Preparation and Properties of Embeddable Ag/Ag Cl Gelling Reference Electrode for Rebars Corrosion Monitoring in Concrete

Reference electrodes are a key part for corrosion monitoring and measurement of rebars in concrete. A reference electrode that can be buried in concrete is fabricated by using Ag/Ag Cl electrode and methyl cellulose gelling electrolyte. The stability, repeatability and anti-polarization of the reference electrode are investigated; the influences of the inner electrolyte loss, exterior OH- contamination, and temperature on the potential of the reference electrode are also investigated in this paper. The results show that the reference electrode has good stability, repeatability, and antipolarization. The influences of inner electrolyte loss, exterior OH- contamination, and temperature on the potential of the reference electrode are minimal. Therefore, it can be used for corrosion monitoring and measurement of rebars in concrete.     

壳聚糖在1mol／LHCl中对Q235碳钢的缓蚀性能及机理研究

用失重法、动电位极化测试考察不同质量浓度、温度下,壳聚糖在lmol／LHCl溶液中对碳钢的缓蚀作用及机理。结果表明：随缓蚀剂质量浓度增加,壳聚糖的缓蚀效率升高,腐蚀速率下降;温度升高,腐蚀速率加快,但缓蚀效率并未下降,333K时缓蚀效率仍可达93．8％;壳聚糖在金属表面的吸附行为符合Langmuir吸附等温线,其与金属...     

基于最小二乘法与RBF神经网络的溶解氧检测系统设计

为克服温度对溶解氧传感器的影响,对极谱型溶解氧检测系统的溶解氧电极激励源、高精度信号采样、软件标定和温度补偿等方面进行研究。通过对极谱型溶解氧传感器工作原理进行分析,设计了极谱型溶解氧传感器检测电路;根据溶解氧电极的温度特性,设计了基于NTC（负温度系数）热敏电阻的硬件温度补偿电路,并利用最小二乘法及RBF神经网络构建了软件温度补偿模型。利用饱和蒸馏水进行温度补偿实验,结果表明：经温度补偿后,该溶解氧检测系统的相对误差及采样波动均在1%以内,大大减小了传感器的非线性误差,测量精度和稳定性均可满足应用要求。     

用于深海极端环境下的pH电极制备方法改进

pH值是表征深海热液环境以及扩散流区域溶液化学性能的基本参数,因此原位精确获取溶液pH值是很多海洋科学研究者关注的问题。以前试制的电化学原位传感器IrOx电极,在实际海试中虽然对海底异常信号有响应,但由于信号漂移问题,电极只能用于定性地发现异常。基于熔融碳酸锂氧化金属原理,提出了改进传统熔融碳酸锂法,并设计了强制空气对流和碳酸锂添加过氧化钠两种制备方法。通过实验室的性能测试以及相应的表面扫描电镜测试表明,用改进的方法制得的电极,校正曲线均符合能斯特定律。用强制空气对流和混合碳酸锂/过氧化钠法制得的电极,其性能均明显优于传统熔融碳酸锂法。可推断,在熔融碳酸锂氧化贵金属铱的过程中,氧含量的充分与否是影响IrOx电极的性能和表面形态的重要因素,其中性能最优的是混合碳酸锂/过氧化钠法制得的电极。该类电极具有如下优点:重复性好;在大跨度pH溶液之间的响应快速稳定,长时间连续监测的漂移小于5 mV;同一批次所制备电极性能几乎相同;使用寿命长等。因此,该pH电极可用于深海的原位探测。该工作为进一步制备高性能的IrOx电极奠定了坚实的基础。     

深海腐蚀检测用水密电子舱设计

设计了一种可在300 m 水深条件下进行腐蚀电化学在线检测作业的水密电子舱, 它主要由耐压水密壳体以及集成在壳体外部的插接件式电极系统和多孔屏蔽罩组成。耐压壳体由圆柱形筒体和加强型平盖构成, 满足设计条件下的强度、密封、防腐要求。三电极系统采用水密接插件式设计, 安装在加强型平盖上; 电极系统与外部多孔罩组成开放屏蔽式电解池, 可在水下进行在线电化学测试。     

一种新型电镀法制备的Ir/Ir(OH)x pH电极及其在加州纽波特港海域的应用研究

Resulting from the rising levels of atmospheric carbon, ocean acidification has become a global problem. It has significant impacts on the development, survival, growth and physiology of marine organisms. Therefore, a highprecision sensor is urgently needed to measure the pH of sea-water. Iridium wire with a diameter of 0.25 mm is used as the substrate, and an Ir/Ir(OH)_x pH electrode is prepared by a one-step electrochemical method in a Li OH solution at the room temperature. A scanning electron microscope(SEM) observation reveals that it is coated with nanoscale particles. In laboratory tests, the electrode exhibits a very promising pH response, with an ideal Nernst slope(56.14–59.52), fast response, good stability and long life-span in tested pH buffer solutions. For a sea trial,four pH electrodes and one Ag/Ag Cl reference electrode are integrated with a self-made chemical sensor, and a profile detection of nearly 70 m is implemented near Newport Harbor, California on August 3, 2015. The results reflect that the pH value measured by the sensor is very close to the data given by Sea-Bird 911 plus CTD, with a difference value ranging from 0.000 075 to 0.064 719. And the sensor shows a better data matching degree in 0–40m water depth. In addition, the high precision and accuracy of the sensor make it possible to use in the ocean observation field.     

八所港矿砂码头混凝土腐蚀现状分析

针对海南八所港矿砂码头服役近30年的混凝土梁、柱和70年的甬道等结构腐蚀状况进行现场调研,发现钢筋混凝土结构出现钢筋锈蚀、混凝土剥落,部分混凝土严重破损。测量了其混凝土梁、柱、甬道等不同位置混凝土和铁锈中氯离子含量,分析了局部环境对氯离子分布的影响。根据调研结果总结分析了其破损原因。结果表明混凝土中氯离子分布呈现规律性变化,且铁锈中的氯离子含量远小于混凝土中氯离子含量。     

氯盐干湿环境下受弯横向裂缝对钢筋混凝土耐久性影响

为了研究持续开裂状态下横向裂缝对钢筋混凝土结构耐久性的影响特性,开展了8根受弯开裂钢筋混凝土梁构件的盐溶液干湿循环试验;借助无损检测技术和破损实测方法,分别对氯离子侵入量、钢筋半电池电位、腐蚀电流密度以及平均锈蚀率等进行了对比分析。研究结果表明,裂缝的存在将提高混凝土的渗透性,裂缝处及周围混凝土内的氯离子含量明显增大;对于一定裂缝分布状况的钢筋混凝土试验梁,内部钢筋的腐蚀电位、腐蚀电流密度以及平均锈蚀率均高于裂缝自愈及无裂缝的试验梁,并受到保护层厚度与裂缝开展状态的影响,其影响规律可用单位长度内的平均裂缝宽度与保护层厚度的比值wm/c来进行综合评价。综合试验结果,初步建议海洋干湿侵蚀环境下钢筋混凝土构件的最大裂缝宽度wmax宜小于0.003 3 c,相关结论可为海洋混凝土结构的耐久性设计提供参考。     

氯离子侵蚀对钢筋混凝土构件抗力影响的研究

氯化物是钢筋混凝土结构在使用寿命期内可能遇到的一种最危险的侵蚀介质,混凝土中钢筋表面的氯离子浓度超过一定的限值,钢筋就可能会发生锈蚀,锈蚀的钢筋会导致混凝土构件的承载力下降.通过分析国内外研究者所做的大量工作,讨论了氯离子侵入引起的锈蚀钢筋混凝土构件的抗力计算方法,为氯化物环境条件下混凝土结构的耐久性评估提供参考.     

Numerical investigation of the uplift performance of prestressed fiber-reinforced polymer floating piles

Finite element analyses of prestressed fiber-reinforced polymer floating piles subjected to uplift force have been conducted in this paper. First, parameters of the modified BPE model (bond–slip model at the fiber-reinforced polymer–concrete interface) were calibrated using existing pullout testing data on fiber-reinforced polymer rebars embedded in concrete. Nonlinear spring elements were used in numerical modeling to characterize the bond–slip behavior at the fiber-reinforced polymer–concrete interface. A parametric study was performed to assess the influence of rebar diameter, fiber-reinforced polymer material, embedment length, and concrete strength on the mobilized bond stress. Upon the successful modeling of the pullout performance of fiber-reinforced polymer rebars in concrete, numerical models were developed to investigate the dependence of the uplift performance of floating piles on the prestress level, uplift force, fiber-reinforced polymer type, and compressive strength of concrete.     

Control of the repeatability of high frequency multibeam echosounder backscatter by using natural reference areas

The increased use of backscatter measurements in time series for environmental monitoring necessitates the comparability of individual results. With the current lack of pre-calibrated multibeam echosounder systems for absolute backscatter measurement, a pragmatic solution is the use of natural reference areas for ensuring regular assessment of the backscatter measurement repeatability. This method mainly relies on the assumption of a sufficiently stable reference area regarding its backscatter signature. The aptitude of a natural area to provide a stable and uniform backscatter response must be carefully considered and demonstrated by a sufficiently long time-series of measurements. Furthermore, this approach requires a strict control of the acquisition and processing parameters. If all these conditions are met, stability check and relative calibration of a system are possible by comparison with the averaged backscatter values for the area. Based on a common multibeam echosounder and sampling campaign completed by available bathymetric and backscatter time series, the suitability as a backscatter reference area of three different candidates was evaluated. Two among them, Carré Renard and Kwinte, prove to be excellent choices, while the third one, Western Solent, lacks sufficient data over time, but remains a valuable candidate. The case studies and the available backscatter data on these areas prove the applicability of this method. The expansion of the number of commonly used reference areas and the growth of the number of multibeam echosounder controlled thereon could greatly contribute to the further development of quantitative applications based on multibeam echosounder backscatter measurements.     

Calibration of a chalcogenide glass membrane ion-selective electrode for the determination of free Fe in seawater: I. Measurements in UV photooxidised seawater

Calibration of a chalcogenide glass membrane, Fe(III)ISE [Fe_2.5(Ge₂₈Sb₁₂Se₆₀)_97.5], in buffered saline media has been undertaken in order to assess the suitability of this ISE for seawater analyses. The electrode slopes in saline citrate and salicylate buffers were 26.3 and 28.2 mV/decade, respectively, for Fe³⁺ concentrations ranging from 10⁻¹⁰ M to less than 10⁻²⁵ M Fe³⁺. The calibration lines in the citrate and salicylate buffers were essentially collinear with the response in unbuffered chloride-free standards containing >10⁻⁵ M Fe³⁺, demonstrating that the response of the FeISE is unaffected by chloride ions. A mechanism involving a combination of charge transfer and ion-exchange of Fe(III), at the electrode diffusion layer, can be used to explain the ≈30 mV/decade slope of the FeISE. The response of the FeISE in UV photooxidised seawater containing 8 nM total Fe was measured as the pH was changed from 8.27 to 3.51. The slope of the response was 24.2 mV/decade [Fe³⁺] calculated as a function of pH using Fe(III) hydrolysis constants for seawater. Moreover, the response was essentially collinear with that in citrate buffers and in unbuffered solutions containing >10⁻⁵ M Fe³⁺ and the slope for the combined data was 26.2 mV/decade. This study was restricted to organic-free seawater because the certainty in Fe(III)–ligand stability constants is insufficient to warrant the selection of an ideal calibration buffer system, and there is evidence that powerful chelating ligands (e.g., EDTA along with humic and fulvic acids) may alter the response of the Fe(III)ISE. The Fe dissolution rate of the FeISE in UV photooxidised seawater was found to be 1.6×10⁻² nmol Fe/min, as measured by cathodic stripping voltammetry (CSV). This would contaminate a 100-ml sample by 0.8–1.6 nM Fe over a typical measurement period of 5–10 min obtained using a stability criterion of 0.5 mV/min. Various methods are proposed for reducing the level of contamination in open ocean samples that contain sub-nanomolar concentrations of iron. The FeISE has the potential to detect free Fe³⁺ at concentrations typically found in natural seawater.     

UCTD海上比测方法探讨

在海洋勘测工作中,对于海洋动力学参量--电导率、温度、深度的测量是最为基础和重要的监测内容.拖曳式温盐深剖面测量系统(Underway Conductivity Temperature Depth Measure System,简称UCTD)是最新发展起来的一种高技术走航CTD剖面测量装置.文中介绍了UCTD海上定点比...     

Importance of Reference Dataset Improvements for Argo Delayed-Mode Quality Control

For the Argo Project, monitoring the global upper ocean by a large number of profiling floats, maintaining the quality of salinity data is critical; the goal for measurement accuracy is ±0.01. Experiments using the method of Wong et al. (2003), the standard delayed-mode quality control (dQC) for the Project, show that its performance depends critically on the reference datasets used. This study concludes that the method is useful for Argo and has sufficient potential to achieve the goal for salinity measurement in the North Pacific, when suitable reference datasets are prepared. Considering the Wong et al. (2003) algorithms, we suggest that reference datasets with the following characteristics will be most suitable for Argo dQC: They should be basically derived from the most extensive datasets, such as the latest World Ocean Database; in regions with denser observations, datasets with carefully quality controls should be used; in the regions with subsurface temperature inversions, such as the subarctic North Pacific, the profiles used for the reference must extend below the deepest temperature maximum to prepare proper salinities for the deep layer reference.     

海底砂土中气体运移过程电阻率监测探针设计与实验

在浮力和动、静压力作用下,海底浅层气会在高渗透性土中发生垂直和水平方向的运移、聚集,诱发地层变形,甚至失稳破坏。为探索一种新型的气体运移过程原位监测技术,实现气致灾害实时监测预警,根据静电场测量原理,设计、制作了点状电极和环状电极两种形式电阻率探针。在分析了两种探针探测精度基础上,以砂土中气体扩散过程监测为例,利用其对3种速率气体运移过程进行连续监测实验。实验结果表明,两种探针电阻率测量误差均小于0.1%。点状电极探针测量灵敏度较高,可准确监测布设点含气量的变化、气体汇聚、消散过程及相应速率;环状电极探针测量灵敏度相对较低,但可监测气体在砂土中的时空运移过程。两种探针各有利弊,都可实现气体运移过程的有效监测。     

Concrete sulfate corrosion coupled with hydraulic pressure

Abstract

A type of sealed steel box was designed to simulate sulfate attack and hydraulic pressure on concrete. Cup-shaped concrete specimens with water/cement (w/c) ratios of 0.4, 0.5, and 0.6 were fabricated. During the 270 days corrosion time, corrosion behavior on concrete surfaces was observed every 30 days. The extent of damage on concrete was calculated on the basis of the results of periodic ultrasonic testing. After the completion of experiments, X-ray fluorescence analysis was conducted on the element contents at different depth locations of partial specimens. Experimental results showed that hydraulic pressure accelerated the sulfate attack on concrete, and high pressure yielded serious damage. In comparison with zero pressure, the accelerating coefficients of 0.1, 0.2, and 0.3?MPa hydraulic pressures were 1.48, 1.75, and 2.35, respectively. Hydraulic sulfate corrosion can bring additional sulfate ions into concrete and cause chemical and physical sulfate corrosions on concrete simultaneously, thereby resulting in serious damage on concrete. The reduction of w/c ratio and incorporation of fly ash are beneficial for concrete to resist hydraulic sulfate attack.     

Circular time-domain reflectometry system for monitoring bridge scour depth

Abstract

Sediment has a severe effect on bridge stability, and time-domain reflectometry (TDR) is a suitable method for assessing scour depth. This paper presents a fundamental study to demonstrate the suitability of a circular TDR system to enhance the resolution when monitoring scour depth with consideration of detailed local changes over a wide area around piers. A total of 32 electrodes are vertically installed on a cylinder pier around the circumference at ～7.36?mm intervals. Scour depth is investigated through small-scale laboratory experiments, where a measured waveform reflects the artificially constructed scour depth with high resolution (≈5?mm). Different scour types including circular, mushroom, elliptical, and irregular shapes are developed to verify the application of circular TDR, and shapes are predicted through the detailed local distribution. The influences of the reflected waveform according to water level change, temperature variation, and salinity effect are investigated as additional considerations, and the relative deviation of scour depth is analyzed. This study demonstrates that the proposed circular TDR system achieves better resolution than existing single TDR systems and may provide a better alternative technique for monitoring scour depth.     

Measuring lysosomal stability as an effective tool for marine coastal environmental monitoring

The use of lysosomal stability in the mussel, Mytilus galloprovincialis, as a potential biomarker of environmental contamination has been evaluated along the Portuguese coast. To this end, the neutral red retention (NRR) time was measured in mussel haemocytes gathered from nine different locations reflecting different degrees of anthropogenic contamination. Mussels collected in the vicinity of industrial and urban areas showed the lowest lysosomal stability. Additionally, no significant seasonal variability (winter-spring/summer) for NRR time was observed. In order to further support the usefulness of this method as an integrated tool for monitoring marine coastal environments, we compared the levels of xenobiotics in mussel tissues with the obtained NRR values. The results highlighted a consistent pattern, with the lowest lysosomal stability intimately correlated with the higher contaminant concentrations. In summary, this integrated approach further demonstrated that the NRR assay can provide useful and objective indications of the real health status of organisms subjected to different stress agents, being a valid option for environmental monitoring.     

海水中钙的电位滴定

钙离子选择性电极为指示电极,饱和甘汞电极作参比,用硼砂盐缓冲液控制ｐＨ,以ＥＧ－ＴＡ为滴定剂进行电位滴定。与现行用ＧＨＡ为指示剂、ＥＧＴＡ为滴定剂的络合滴定法相比,可减小络合滴定中目测终点的人为误差,故测量精度优于０．０８％。