The properties of electroactive ruthenium oxide coatings supported by titanium-based ternary carbides

Electroactive oxide coatings on titanium, known in industrial chlorine production as dimensionally stable anodes (DSA), are of limited service life owing to the dissolution of active oxide, but also due to low corrosion stability of titanium, at high anodic potentials and elevated temperatures. In order to improve the anode stability, ternary carbide, Ti₃SiC₂, could be a promising material for the coating support, since chemical corrosion stability of Ti₃SiC₂ is significantly higher if compared to Ti. In this work, the possibility of the sol-gel preparation of RuO₂-TiO₂ coating on Ti₃SiC₂ is investigated and comparison of the basic characteristics of sol-gel processed oxide coating, Ru_0.5Ti_0.5O₂, applied onto Ti₃SiC₂ and Ti, is reported. Microscopic investigation of the coating surface showed that considerably less cracked coating is formed onto the Ti₃SiC₂ support. Slightly higher voltammetric currents are registered for Ti₃SiC₂-supported coating in H₂SO₄ and NaCl solution. The activity for chlorine evolution is higher, while the currents of oxygen evolution reaction are lower for Ru_0.5Ti_0.5O₂/Ti₃SiC₂ anode in comparison to Ru_0.5Ti_0.5O₂/Ti anode. Even though these preliminary results on the basic electrochemical properties of Ru_0.5Ti_0.5O₂/Ti₃SiC₂ anode and chemical stability of Ti₃SiC₂ are promising, the accelerated stability test in NaCl solution showed that coated Ti₃SiC₂ is not anodically stable and lasts considerably shorter than Ru_0.5Ti_0.5O₂/Ti anode prepared and tested under the same conditions.     

A Semi‐Batch Process for Nitroxide Mediated Radical Polymerization

Summary: A semi‐batch process using nitroxide mediated polymerization, was explored for the design of low molecular weight solvent‐borne coatings, typical of those used in the automotive industry. While living radical polymerization (LRP) offers many advantages in the control of polymer chain microstructure that may confer important physical and chemical property benefits to coatings, adapting LRP to a semi‐batch process poses significant challenges in the design and operation of the process. Using styrene monomer, various two‐component initiating systems (free radical initiator, 4‐hydroxy‐TEMPO) were studied to understand the effects of different initiators on the course of polymerization. In addition, an alkoxyamine was synthesized and used as the initiating source. The initiators Luperox 7M75 and Luperox 231 give higher polymerization rates and reasonable control over polymerization, while benzoyl peroxide (BPO), Vazo 67, and the alkoxyamine are less effective. The number of polymer chains in the final product is always less than the theoretical value, reflecting poor initiation efficiency, probably resulting from undesirable termination reactions that become important due to the nature of the semi‐batch process. Adding camphorsulfonic acid (CSA) or charging initiator concurrently with monomer during semi‐batch feed, can increase the polymerization rate while maintaining the living character of the polymerization. The copolymerization of styrene and butyl acrylate is also shown to exhibit living character.

Schematic representation of the exchange reaction to produce N‐TEMPO capped polymer chains.     

A CCD–ADI method for unsteady convection–diffusion equations

With a combined compact difference scheme for the spatial discretization and the Crank–Nicolson scheme for the temporal discretization, respectively, a high-order alternating direction implicit method (ADI) is proposed for solving unsteady two dimensional convection–diffusion equations. The method is sixth-order accurate in space and second-order accurate in time. The resulting matrix at each ADI computation step corresponds to a triple-tridiagonal system which can be effectively solved with a considerable saving in computing time. In practice, Richardson extrapolation is exploited to increase the temporal accuracy. The unconditional stability is proved by means of Fourier analysis for two dimensional convection–diffusion problems with periodic boundary conditions. Numerical experiments are conducted to demonstrate the efficiency of the proposed method. Moreover, the present method preserves the higher order accuracy for convection-dominated problems.     

Chemical and Isotopic Tracer Evaluation of Water Mixing and Evaporation in a Dammed Texas River During Drought

The interaction between drought and river regulation is monitored to better understand river flow mixing, evaporation and surface‐groundwater exchange in changing regional climates and in increasingly regulated waterways. This study compared Brazos River stable isotope (δ¹⁸O and δD) and electrical conductivity values with reservoir, creek and aquifer samples in the Brazos watershed, the largest watershed in Texas. The combination of tributaries, rainfall and the Brazos River Alluvium Aquifer, on the one hand, and the Lake Whitney reservoir, on the other hand, represent endmembers of dilute run‐off water and evaporated saline water, respectively. A simple isotope mixing model that uses monthly river discharge, Lake Whitney discharge, historical monthly precipitation δ¹⁸O and pan evaporation accurately reconstructs river δ¹⁸O (±0.5‰ on average). Data and isotope balance modelling support continued evaporation of ¹⁸O‐enriched Lake Whitney water as it flows downstream, although the most evaporation took place in Lake Whitney. The difference between river and precipitation δ¹⁸O, or Δ¹⁸O_RIV‐_PPT, here a measurement of degree of evaporation, ranged from ?0.1‰ for a small creek, to 1.7‰ for the Brazos River, to at least 2.7‰ in Lake Whitney. This study indicates that drought in regulated rivers may enhance reservoir discharge dominance in river flows during peak drought conditions when combined run‐off and baseflow dominance would be expected in a similar undammed river. Copyright © 2016 John Wiley & Sons, Ltd.     

Transformations of residual fertilizer P in a semi-arid tropical soil under eight-year peanut-wheat rotation

Long-term transformations of residual phosphorus (P) governs the availability of phosphorus to crops. Very limited information is available on the transformations of residual fertilizer P in semi-arid tropical soils under long-term crop rotations. Therefore, using sequential phosphorus fractionation procedure, we studied changes in labile and stable forms of inorganic and organic P in a semi-arid alluvial soil (Typic Ustisamments) after eight years of annual fertilizer P application either to one crop (alternate) or to both crops (cumulative) in a peanut (Arachis hypogaea) — wheat (Triticum aestivum) rotation.Total residual fertilizer P in soil (P recovered from P-fertilized minus control plots) ranged from 62 to 176 mg P kg^–1. In the alternate P treatments (P applied to peanut or wheat only), on an average of 3 rates of applied P (13, 26 and 39 kg P ha^–1), in surface (0–15 cm) and subsurface (15 to 30 cm) soil, respectively, residual fertilizer P consisted of 14.8 and 2.2% resin-P, 8.6 and 2.8% NaHCO₃-P, 6.3 and 0% microbial-P, 31.4 and 4.2% NaOH-P, 7.8 and 3.0% aggregate protected-P, 12.5 and 3.0% HCl-P, 3.4 and 0% H₂SO₄-P. The corresponding values for surface and subsurface soils of cumulative P treatments (P applied to both peanut and wheat) were: 12.8 and 1.6% resin-P, 6.9 and 2.3% NaHCO₃-P, 4.7 and 0% microbial-P, 32.5 and 4.2% NaOH-P, 5.6 and 2.0% aggregate protected-P, 14.8 and 3.8% HCl-P, 6.7 and 2.1% H₂SO₄-P. Considerable lower values for the 15–30 cm depth indicate only a very small movement of residual P to the subsoil.Significantly lower amount of fertilizer P (28% and 44%) found in labile (resin, NaHCO₃ and microbial P) and semi-labile (NaOH and sonicated NaOH P) fractions for the cumulative P treatment than alternate P treatment (35 and 46%, respectively) suggests that increased rates and frequency of applied P tend to enhance the conversion of residual P to stable forms which are less available to plants. About 12 to 19% of residual fertilizer P found as organic P in labile and semi-labile forms confirmed that organic P increased with long-term fertilizer management. In conclusion, the results of our study suggest that the alternate application of fertilizer P to a crop, as is shown for wheat, helps reduce the transformations of residual P to stable P forms.     

原子磁强计检测光闭环稳定系统设计

SERF态原子磁强计已实现人类历史上最高的0.16fT/Hz1/2的灵敏度。其检测方法主要是法拉第调制法。但法拉第调制法中光电流摄动或环境温度变化等干扰导致的检测光强的起伏会造成检测结果的不准确。为抑制检测光强起伏,设计了闭环原子磁强计检测光稳定系统。在法拉第调制法的基础上,增加了光路子系统和控制子系统对检测光强进行闭环稳定控制。通过对随机干扰进行闭环控制仿真与实验,验证本系统可以有效抑制各种干扰引起的光强起伏,使系统抗干扰能力提高1.2%,从而提高原子磁强计的检测精度。     

SBR/LDPE复合改性沥青高温性能研究

研究了SBR／LDPE熔融共混物改性沥青的高温贮存稳定性及其粘温特性和动态力学性能，并利用光学显微镜观察了各种改性沥青在高温下随时间的变化。结果表明：采用预先制备的SBR／LDPE共混物所得到的改性沥青能够在高温下稳定贮存。同时，相形态观察也表明。这种共混物改性沥青的高温相形态也不随时间变化。而聚合物的加入在一定程度上降低了沥青的温度敏感性，提高了沥青的高温使用等级。     

固体三元稳态ClO2急性经口、遗传及蓄积毒性研究

固体三元稳态二氧化氯是为了解决二元产品活动化率低、活化酸度高、活化损失大的缺点而研制出的新型固体ClO2产品。通过对其急性经口毒性、遗传毒性及蓄积毒性的试验研究，发现雌雄小鼠的急性经口LD50值均大于21．5g/kg，该产品属于实际无毒级；剂量达5．00g/kg，未检出对雌雄小鼠骨髓嗜多染红细胞的诱变活性；给药20d后，动物死亡仍未足半数，K＞5，该产品为弱蓄积性。     

武汉市大气降水δD和δ~(18)O变化特征及水汽来源

为了确定长江流域中游大气降水特征和水汽来源,以全球大气降水观测网(GNIP)武汉站点多年大气降水稳定同位素数据为基础,探讨了长江中游武汉地区大气降水稳定同位素随季节变化特征。通过建立当地大气降水方程,结合气象因素和降水氘盈余变化,揭示了武汉地区不同季节大气降水水汽来源。结果表明:大气降水在降落地面之前经历了非平衡分馏过程,且平衡程度接近于东部季风沿海地区;大气降水稳定同位素表现出明显的季节性特征,且冬季和夏季降水δD和δ~(18)O值与雨量之间负相关,表现出明显的"雨量效应";大气降水水汽来源主要受季风活动的控制,冬季水汽主要来自北方大陆冷湿气流,而春季降水表现出局地蒸发来源,夏季和秋季降水来源受西南季风和东南季风的双重影响。     

三芳基甲烷树脂的磁性行为

介绍了ＢＡ／Ｐｙ，ＢＡ／Ｐｈ和ＰＨＢＡ三种具有三芳基甲烷结构Ｂ阶树脂的合成方法及分子链的单元结构形式。对用紫外光和激光照射法进行脱氢反应的实验条件及脱氢化后树脂的磁性能（磁滞现象，矫顽力和磁化强度）进行考查。