Cathodic protection of reinforced concrete:anodic processes in cements and related electrolytes

The nature and kinetics of electrode reactions and processes occurring for four lightweight anode systems which have been utilised in reinforced concrete cathodic protection systems have been studied. The anodes investigated were flame sprayed zinc, conductive paint and two activated titanium meshes. The electrochemical properties of each material were investigated in rapidly stirred de-oxygenated electrolytes using anodic potentiodynamic polarisation. Conductive coating electrodes were formed on glass microscope slides, whilst mesh strands were immersed directly. Oxygen evolution occurred preferentially for both mesh anodes in saturated Ca (OH)2/CaC12 solutions but was severely inhibited in less alkaline solutions and significant current only passed in chloride solutions. The main reactions for conductive paint was based on oxygen evolution in all electrolytes, although chlorides increased the electrical activity. Self-corrosion of zinc was controlled by electrolyte composition and the experimental set-up, chlorides increasing the electrical activity. Impressed current cathodic protection was applied to 25 externally exposed concrete slabs over a period of 18 months to investigate anode degradation mechanisms at normal and high current densities. Specimen chloride content, curing and reinforcement depth were also variables. Several destructive and non-destructive methods for assessing the performance of anodes were evaluated including a site instrument for quantitative "instant-off- potential measurements. The impact of cathodic protection on the concrete substrate was determined for a number of specimens using appropriate methods. Anodic degradation rates were primarily influenced by current density, followed by cemendtious alkalinity, chloride levels and by current distribution. Degradation of cementitious overlays and conductive paint substrates proceeded by sequential neutralisation of cement phases, with some evidence of paint binder oxidation. Sprayed zinc progressively formed an insulating layer of hydroxide complexes, which underwent pitting_ attack in the presence of sufficient chlorides, whilst substrate degradation was minimal. Adhesion of all anode systems decreased with increasing current density. The influence of anode material on the ionic gradients which can develop during cathodic protection was investigated. A constant current was passed through saturated cement paste prisms containing calcium chloride to central cathodes via anodes applied or embedded at each end. Pore solution was obtained from successive cut paste slices for anion and cation analyses. Various experimental errors reduced the value of the results. Characteristic S-shaped profiles were not observed and chloride ion profiles were ambiguous. Mesh anode specimens were significantly more durable than the conductive coatings in the high humidity environment. Limited results suggested zinc ion migration to the cathode region. Electrical data from each investigation clearly indicated a decreasing order of anode efficiency by specific anode material.

Corrosion of stainless steel components in seawater reverse osmosis desalination plants-investigations on adapted internal cathodic protection

Stainless steel is widely used in seawater reverse osmosis units (SWRO) for both good mechanical and corrosion resistance properties. However, many corrosion failures of stainless steel in SWRO desalination units have been reported. These failures may often be attributed to un-adapted stainless steel grade selection and/or to the particular aggressive seawater conditions in "warm" regions (high ambient temperature, severe biofouling, etc.). Cathodic protection (CP) is a well-known efficient system to prevent corrosion of metallic materials in seawater. It is successfully used in the oil and gas industry to protect carbon steel structures exposed in open-sea. However, the specific service conditions of SWRO units may seriously affect the efficiency of such anti-corrosion system (high flow rates, large stainless steel surfaces affected by biofouling, confinement limiting protective cathodic current flow, etc.). Hence, CP in SWRO units should be considered with special care and modeling appears as useful tool to assess an appropriate CP design. However, there is a clear lack of CP data that could be transposed to SWRO service conditions (i.e. stainless steel, effect of biofouling, high flow rate, etc.). From this background a Join Industry Program was initiated including laboratory exposures, field measurements in a full scale SWRO desalination plant, and modeling work using PROCOR software. The present paper reviews the main parameters affecting corrosion of stainless steel alloys in seawater reverse osmosis units. CP on specific stainless steel devices was investigated in order to assess its actual efficiency for SWRO units. Severe environmental conditions were intentionally used to promote corrosion on the tested stainless steel products in order to evaluate the efficiency of CP. The study includes a modeling work aiming at predicting and designing adapted CP protection to modeled stainless steel units. An excellent correlation between modeling work and field measurements was found.

A new study on binder performance and formulation modification of anti-corrosive primer based on ethyl silicate resin

Zinc-rich ethyl silicate coatings are quite successful in protecting steel against corrosion under severe exposing conditions. In spite of providing excellent cathodic protection to steel structure after film curing, two-component zinc-rich ethyl silicate coatings have some limitations, one of which is inadequate shelf life as a result of in-can binder gelation. In this work, the preparation steps of ethyl silicate such as pre-hydrolysis, dehydration and organometallic reactions were surveyed and herein an approach towards understanding the cause and effect relationship of the use of ingredients is presented. The effects of water and catalytic acid dosages on gel time under accelerated conditions and the effect of alcoholic solvent order on the rate of the hydrolysis and dehydration reactions were studied via Karl-Fischer test determining the water content of hydrolysate. A thriving optimization in shelf life without any loss in physical–mechanical characteristics of the final film (e.g. hardness, adhesion, solvent and salt spray resistance) was obtained.

铜管不锈钢管腐蚀性能及铁牺牲阳极保护研究

铜管一直是电厂凝汽器的主要应用管材，但由于其抗冲刷和抵御污染物腐蚀的能力差，特别不耐氨蚀，美国和欧洲大量使用不锈钢管替代铜管作为冷凝管，然而不锈钢管在我国的运用仅处于初步阶段。 常使用锌、铝阳极对铜管进行牺牲阳极保护，然而存在着电位差过大、阳极溶解过快的问题。铁基牺牲阳极与铜电位差适当、来源广泛、价格便宜，在一些工程上有所应用，但是目前针对铁基牺牲阳极的理论研究报道很少。 本文选用紫铜管、304不锈钢管作为实验用管材，首先运用实验室全浸实验、极化曲线和电化学阻抗研究了二者在海水和淡水中的腐蚀性能以及CO2、溶解氧对其腐蚀的影响。结果表明：CO2会加速二者的腐蚀，溶解氧却对它们的腐蚀影响不同，促进铜管的腐蚀却抑制不锈钢管的腐蚀；随浸泡时间的延长，紫铜管由于表面产物膜的生成耐蚀性提高，304不锈钢管的耐蚀性却降低；淡水中，304不锈钢管和紫铜管都具有很好的耐蚀性能。随后，运用失重法和极化曲线对比研究了紫铜管、304不锈钢管的氨蚀性能，运用SEM分析和电化学阻抗研究了紫铜在不同浓度氨溶液中的腐蚀机理。发现，304不锈钢管的耐氨蚀能力远远好于铜管；溶解氧是影响氨蚀的关键因素，其对二者氨蚀的影响也不同；紫铜管在低氨浓度和高氨浓度溶液中腐蚀机理和产物不同，低氨浓度时形成保护性的产物膜（CuO 和Cu(OH)2），高氨浓度时由活化溶解控制，生成可溶的[Cu (NH3)4]2+。 选用工业纯铁、35钢为牺牲阳极材料。恒电流实验结果表明它们具有良好的牺牲阳极性能；通过极化曲线和自腐蚀电位测试分析，认为将二者用于铜管牺牲阳极保护是可行的；实验室阴极保护效果测试表明，工业纯铁和35钢对紫铜管具有良好的保护效果，保护度达90%以上。

海水和海泥中阴极保护系统的边界元计算

随着人们对能源需求的不断增加，深海海洋油气开发已引起了人们越来越大的兴趣，随之而来的是对海洋构筑物的设计和防护提出了更高的要求。由于在传统的阴极保护工程设计中，大多采用实际测量或经验估计的方法来掌握电位分布规律，很难真实的反映构筑物的实际状态，为了确保安全，往往采用较大的安全系数，不但会造成金属材料的浪费，而且还会在构筑物的局部造成保护不足或过保护。 本文研究了边界元方法（BEM）利用数值仿真技术对阴极保护状态下的海洋构筑物的保护状态进行模拟，从而获得阴极保护状态下的金属材料的电位分布。采用常数单元对于二维问题进行了研究，推导出了边界积分方程的离散化形式，并结合阴极保护环境下的阳极和阴极的极化曲线作为边界条件，建立了线性方程组。采用Newton-Raphson 迭代法和分段拟线性化的方法对边界条件做了线性化处理，应用FORTRAN语言开发出阴极保护的边界元仿真求解程序CPBEM，并利用该程序选择合适的算例进行了验证，结果表明该程序是有效和可行的。 通过管线钢在不同温度海泥埋片的腐蚀失重实验，证明了如果有充足的氧的供给的情况下，温度每增加10oC，腐蚀速度便增加一倍。阴极保护系统数值仿真的精确度最主要的影响因素就是阴极和阳极的极化曲线。而金属材料的极化曲线往往受到多种环境因素的影响，本文系统的讨论了在海泥介质中两种管线钢的腐蚀行为，对管线钢极化行为产生影响的各种环境因素，以及这些因素与金属的腐蚀速度之间的关系。首次将灰关联分析的手段运用到海泥介质的腐蚀，研究了环境因素对于ERW，SML两种管线钢在海泥中的腐蚀速率的影响。

Corrosion behaviour of hot dip zinc and zinc-aluminium coatings on steel in seawater

A comparative investigation of hot dip Zn-25Al alloy, Zn-55Al-Si and Zn coatings on steel was performed with attention to their corrosion performance in seawater. The results of 2-year exposure testing of these at Zhoushan test site are reported here. In tidal and immersion environments, Zn-25Al alloy coating is several times more durable than zinc coating of double thickness. At long exposure times, corrosion rate for the Zn-25Al alloy coating remains indistinguishable from that for the Zn-55Al-Si coating of similar thickness in tidal zone, and is two to three times lower than the latter in immersion zone. The decrease in tensile strength suggested that galvanized and Zn-55Al-Si coated steel suffer intense pitting corrosion in immersion zone. The electrochemical tests showed that all these coatings provide cathodic protection to the substrate metal; the galvanic potentials are equal to - 1,050, - 1,025 and - 880 mV (SCE) for zinc, Zn-25Al alloy and Zn-55Al-Si coating, respectively, which are adequate to keep the steel inside the immunity region. It is believed that the superior performance of the Zn-25Al alloy coating is due to its optimal combination of the uniform corrosion resistance and pitting corrosion resistance. The inferior corrosion performance by comparison of the Zn coating mainly results from its larger dissolution rate, while the failure of the Zn-55Al-Si coating is probably related to its higher susceptibility to pitting corrosion in seawater.

Pure mechanical wear loss measurement in corrosive wear

The method for the measurement of the pure mechanical wear loss for 321 stainless steel, 1045 steel and pure iron in the study of the synergy between corrosion and wear was studied, The methods studied included the measurement in distilled water, by cathodic protection and by adding inhibitor KI, and all were compared with the wear loss in air. The experiment showed that the pure mechanical wear losses and friction coefficients obtained by the three methods were close to each other and can be used to calculate the various wear components in the study of the interaction of corrosion and wear, but the measurements in distilled water for pure iron and 1045 steel are not recommended due to their corrosion.

Corrosion fatigue of welded joints of steel for marine platform

Experiments on the corrosion fatigue behaviour of welded joints of the steel for marine platform in air and seawater, and of the joints in seawater with cathodic protection, yielded data for linear regression to obtain fatigue life curves (Delta S-N-f). The laws of corrosion fatigue in welded joints of test steel are discussed with reference to those of A(587) and A(131) steel. In these experiments, the fatigue damage occurring at all welded joints around the weld interface resulted in the cracks and fractures. The fatigue life of the specimens in seawater with cathodic protection is longer than that in seawater Without protection.

Ação antioxidante da água catódica: estudos preliminares em sementes de café

Coffee seeds have limitations regarding to its conservation because of their sensitivity to desiccation and storage behavior. The establishment of a methodology for seed storage is difficult due to its deterioration. Deterioration can enhance the production of reactive oxygen species and cause lethal oxidative damage to plant tissues. The damage caused by harmful levels of free radicals can be softened by the action of endogenous or exogenous antioxidants. Recent research shows new antioxidative protection technologies, being cathodic protection a promising technique with relevant results in other recalcitrant species and even in other living organisms. Thus, the aim of this work was to verify the antioxidant effect of cathodic water in Coffea arabica L. seeds with the purpose of investigating a new technology to improve seed quality. The study was conducted at the Central Seed Laboratory, Department of Agriculture, at the Federal University of Lavras. Coffea arabica L. seeds were used. The study was conducted in two stages, in the first a preliminary analysis of the use of cathodic water was carried out in batches with different levels of quality. In the second it was evaluated the effect of light and of the imbibition period of the seeds in cathodic water. The seeds were immersed in distilled water and in cathodic water for eight distinct soaking periods, in absence and presence of light and then evaluated by physiological tests. It can be concluded that cathodic water can positively influence the physiological performance of the coffee seeds with poor quality, especially when embedded during periods between 4.5 to 7.5 hours in the absence of light.

Protección catódica en estructuras sumergidas. Aplicación al proyecto de boyas y tuberías de un terminal portuario de descarga de crudo.

Este proyecto tiene por objeto el diseño de la protección catódica contra la corrosión de las boyas y las tuberías sumergidas en agua de mar de un terminal portuario de descarga de crudo. La protección catódica consiste en la igualación de los potenciales de las áreas anódicas y catódicas del material por el flujo de electrones suministrado. En el proyecto se han empleado los métodos de ánodos de sacrificio y de corriente impresa para analizar la protección catódica más adecuada de cada componente. Para los cálculos de los ánodos necesarios para la protección catódica se utilizó el procedimiento de la masa, seleccionando así el método, ánodos de sacrificio o corriente impresa, y los ánodos más apropiados para la protección catódica de las boyas y de las tuberías. ABSTRACT The aim of this project was to design the cathodic protection against corrosion of a crude oil unloading port terminal’s buoys and under sea water pipelines. The cathodic protection consists in the equating of anodic and cathodic material areas by the electrons flow supplied. In this project, sacrificial anodes and impressed current methods were used for analyze the most suitable cathodic protection for each component. For the cathodic protection required anodes calculations, the weight procedure was used, thereby selecting the method, sacrificial anodes or impressed current, and the most appropriate anodes, for the cathodic protection of the buoys and pipelines

Technology of repair for corroded reinforced concrete

A number of factors relating to various methods of repair for chloride initiated corrosion damage of reinforced concrete have been studied. A novel methodology has been developed to facilitate the measurement of macro and micro-cell corrosion rates for steel electrodes embedded in mortar prisms containing a chloride gradient. The galvanic bar specimen comprised electrically isolatable segmental mild steel electrodes and was constructed such that macro-cell corrosion currents were determinable for a number of electrode combinations. From this, the conditions giving rise to an incipient anode were established. The influence of several reinforcement and substrate primer systems upon macro-cell corrosion, arising from an incipient anode, within a patch repair have been investigated. Measurements of electrochemical noise were made in order to investigate the suitability of the technique as an on-site means of assessing corrosion activity within chloride contaminated reinforced concrete. For this purpose the standard deviation of potential noise was compared to macro-cell galvanic current data and micro-cell corrosion intensity determined by linear polarisation. Hydroxyl ion pore solution analyses were carried out on mortar taken from cathodically protected specimens. These specimens, containing sodium chloride, were cathodically protected over a range of polarisation potentials. Measurement of the hydroxyl ion concentrations were made in order to examine the possibility of alkali-silica reactions initiated by cathodic protection of reinfored concrete. A range of mortars containing a variety of generic type additives were examined in order to establish their resistances to chloride ion diffusion. The effect of surfactant addition rate was investigated within a cement paste containing various dosages of naphthalene sulphonate.

Study of carbon-supported Au catalyst as the cathodic catalyst in a direct formic acid fuel cell prepared using a polyvinyl alcohol protection method

In this paper, it is reported for the first time that a carbon-supported Au (Au/C) catalyst for the cathodic catalyst in a direct formic acid fuel cell (DFAFC) was prepared using a polyvinyl alcohol (PVA) protection method. The results indicated that for oxygen reduction, the electrocatalytic activity of the Au/C catalyst prepared with the PVA protection method is much better than that of a Au/C catalyst prepared with the pre-precipitation method. This is due to the small average size and low relative crystallinity of the An particles in the Au/C catalyst prepared by the PVA protection method, compared to that of the Au/C catalyst prepared by the pre-precipitation method, illustrating that the average size and the relative crystallinity of the ALL particles has an effect on the electrocatalytic activity of the Au/C catalyst for oxygen reduction. In addition, because An has no electrocatalytic activity for the oxidation of formic acid, the Au/C catalyst possesses a high formic acid tolerance. After the electrocatalytic activity of the Au/C catalyst for the oxygen reduction is improved, it is suitable to be used as the cathodic catalyst in DFAFC.