series of Co_3xCu_3-3x(PO₄)₂ with different x were synthesized and the catalytic behavior in AB hydrolysis was examined. At the optimal x of 0.8, an ultrahigh turnover frequency of 72.6 min⁻¹ was achieved. Additionally, the synergistic effect between Cu₃(PO₄)₂ and Co₃(PO₄)₂ was experimentally confirmed, and the reaction kinetics of AB hydrolysis catalyzed by Co_2.4Cu_0.6(PO₄)₂ were investigated. This work provides a simple route and some new insights for the fabrication of a cheap P-containing catalyst with robust catalytic performance.     

Recovery of phosphate ores in the modified three-product column (3PC) flotation cell

This work details the results obtained for the rougher flotation of phosphates in a modified flotation cell known as a three-product column (3PC), at both the laboratory and pilot plant scales. Results were compared to a conventional column cell-CCC. The 3PC cell separates the drained (rejected) particles from the froth zone (third product) and uses a secondary wash water system between the feed and the froth zone (II). Bench-scale studies measured the effect of the two water surface rates on mass and metallurgical recoveries and concentrate grades (P₂O₅, Fe₂O₃, and SiO₂) in all the flows. At pilot scale, the influence of wash water (J_W2) and column design on the flotation separation parameters was studied. Results showed that, compared with the conventional column cell (CCC), the 3PC yielded, in all cases, clean high-grade concentrates, with a minor concentration of impurities (Fe₂O₃ and SiO₂). Concentrate recoveries ranged from 40% to 70% for apatite and were lower when compared to CCC, but it is believed that the third product could be recycled to the fee. This drop-back product operating with J_W2 = 0.0 cm s⁻¹ might yield 5–10% extra in apatite recoveries and enhancing this J_W2 values, the apatite recovery decreased by 0.5–3% but rejection of impurities was very high. Results appear to show that the 3PC may be used as a rougher-flash or Cleaner unit with an optional recycle of the third product into the rougher or simply discarding it. Data on the influence of some cell design and gas dispersion parameters on process efficiency are reported, and the potential practical applications for this type of cell are envisaged.     

A mixed collector system for phosphate flotation

Flotation has been used in industry for more than a half century as the primary technique for upgrading phosphate. While the flotation of phosphate was inefficient when oleic acid was used alone as a collector, therefore a mixed collector of oleic acid (HOl), linoleic acid (LA) and linolenic acid (LNA) was employed to improve the recovery of phosphate flotation. The batch flotation results showed that the optimal composition of the mixed collector was 54 wt.% HOl, 36 wt.% LA and 10 wt.% LNA. Additionally, the effect of pH on the mixed collector application was studied while considering the surface tension, contact angle and micro-flotation. The results showed that the mixed collector should be used at a pH of 9.5. Above a pH of 9.5, the adsorption of fatty acids dimers on the apatite surface hindered phosphate flotation. The influence of the mixed collector assembly on apatite flotation was also investigated. It was demonstrated that due to its low critical micelle concentration, a sufficiently hydrophobic apatite surface could be generated at a collector concentration of 60 mg/L. In addition, zeta potential experiments suggested that collector adsorption was governed by chemisorption. FTIR and XPS spectra studies further indicated that the chemical reaction involved the carboxyl groups of fatty acids and Ca species at the apatite surface for each fatty acid in the mixed collector.     

Optimized structural and mechanical properties of borophosphate glass

A series of phosphate glasses composed of (65-x)P₂O₅–15BaO–5Al₂O₃–5ZnO–10Na₂O-xB₂O₃ (x = 0, 2, 4, 6, and 8 mol%) were successfully prepared using the melt-quenching method. The effects of the addition of boron trioxide (B₂O₃) on the physical, structural, and mechanical properties of the glasses were investigated. As the added content of B₂O₃ increased from 0 to 6 mol%, the glass exhibited increased density and transition temperature, and decreased molar volume, indicating optimization of the glass stability. Raman spectroscopy revealed that the introduction of B₂O₃ transformed the glass from a chain structure to a three-dimensional network structure, which enhanced the chemical stability of the glass by the cross-linking of long phosphate chains with boron ions. Regarding the mechanical properties, when the boron content was 6 mol%, the flexural strength of the glass was 41% higher than that of the undoped boron, while the Vickers hardness and Knoop hardness values increased by 20.58% and 7.05%, respectively, and the fracture toughness was slightly decreased. In general, improving the mechanical properties of phosphate glass is of great significance for increasing the applications of this glass.     

Protective properties of cataphoretic epoxy coating on aluminium alloy AA6060 modified with electrodeposited Ce-based coatings: Effect of post-treatment

Ce-based conversion coatings (CeCCs) are a promising alternative to toxic chromate coatings on the metal substrates. In this work the CeCCs were electrodeposited on aluminium alloy AA6060 from aqueous solution of Ce(NO₃)₃ at different potentials (−0.95 V, −1.2 V and −1.4 V). Effect of deposition potential and post-treatment in the phosphate solution on morphology and protective properties of CeCCs with top cataphoretic epoxy coating was studied. To assess the differences between the protective systems, originating from the different CeCCs pre-treatments, electrochemical impedance spectroscopy (EIS), polarization measurements, AFM and SEM/EDS analysis were used. The EIS study was undertaken to follow the evolution of corrosion behaviour of epoxy coating/CeCCs protective systems over prolonged time of exposure to the chloride environment (3 wt.% NaCl). Results suggest significantly improved corrosion stability of epoxy coating on AA6060 with as-deposited CeCCs sub-layers with respect to the same epoxy coatings with phosphate post-treated CeCCs. The far best protective properties, i.e., the greatest value of pore resistance and the lowest value of corrosion current density were provided by the epoxy coating/CeCC protective system with CeCC deposited at −1.2 V and without post-treatment.     

Prediction of sediment,particulate nutrient and dissolved nutrient concentrations in a dry tropical river to provide input to a mechanistic coastal water quality model

A Generalised Additive Modelling (GAM) approach is applied to prediction of both particulate and dissolved nutrient concentrations in a wet-tropical river (the Fitzroy River, Queensland, Australia). In addition to covariant terms considered in previous work (i.e. flow, discounted flow and a rising-falling limb term), we considered several new potential covariates: meteorological and hydrological variables that are routinely monitored, available in near-real time, and were considered to have potential predictive power. Of the additional terms considered, only flows from three tributaries of the Fitzroy River (namely, the Nogoa, Comet and Isaac Rivers) were found to significantly improve the model. Inclusion of one or more of these additional flow terms greatly improved results for dissolved nitrogen and dissolved phosphorus concentrations, which were not otherwise amenable to prediction. In particular, the Nogoa sub-catchment, dominated by pasture for cattle, was found to be important in determining dissolved inorganic nitrogen and phosphorus concentrations reaching the river mouth. This insight may direct further research, including future refinement of processed-based catchment models. The GAMs described here are used to provide near real-time river boundary conditions for a complex coupled hydrodynamic and biogeochemical model of the Great Barrier Reef Lagoon, and can be coupled with a forecasting hydrological model to allow integrated forecasting simulations of the catchment to coast system.     

Corrosion of phosphate added high-chrome refractory materials in an entrained-flow gasifier

Durability of the refractory liner located in an entrained-flow gasifier is one of the main factors affecting the efficiency and cost of gasification process. This study investigates the corrosion mechanism of phosphate added high-chrome refractories in a commercial entrained-flow gasifier and the effect of phosphate additives on the improvement of service life combining thermodynamic simulation calculations. The microstructures, chemical compositions, and mineral phases of the corroded samples were analyzed by scanning electron microscopy (SEM and EDS) and X-ray powder diffraction (XRD). The results demonstrated that chemical corrosion mainly occurred at the slag-matrix interface and the junction of aggregates and matrix regions. Complex spinel solid solutions were formed at the slag-refractory interface. Phosphate additives decomposed into gaseous products (such as O₂, P₂O₃) and diffused into the interior of refractories at or close to the slag-refractory interface, not only causing an oxidizing environment but also increasing the phosphate contents in the interior of refractories. Phosphate additives in the infiltration layer occupied the gaps between crystal grains of (Cr, Al)₂O₃ solid solutions, reduced the infiltration of silicate phases, and absorbed Ca and Na in the slag, which subsequently increased the viscosity of the slag.     

2,2'-亚甲基双(4-叔丁基苯基)磷酰氯的制备及表征

以2,2'-亚甲基-双(4-叔丁基苯)酚和三氯氧磷为原料,通过滴加缚酸剂和催化剂三乙胺,反应生成了2,2'-亚甲基双(4-叔丁基苯基)磷酰氯。主要研究了加料顺序、时间、温度和溶剂量对反应产物和收率的影响。当滴加三乙胺,加入25 mL溶剂,反应时间2 h和反应温度为45℃时收率可以达到68%。对产物进行了傅里叶红外变换光谱仪(FTIR)、核磁共振仪(NMR)、质谱仪(MS)和差式扫描量热分析(DSC)表征,各项检测表明,合成的产物为2,2'-亚甲基双(4-叔丁基苯基)磷酰氯。