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At least 19 records

On the Use of Voltammetry to Estimate the Effectiveness of Cathodic Protection of Buried Steel Structures

Buried steel structures, e.g., oil and gas pipelines, are often protected against corrosion by the combination of organic coating and cathodic protection. The effectiveness of cathodic protection can be monitored over time using voltammetry via a computer fitting of the polarization curves with theoretical electrochemical kinetic laws. In this study, the influence of the scan rate and the procedure used for the acquisition of the polarization curve was investigated. Reliable, though slightly overestimated, residual corrosion rates were obtained using a specific procedure and a low potential scan rate. However, the residual corrosion rate has a meaning only if the wet area of the electrode is known, which can be achieved by measuring another parameter linked to the wet area, e.g., the electrolyte resistance R{sub s}. In a soil at 25% saturation, the wet area, which is the surface of the metal in contact with the soil electrolyte, may be actually significantly different from the whole surface of the electrode.

36 MATERIALS SCIENCE↗

Structural underpinnings of cathode protection by in situ generated lithium oxyfluorophosphates

The in situ strategy of cathode protection opportunistically uses PF$_6^-$ anions in electrolyte as chemical reagents to convert inactive precursor molecules to active electrolyte additives. With our approach, a bifunctional x(SiMe 3 ) 2 precursor replaces fluoride in the hexafluorophosphate, forming either a bidentate monoanion P(x)F$^-_4$ or a linear x(PF$_5^-$) 2 dianion, depending on the bridge $x$ (e.g., oxalato, malonato, succinato, and catecholato). While the efficiency of these species as cathode protective agents has been demonstrated, the mechanism for their beneficial action remains unknown. In this study, several molecular precursors have been synthesized, and the topology and energetics of secondary anions were correlated with their cycling performance. Regardless of their structural motif, all such additives demonstrated improved electrochemical performance by reducing initial cathode impedance and lowering the rate of capacity fade compared to the baseline electrolyte. However, we note bidentate monoanions with a malonato bridge showed significant advantage over other molecular designs for mitigating the impedance rise, suggesting that structural strain in the anion is important for easing surface modification of the cathode.

25 ENERGY STORAGE↗

Apollo/Saturn C00.00.19.3 operations and maintenance. Cathodic protection of communication cables

Operating and maintenance instructions for cathodic protection of communication cables at the Cape Kennedy Launch Complex are presented. The system is designed to prevent or arrest corrosion of communication cables buried in soil or submerged in water by impressing sufficient direct current from the rectifier through the anodes to the cable. This process neutralizes or counteracts current flowing from the cable into the soil or water, thus preventing or arresting corrosion of the cable sheath material.

Source record↗

Cathodic Protection Deployment on Space Shuttle Solid Rocket Boosters

Corrosion protection of the space shuttle solid rocket boosters incorporates the use of cathodic protection(anodes) in concert with several coatings systems. The SRB design has large carbon/carbon composites(motor nozzle) electrically connected to an aluminum alloy structure. Early in the STS program, the aluminum structures incurred tremendous corrosive attack due primarily to the galvanic couple to the carbon/carbon nozzle at coating damage locations. Also contributing to the galvanic corrosion problem were stainless steel and titanium alloy components housed within the aluminum structures and electrically connected to the aluminum structures. This paper will highlight the evolution in the protection of the aluminum structures, providing historical information and summary data from the operation of the corrosion protection systems. Also, data and information will be included regarding the evaluation and deployment of inorganic zinc rich primers as anode area on the aluminum structures.

Zook, Lee M.↗

Photovoltaic power without batteries for continuous cathodic protection

The COASTSYSTA designed, installed, and started up on 20 Jan. 1990, a state-of-the-art stand alone photovoltaic powered impressed current cathodic protection system (PVCPSYS) not requiring any auxiliary/battery backup power for steel and iron submerged structures. The PVCPSYS installed on 775' of steel sheet piling of a Navy bulkhead is continuing to provide complete, continuous corrosion protection. This has been well documented by COASTSYSTA and verified on-site by the U.S. Army Civil Engineering Research Laboratory, Champaign, Illinois and the Navy Energy Program Office-Photovoltaic Programs, China Lake, California. The Department of Defense (DoD) Photovoltaic Review Committee and Sandia National Laboratories consider this successful and cost effective system a major advance in the application of photovoltaic power. The PVCPSYS uses only renewable energy and is environmentally clean. A patent is pending on the new technology. Other possible PVCPSYS applications are mothballed ships, docks, dams, locks, bridges, marinas, offshore structures, and pipelines. The initial cost savings by installing a PVCPSYS vs. a conventional CP system was in excess of $46,000.00.

Muehl, W. W., Sr.↗

Photovoltaic Power Without Batteries for Continuous Cathodic Protection

The objective of this project was to successfully demonstrate that renewable energy can efficiently and economically replace dedicated non-renewable power sources. The COASTSYSTA designed, installed, and started up on 20 Jan. 1990, a state-of-the-art photovoltaic powered impressed current cathodic protection system (PVCPSYS) for steel and iron submerged structures. This system does not require any auxiliary/battery backup power. The PVCPSYS installed on 775 ft. of steel sheet piling of a Navy bulkhead is continuing to provide complete, continuous corrosion protection. This installation is well documented by COASTSYSTA and was verified on-site by the U.S. Army Corps of Engineers. The PVCPSYS uses only renewable energy and is environmentally clean. A patent is pending on the new technology. Other possible PVCPSYS applications are mothballed ships, docks, dams, locks, bridges, marinas, and pipelines. The Department of Defense Photovoltaic Review Committee and Sandia National Laboratories consider this successful and cost effective system a major advance in the application of photovoltaics.

Muehl, W. W., Sr.↗

Viability of Cathodic Protection for Preventing Corrosion of Stainless Steel 316H in Molten LiF-NaF-KF

Molten fluoride salts are candidate heat transfer fluids in a number of applications such as generation IV molten salt nuclear reactors and concentrated solar power plants. However, a chief concern in the design of these systems is the corrosion of structural materials that come in contact with these molten salts. Redox control methods such as the purification of salt, the addition of active elements, and applied electrochemical potential can be efficient methods for preventing the corrosion of structural materials in molten fluoride salts. Applied electrochemical potential as a redox control method for application in molten fluoride salts has rarely been explored. This study seeks to understand the viability of impressed current cathodic protection (CP) at various currents as a redox control method to prevent corrosion of stainless steel 316H in molten LiF-NaF-KF (FLiNaK) salt. Results show that application of CP can be an effective method to prevent corrosion of SS316H in molten FLiNaK salt, but the applied current will have to be optimized to prevent undesirable side effects such as reduction of salt constituents, salt deposition on electrodes, etc.

Materials Science↗

Cathodic Protection Modeling for Hanford Underground Double-Shell Tank Farms

Hanford stores millions of gallons of radioactive and chemically hazardous waste from the production of weapon materials in tank farms consisting of underground carbon-steel storage tanks surrounded by reinforced concrete. Six of these Hanford tank farms use double-shell storage tanks (DSTs). The DST farms were constructed from 1968 to 1986 with a planned 40–50 year design life, so some are already operating beyond their initial life expectancy. Ultrasonic testing (UT) has indicated significant thinning on the bottom of the secondary (outer) liner of these tanks, believed to arise from groundwater intrusion driving concrete side corrosion. There is no direct access to the steel/concrete interface between the tank and the concrete pad, making it difficult to apply a chemical-based mitigation strategy or to conduct repairs, but cathodic protection (CP) is a possible method to inhibit further concrete-side corrosion. Hanford already uses CP to protect below grade steel piping within the tank farms and connected to the tanks, but this system was not designed to protect the tank bottoms. CP design must account for the structures surrounding the DSTs, including the steel reinforcing bars (rebar) within the concrete pad and vault, various process lines, and the existing CP system. In this study, finite element analysis (FEA) modeling was carried out to simulate CP protection of 1) a single tank and CP anode to develop options for modeling the rebar and to compare to a simpler circuit model and 2) the entire Hanford AN tank farm as a representative example consisting of seven tanks, associated piping, and both existing and new CP anodes. Both circuit and FEA models predict that significant protective current could be delivered to the bottoms of the tanks with the addition of tank-protection anodes below the depth of the tanks. Simulations with only the existing pipe-protection anodes active confirmed that only a very small current to the tank bottoms is predicted under present conditions. Multiple simplified representations of the dome and wall rebar were tested to reduce the computational complexity of the tank-farm simulations, resulting in modeling the rebar as edge elements with a prescribed effective circumference that matches the real rebar surface area. The geometry of the rebar is also simplified into horizontal hoops around the tank walls and radial rebar over the dome with increased effective circumference to retain the target surface area. This simplification was found to greatly reduce the complexity and solution time of the models without large changes in current distributions, especially to the tank bottom. A range of values were tested for model parameters such as soil and concrete resistivities and polarization resistance to investigate their impact on the current and electric potential distributions. Depending on the parameters used, FEA simulations predict some risk of overprotection, particularly on the piping system; since overprotection can also lead to surface damage associated with hydrogen gas generation at the interface (e.g. hydrogen embrittlement or damage to coatings), this needs to be considered when refining the design of the new CP system. Comparison between the FEA models and the circuit model representation demonstrated that the circuit model could not match the predicted FEA current distribution, even when using the exact same surface areas. This discrepancy appeared to be at least partly attributable to the impact of the relative positions of the tank components and anodes to each other and to the ground surface. The FEA model accounts for the relative positions since it solves the governing equations in three dimensions, but the circuit model cannot account for the positioning. In particular, the circuit model underpredicts the current to the tank bottom and overpredicts the current to the dome compared to FEA for the baseline geometry. The FEA models omitted the electrically isolated rebar in the bottom concrete slab. However, a circuit based stray current model estimated that only 2.1% of the total current through the slab would stray into the rebar, corresponding to ~0.21 A for a target current density of 2 mA/ft2 to the tank bottom. The estimated corrosion driven by this amount of stray current is predicted to yield a lifetime of >400 years for the minimum rebar diameter, assuming an acceptable cross-section area loss of 10%.

d'Entremont, Anna [Savannah River National Laborat↗

Application of Direct Assessment Approaches and Methodologies to Cathodically Protected Nuclear Waste Transfer Lines

The U.S. Department of Energy's (DOE) Hanford Site is responsible for the safe storage, retrieval, treatment, and disposal of approximately 54 million gallons (204 million liters) of radioactive waste generated since the site's inception in 1943. Today, the major structures involved in waste management at Hanford include 149 carbon steel single-shell tanks, 28 carbon-steel double-shell tanks, plus a network of buried metallic transfer lines and ancillary systems (pits, vaults, catch tanks, etc.) required to store, retrieve, and transfer waste within the tank farm system. Many of the waste management systems at Hanford are still in use today. In response to uncertainties regarding the structural integrity of these systems,' an independent, comprehensive integrity assessment of the Hanford Site piping system was performed. It was found that regulators do not require the cathodically protected pipelines located within the Hanford Site to be assessed by External Corrosion Direct Assessment (ECDA) or any other method used to ensure integrity. However, a case study is presented discussing the application of the direct assessment process on pipelines in such a nuclear environment. Assessment methodology and assessment results are contained herein. An approach is described for the monitoring, integration of outside data, and analysis of this information in order to identify whether coating deterioration accompanied by external corrosion is a threat for these waste transfer lines.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Feasibility Study for Cathodic Protection of Waste Tanks at Hanford

The Hanford Nuclear Reservation site contains approximately 211 million liters of radioactive and chemically hazardous waste arising from nuclear weapons production, beginning with World War II, and continuing through the Cold War. The waste is stored in 177 carbon-steel underground storage tanks, of which 149 are single-shell tanks (SSTs) and the remaining are double-shell tanks (DSTs). The mission of an ongoing River Protection Project is to retrieve the waste from the underground storage tanks and then treat and immobilize (i.e., vitrify) it for disposal. Waste from the older SSTs is being progressively retrieved into the newer DSTs for storage pending treatment, immobilization, and disposal. Waste chemistry controls are in place to mitigate general corrosion, pitting corrosion, and stress corrosion cracking (SCC) and minimize corrosion risks to the carbon steel tank liners of DST at the Hanford Site. The chemistry control program focuses on preserving liner integrity while balancing the need for caustic/nitrite additions that have large downstream impacts on vitrification. Some of the DSTs store salt cake or sludge waste layers contain out-of-specification interstitial liquids that contact the primary tank bottom or sidewall. Remediation of such layers through chemical additions is not practical. At the present time, the most significant leak integrity concern at Hanford is for corrosion of the tank bottoms of DSTs where the solids layer is out of specification because of hydroxide ion depletion and consequently, pH values that are less than 12. Cathodic protection (CP) has been proposed as a possible way to protect the liners of such tanks against corrosion. The objective of this project was to investigate the feasibility of applying CP to Hanford DSTs to mitigate internal corrosion of the carbon steel tank primary liners. The scope of the project included (1) a literature review on the application of CP to storage tank systems, in general, and to waste tanks at the Savannah River Site (SRS) and Hanford, (2) a review of the finite element analysis (FEA) model recently developed to evaluate potentials for a DST, and (3) the development of a boundary element analysis (BEA) model for CP for a DST. Tank AN-107, one of the Hanford DSTs, was selected for this work because (1) the bottommost waste layer in the tank is out-of-specification, and (2) electrochemical and resistivity data, based on recent waste sampling and testing, are available for this tank. The overarching conclusion of this study is that, based on the available information, it is feasible to apply CP to mitigate internal corrosion of the primary liners of the Hanford DSTs. However, significant additional information and work are required before a CP system can be designed. Recommendations for next steps in the design of the CP system will be presented.

WIERSMA, BRUCE↗

Facile in Situ Syntheses of Cathode Protective Electrolyte Additives for High Energy Density Li-Ion Cells

Increasing the energy densities of Li-ion batteries necessitates operation of layered lithiated oxide cathodes at potentials exceeding 4 V vs Li/Li + . When continually exposed to such high potentials, these materials gradually deteriorate unless protected by sacrificial agents called electrolyte additives. During the formation cycles, these electrolyte additives decompose on the electrodes forming thin protective layers of insoluble products impeding further deleterious reactions. Some of these electrolyte additives spontaneously react when introduced into the electrolyte to yield specific surface-modifying products that alone protect the cathode; in other words, the nominal additive is the precursor and the secondary product is the protective agent. Guided by this insight, we used molecular engineering to obtain such surface-active secondary products in situ with 100% yield. Two of these electrolyte additives proved exceptional in that they delay both the impedance rise and capacity fade in the Li-ion cells. We demonstrate this protective action and scrutinize the activation of these additives in the electrolyte. As a result, by “taming” spontaneous reactions and regaining full control over the chemical structure, new avenues open to targeted synthesis of electrolyte additives extending the operation of high voltage Li-ion batteries.

25 ENERGY STORAGE↗

A General Overview of Cathodic Protection in Reinforced Concrete

Corrosion of reinforcement steel in concrete is a prevalent issue in infrastructures worldwide, with the direct costs of repair estimated to be $1 trillion annually. Treatment options are complicated by the concrete’s role in the corrosion process. Ordinary, modern-day cement is so alkaline that it maintains a thick passive layer on the steel surface, reducing corrosion to inconsequential rates. However, environmental contaminants in the form of carbon dioxide or chlorides may cause a breakdown in the passive layer, exposing the steel surface to corrosion. Galvanic cells will be free to form due to potential differences along the rebar, and anode sites will create dissolved iron ions that cannot travel far through the still concrete. Thus, rust products will accumulate directly onto the steel/concrete interface. Iron oxides have a much higher volume relative to steel, and even a miniscule amount of rust can produce enough volumetric stress to cause cracking, spalling and delamination of the surrounding concrete, increasing the risk of structural failure. Safeguards and inhibiting technology exist to limit the chances of corrosion initiation by either species, but cracking of the concrete cover and gradual accumulation of contaminants means that corrosion is unavoidable in certain environments and will initiate, given enough time.

36 MATERIALS SCIENCE↗

Vacuum ultra-violet emission of plasma discharges with high Xe partial pressure using a cathode protective layer with high secondary electron emission

In this work, the mechanism of the vacuum ultra-violet (VUV) emission of plasma discharges, with high Xe partial pressure and high ion-induced secondary electrons emission protective layer, is studied by measuring the VUV light emission directly and comparing it with two-dimensional simulations. From the panel measurement, we find that the high intensity of excimer VUV mainly contributes to the high luminous efficacy of SrCaO-plasma display panels (PDP) at a low sustain voltage. The unchanged Xe excitation efficiency indicates that the electron temperature is not decreased by the high secondary electrons emission protective layer, even though the sustain voltage is much lower. From the two-dimensional simulations, we can find that the ratio of excimer VUV to resonant VUV, which is determined by the collision rate in the discharge, is only significantly affected by the Xe partial pressure, while it is independent of the sustain voltage and the secondary-electrons-emission capability of protective layer. The unchanged average electron energy at the moment when the electric field becomes maximum confirms that the improvement of the VUV production efficiency mainly is attributed to the increase in electron heating efficiency of a PDP with high ion-induced secondary electrons emission protective layer. Combining the experimental and the simulation results, we conclude about the mechanism by which the VUV production is improved for the plasma display panel with a high Xe partial pressure and a cold cathode with high ion-induced secondary electrons emission.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Protective cathode coatings for lithium-ion batteries

Cathode coatings for lithium ion batteries, cathodes coated with the coatings, and lithium ion batteries incorporating the coated cathodes are provided. The coatings, which are composed of binary, ternary, and higher order metal oxides and/or metalloid oxides, can reduce the hydrofluoric acid (HF)-induced degradation of the electrolyte and/or cathodes, thereby improving the performance of lithium ion batteries, relative to lithium ion batteries that employ bare cathodes.

Aykol, Muratahan↗