用失效的C－Pd催化剂生产氯化钯

介绍了用锌镁粉直接还原与处理失效废弃的Ｃ－Ｐｄ催化剂，并用自制混酸直接生产氯化钯的工艺。该工艺比传统的铝粉置换法更快捷，钯收率更高。     

Round-Robin Test on methods for determining chloride transport parameters in concrete

This paper presents the results of a Round-Robin Test on methods for determining chloride transport parameters in concrete, carried out by the Technical Committee TC 178-TMC: “Testing and Modelling Chloride Penetration in Concrete” in which 27 different laboratories around the world have participated, using 13 different methods, in triplicate specimens, for 4 different mixes of concrete cast with different binders. Four different groups of methods have been tested: Natural diffusion methods (D), Migration methods (M), Resistivity methods (R) and Colourimetric methods (C). The statistical treatment of the data has been carried out according to the International Standard ISO 5725-2:1994 for the determination of the accuracy (trueness and precision) of measurement methods and results. Part 2: Basic method for the determination of the repeatability and reproducibility of a standard measurement method. In order to make an evaluation of these methods, four indicators have been identified and within each of them, several sub-indicators have been assigned. According to this system of classification, the methods have been classified following each indicator (trueness, precision, relevance and convenience), and also globally, by assigning different factors of importance, F.I., to the different indicators.     

Electrochemical corrosion behavior of carbon-based thin films in chloride ions containing electrolytes

Commercially available carbon-based thin films consisting of single layers of amorphous diamond-like carbon or multilayers of crystalline TiAlN or CrN with diamond-like carbon top coatings were evaluated in relation to their electrochemical corrosion behavior in chloride ions containing electrolytes. The hardened working steel (an alloy of 0.9% C, 4.1% Cr, 4.9% Mo, 1.8% V, 6.4% W) was used as a substrate material.The potentiodynamic corrosion behavior of coated samples was tested in 3.5 wt.% NaCl solution and Hank's balanced body solution, HBBS (0.89 wt.% NaCl, further chlorides, sulfates, carbonates and phosphates). The multi-layers TiAlN + a-C:H:W and CrN + a-C:H:W exhibited only a minor improvement in corrosion resistance. Single layers of amorphous diamond-like carbon coating without hydrogen (a-C) spall off during the corrosion tests in chloride containing media. A minor improvement of the corrosion resistance is possible. The a-C:H and the a-C:H:Si, which contain hydrogen, showed the best corrosion resistance with a 100 times lower corrosion current density.     

阴离子交换树脂吸附镉的动力学研究

研究了强碱性阴离子交换树脂吸附镉的主要动力学因素。通过实验找出了过程的限制环节，推算出交换反应的活化能、反应级数及动力学方程。     

Quantitative study of the kinetics of hydrogen evolution reaction on aluminum surface and the influence of chloride ion

The behaviors and kinetics of hydrogen evolution reaction (HER) on pure aluminum with passive film in the presence and absence of chloride ion are quantitatively investigated by using the tip generation/substrate collection mode of scanning electrochemical microscopy (SECM) with dual Al/Pt ultramicroelectrode (UME) as tip electrode and Pt UME as substrate electrode. The standard rate constants k⁰ and transfer coefficients α_H of HER in ClO₄⁻- and Cl⁻-containing solution are 6.9 × 10⁻⁷ cm/s and 0.22, 7.1 × 10⁻⁶ cm/s and 0.19, respectively. Results show that the kinetic of HER is slow and the destruction of Cl⁻ on passive film can significantly promote the HER on Al surface. Moreover, these α_H far less than commonly used 0.5 in corrosion research, can explain the great difference between theoretical Tafel slopes and experimental results. Besides, the existence of current plateau in Al electrode explains the large difference in corrosion potential during parallel testing.     

Stress corrosion cracking in 316L stainless steel bellows of a pressure safety valve

There were three consecutive occurrences of bellows failure in a particular pressure safety valve (PSV) of a petroleum refinery within a time span of one week. The bellows were made of 316L grade austenitic stainless steel, and the PSV was mounted on one of the vessels of vacuum gas oil service in a hydrocracker unit. Metallurgical analysis of the failed bellows revealed that the failure had occurred by stress corrosion cracking (SCC). It was found that the SCC was promoted in the bellows due to the presence of high amount of chloride ions in the operating environment. Studies confirmed that SCC had initiated from the outer surface of the bellows and propagated inwards, resulting in leakage of hydrocarbon from the PSV. The source of chlorine in the environment was identified. It was discovered that SCC in the bellows was caused due to a previous failure in the heavy polynuclear aromatics (HPNA) absorption bed located upstream the process flow line. This failure was due to the presence of high concentrations of chlorine in the granulated activated carbon that was used in the HPNA absorption bed. During the repair of the HPNA bed, there was deposition of carbon soot on the body of the PSV. This carbon soot was the source of chloride ions for SCC to occur in the bellows. Generally, in chloride SCC, crack propagation in 316L SS takes place by transgranular mode. In the present case, however, the crack propagation was predominantly by intergranular mode. The metallurgical factors responsible for this change in micro-mechanism of crack propagation during SCC have been discussed.     

Effect of fine crack width and water cement ratio of SHCC on chloride ingress and rebar corrosion

SHCC (Strain Hardening Cement-based Composite) is a material known for its strain-hardening behavior under tensile and bending stress and its characteristic numerous small cracks. SHCC is expected to show superior durability because of the fineness of the cracks. In this study, chloride ingress through cracks into SHCC and progress of rebar corrosion in three mixtures of SHCC with various water-cement ratios were investigated. Through a chloride solution immersion test, it was confirmed that chloride could penetrate through even very fine cracks. The resistivity of cracked SHCC against chloride ingress is mainly governed by the accumulated crack width and the water cement ratio. Chloride pre-mixed SHCC specimens were left in a high-temperature, high-humidity chamber for 11 months to promote rebar corrosion. While the accumulated crack width and the water cement ratio were both influential to an increase in corrosion area, only the water cement ratio had bearing on corrosion loss.     

Sensitivity of uncertainties in performance prediction of deteriorating concrete structures

Deterioration models for the condition and reliability prediction of civil infrastructure facilities involve numerous assumptions and simplifications. Furthermore, input parameters of these models are fraught with uncertainties. A Bayesian methodology has been developed by the authors, which uses information obtained through health monitoring to improve the quality of prediction. The sensitivity of prior and posterior predicted performance to different input parameters of the deterioration models, and the effect of instrument and measurement uncertainty, is investigated in this paper. The results quantify the influence of these uncertainties and highlight the efficacy of the updating methodology based on integrating monitoring data. It has been found that the probabilistic posterior performance predictions are significantly less sensitive to most of the input uncertainties. Furthermore, updating the performance distribution based on ‘event’ outcomes is likely to be more beneficial than monitoring and updating of the input parameters on an individual basis.     

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。     

PE/PVC共混物与PE界面黏结性能研究

为改善聚氯乙烯(PVC)和聚乙烯(PE)界面黏结性能,制备了一系列PE/PVC共混物及其与PE的黏结材料,探究了原料比例和成型温度对(PE/PVC)/PE界面黏结性能的影响。结果表明,PE/PVC共混物为不相容体系。共混物中随着PE含量升高,体系拉伸强度增大,断裂伸长率升高。(PE/PVC)/PE材料中,随着PE/PVC共混物中PVC含量升高,PE/PVC与PE的界面黏结强度先升高后降低。成型温度升高,界面黏结性能提高。在PE/PVC比例为60/40、黏结温度为100℃时,PE/PVC共混物与PE的界面黏结强度最大,可与共混物拉伸强度接近。