Preparation and Properties of Embeddable Ag/AgCl 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/AgCl 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 anti- polarization. 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.     

海洋电场采集电极极差自动补偿方法设计

针对海洋电磁勘探的低频、微弱电场信号采集中电极与放大采集电路的耦合问题,提出了一种支持直流耦合的电极极差自动补偿放大采集电路设计方法,给出了系统设计实现,详细介绍了电极极差自动补偿放大采集电路和自动补偿控制算法.测试结果表明,所设计的电极极差自动补偿方法可将0.1～0.7 mV的电极极差自动补偿至0.043～0.074 mV,均控制在0.1 mV以内,满足了海洋电场采集直流耦合的需求,降低了电场采集电路对不极化Ag/AgC1电极的极差设计要求,可有效应用于海洋低频电场信号采集.     

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.     

The use of buffers to measure the pH of seawater

The pH of seawater can be measured in the field using potentiometric and spectrophotometric methods. The use of pH standards or buffers is an important aspect of the calibration of both methods in a laboratory on a common concentration scale. The buffers can also be used to monitor the performance of pH meter and spectrophotometer during a cruise. A procedure is described for the determination of the pH of seawater, where the proton concentration is expressed as moles kg-H₂O⁻¹ using seawater buffers. The buffers are prepared in synthetic seawater in the laboratory by the methods outlined by Bates and coworkers. We have prepared four buffers (Bis, Tris, Morpholine and 2-Aminopyridine) that cover a pH range from 6.8 to 8.8. The emf values of the buffers were measured with a H₂, Pt/AgCl, Ag electrode system after their preparation and bottling for use at sea. The measured emf values were found to be in good agreement (±0.05 mV) with the original measurements of Bates and coworkers from 0 to 45°C. The measured pH of these buffers are in good agreement (±0.001 pH units) with the values calculated from the equations of Dickson on the total pH scale based on Bates et al. Studies are underway to access the long term stability of these buffers. We have also used these buffers to calibrate systems used to make potentiometric and spectrophotometric measurements of pH on seawater relative to the H₂, Pt/Ag, AgCl electrode from 5 to 45°C.     

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。     

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.     

基于监测数据的深水水下井口循环弯矩计算方法

水下井口的疲劳完整性是海洋油气田长期安全开采的前提。工业界往往采用贴应变片直接测量水下井口应变来计算弯矩和疲劳损伤,但水下井口应变片粘贴困难且不能长时间连续工作。采用对水下井口监测方法,基于隔水管—防喷器组—水下井口的运动和力学特性,考虑防喷器组惯性力矩建立系统耦合动力学方程,最终形成基于监测数据的水下井口循环弯矩计算方法。以南海某深水水下井口为例,建立隔水管—防喷器组—水下井口系统有限元模型并进行动态分析,提取隔水管底部张力、转角、防喷器组加速度及转角等参数,代入所建立的系统耦合动力学模型,得到水下井口弯矩与有限元计算结果吻合良好。研究表明只需通过在线监测获得所需的输入数据,无需监测水下井口应变即可获取水下井口循环弯矩。建立的系统耦合动力学模型可为水下井口疲劳完整性评估提供理论依据。     

Biodynamic modelling of the accumulation of Ag,Cd and Zn by the deposit-feeding polychaete Nereis diversicolor: Inter-population variability and a generalised predictive model

Biodynamic parameters of the ragworm Nereis diversicolor from southern Spain and south England were experimentally derived to assess the inter-population variability of physiological parameters of the bioaccumulation of Ag, Cd and Zn from water and sediment. Although there were some limited variations, these were not consistent with the local metal bioavailability nor with temperature changes. Incorporating the biodynamic parameters into a defined biodynamic model, confirmed that sediment is the predominant source of Cd and Zn accumulated by the worms, accounting in each case for 99% of the overall accumulated metals, whereas the contribution of dissolved Ag to the total accumulated by the worm increased from about 27 to about 53% with increasing dissolved Ag concentration. Standardised values of metal-specific parameters were chosen to generate a generalised model to be extended to N. diversicolor populations across a wide geographical range from western Europe to North Africa. According to the assumptions of this model, predicted steady state concentrations of Cd and Zn in N. diversicolor were overestimated, those of Ag underestimated, but still comparable to independent field measurements. We conclude that species-specific physiological metal bioaccumulation parameters are relatively constant over large geographical distances, and a single generalised biodynamic model does have potential to predict accumulated Ag, Cd and Zn concentrations in this polychaete from a single sediment metal concentration.     

Interpretation of pH measurements in concentrated electrolyte solutions

The residual electrode potential between dilute pH buffers and 0.725 molal NaCl was estimated to be ?3.2 mV. This result is consistent with the operational activity coefficient of the hydrogen ion in seawater.