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At least 127 records · Page 7

Fighting Corrosion

Reinforced concrete structures such as bridges, parking decks, and balconies are designed to have a service life of over 50 years. All too often, however, many structures fall short of this goal, requiring expensive repairs and protection work earlier than anticipated. The corrosion of reinforced steel within the concrete infrastructure is a major cause for this premature deterioration. Such corrosion is a particularly dangerous problem for the facilities at NASA s Kennedy Space Center. Located near the Atlantic Ocean in Florida, Kennedy is based in one of the most corrosive-prone areas in the world. In order to protect its launch support structures, highways, pipelines, and other steel-reinforced concrete structures, Kennedy engineers developed the Galvanic Liquid Applied Coating System. The system utilizes an inorganic coating material that slows or stops the corrosion of reinforced steel members inside concrete structures. Early tests determined that the coating meets the criteria of the National Association of Corrosion Engineers for complete protection of steel rebar embedded in concrete. Testing is being continued at the Kennedy's Materials Science Beach Corrosion Test Site.

Source record↗

Electrochemical Measurement of Atmospheric Corrosion

Corrosion of Shuttle thruster components in atmospheres containing high concentrations of nitrogen tetroxide (NTO) and water is an important issue in ground operations of bipropellant systems in humid locations. Measurements of the corrosivities of NTO-containing atmospheres and the responses of different materials to these atmospheres have been accomplished using an electrochemical sensor. The sensor is composed of alternating aluminum/titanium strips separated by thin insulating layers. Under high humidity conditions a thin film of water covers the surface of the sensor. Added NTO vapor reacts with the water film to form a conductive medium and establishes a galvanic cell. The current from this cell can be integrated with respect to time and related to the corrosion activity. The surface layer formed from humid air/NTO reacts in the same way as an aqueous solution of nitric acid. Nitric acid is generally considered an important agent in NTO corrosion situations. The aluminum/titanium sensor is unresponsive to dry air, responds slightly to humid air (> 75% RH), and responds strongly to the combination of humid air and NTO. The sensor response is a power function (n = 2) of the NTO concentration. The sensor does not respond to NTO in dry air. The response of other materials in this type of sensor is related to position of the material in a galvanic series in aqueous nitric acid. The concept and operation of this electrochemical corrosion measurement is being applied to other corrosive atmospheric contaminants such as hydrogen chloride, hydrogen fluoride, sulfur dioxide, and acidic aerosols.

DeArmond, Anna H.↗

Evaluation of Corrosion and Its Impact on the Mechanical Performance of Al–Steel Joints

Aluminum–steel joints are increasingly used in the automotive industry to meet the requirements for energy saving and emission reduction. Among various joining technologies, self-pierce riveting (SPR) and resistance spot welding (RSW) are two well-established technologies for fabricating dissimilar joints with stable and high mechanical performance. However, corrosion will occur in these joints inevitably due to different electrochemical properties, which can degrade the surface quality and the mechanical performance, such as strength. This paper presents a method of understanding the corrosion mechanisms in joining aluminum and steel. For this understanding, a hybrid method combining experimental observations, mechanical properties identification, and analytical approaches was used to assess the evolution of the impact of corrosion on the joining performance, such as traction separation curves. The study was conducted on common combinations used in the vehicles, e.g., a 1.2 mm thickness aluminum alloy (AA 6022) and 2.0 mm thickness hot deep galvanized steel (HDG HSLA 340) joined by SPR and RSW. After the fabrication of these joints, accelerated cyclic corrosion tests of up to 104 cycles were performed, which reproduced the environmental conditions to which a vehicle was exposed. By investigating the microstructural evolution within the joints, the corrosion mechanisms of SPR and RSW joints were revealed, including the initiation and propagation. Moreover, the intrinsic impact of the corrosion on the mechanical performance, including the strength, axial stiffness, and crashworthiness, was analyzed by performing a lap-shear test. It showed that as corrosion proceeds, the fracture modes and mechanical performance are affected significantly.

Chemistry↗

Corrosion of Zinc Cold Spray Coatings in a Wet Sweet and Sour Gas Environment

Internal corrosion is a problem for steel pipelines transporting natural gas or CO 2 containing water and partial pressures of H 2 S higher than 0.3 kPa (0.05 psi). This work aims to mitigate internal corrosion in steel pipelines transporting natural gas containing H 2 S using cold spray coatings. Two types of the cold spray binary metallic coatings (zinc chromium [ZnCr]. zinc niobium [ZnNb]) were studied using electrochemical techniques: potentiodynamic polarization, linear polarization resistance, and electrochemical impedance spectroscopy. The corrosion resistance of cold spray coatings (ZnCr, ZnNb) was evaluated in an environment containing 4 bar CO 2 pressure, simulating the partial pressures found in gas transmission lines over a solution of 3.5 wt% NaCl heated to 40°C. A concentration of 0.003 M Na 2 S 2 O 3 ·5H 2 O, corresponding to H 2 S partial pressures around 0.079 bar (1.146 psi), was used to simulate sour conditions. Postcorrosion surface characterization was performed using a scanning electron microscope (SEM) equipped with an energy-dispersive x-ray spectroscope (EDS) and x-ray diffraction analysis. The data showed that the presence of 0.003 M Na 2 S 2 O 3 ·5H 2 O shifted the corrosion potential to more anodic values and decreased the corrosion current density. Both coatings showed similar behavior after 1 h of exposure in the CO 2 /H 2 S environment, indicating that similar electrochemical reactions were occurring on ZnNb and ZnCr. SEM images and EDS surface analyses for specimens showed a significant change in the surface chemical composition of carbon steel coated with ZnNb and ZnCr after 24 h of immersion. In the presence of thiosulfate (under sour conditions), the formation of corrosion product layers (ZnCO 3 and ZnS) on top of ZnNb and ZnCr coatings increased their corrosion resistance, which helped to reduce their corrosion by a factor of 2. Under a sweet environment, the corrosion rates for steel coated with cold spray coatings after 14 d of exposure are lower than that for galvanized steel by a factor of 5 due to the ZnCO 3 layer formed on top of the coatings. The ZnCO 3 layer formed on the steel surface acts as a physical barrier against corrosion by blocking the diffusion of corrosive species to the surface. No localized attack was observed. ZnCr Cold spray coating with defect showed promising corrosion protection against CO 2 corrosion (sweet corrosion) after 14 d of exposure to a CO 2 environment. Here, the scratch on the coating simulated damage created in service, and it was deep enough to expose the substrate material (steel). The formation of zinc oxide (ZnO) and zinc carbonate (ZnCO 3 ) on the scratch confirmed the cathodic protection of the steel by ZnCr and ZnNb coatings.

36 MATERIALS SCIENCE↗

Liquid Coatings for Reducing Corrosion of Steel in Concrete

Inorganic coating materials are being developed to slow or stop corrosion of reinforcing steel members inside concrete structures. It is much simpler and easier to use these coating materials than it is to use conventional corrosion-inhibiting systems based on impressed electric currents. Unlike impressed electrical corrosion-inhibiting systems, these coatings do not require continuous consumption of electrical power and maintenance of power-supply equipment. Whereas some conventional systems involve the use of expensive arc-spray equipment to apply the metallic zinc used as the sacrificial anode material, the developmental coatings can be applied by use of ordinary paint sprayers. A coating material of the type under development is formulated as a liquid containing blended metallic particles and/or moisture-attracting compounds. The liquid mixture is sprayed onto a concrete structure. Experiments have shown that even though such a coat resides on the exterior surface, it generates a protective galvanic current that flows to the interior reinforcing steel members. By effectively transferring the corrosion process from the steel reinforcement to the exterior coating, the protective current slows or stops corrosion of the embedded steel. Specific formulations have been found to meet depolarization criteria of the National Association of Corrosion Engineers (NACE) for complete protection of steel reinforcing bars ("rebar") embedded in concrete.

MacDowell, Louis G.↗

Hanford Double Shell Waste Tank Corrosion Studies (Final Report FY2023)

For fiscal year (FY) 2023, the Savannah River National Laboratory (SRNL) focused on two experimental tasks related to Hanford Double Shell Tank (DST) chemistry and integrity. The first task focused on understanding risk of corrosion due to formation of either continuous layers or discrete patches of solids on the tanks’ inner sidewalls and bottoms. Differences in the conductivity between various layers of the tank (e.g., solids, liquid, etc.) could result in differences in the electrochemical potential of the tank metal at various locations. The electrochemical potential difference may result in a corrosion current between the coupled surfaces. In FY23, SRNL investigated test configurations and protocols that could evaluate the presence of a galvanic couple between the tank bottom and the tank wall.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Hexavalent Chrome Free Coatings for Electronics Applications: Joint Test Report

Regardless of the corrosivity of the environment, all metals require periodic maintenance activity to guard against the insidious effects of corrosion and thus ensure that alloys meet or exceed design or performance life. The standard practice for protecting metallic substrates is the application of a coating system. Applied coating systems work via a variety of methods (barrier, galvanic, and/or inhibitor) and adhere to the substrate through a combination of chemical and physical bonds. For years hexavalent chromium has been a widely used element within applied coating systems because of its self healing and corrosion resistant properties. Occupational Safety and Health Administration (OSHA) studies have concluded that hexavalent chromium (hex chrome) is carcinogenic and poses significant risk to human health. On May 5, 2011 amendments to the Defense Federal Acquisition Regulation Supplement (DFARS) were issued in the Federal Register. Subpart 223.73 prohibits contracts from requiring hexavalent chromium in deliverables unless certain exceptions apply. These exceptions include authorization from a general or flag officer and members of the Senior Executive Service from a Program Executive Office, and unmodified legacy systems. Otherwise, Subpart 252.223-7008 provides the contract clause prohibiting contractors from using or delivering hexavalent chromium in a concentration greater than 0.1 percent by weight for all new contracts and to be included down to subcontractors for supplies, maintenance and repair services, and construction materials. National Aeronautics and Space Administration (NASA), Department of Defense (DoD), and industry stakeholders continue to search for alternatives to hex chrome in coatings applications that meet their performance requirements in corrosion protection, cost, operability, and health and safety, while typically specifying that performance must be equal to or greater than existing systems.

Kessel, Kurt↗

Electronic Tongue Containing Redox and Conductivity Sensors

The Electronic Tongue (E-tongue 2) is an assembly of sensors for measuring concentrations of metal ions and possibly other contaminants in water. Potential uses for electronic tongues include monitoring the chemical quality of water in a variety of natural, industrial, and laboratory settings, and detecting micro-organisms indirectly by measuring microbially influenced corrosion. The device includes a heater, a temperature sensor, an oxidation/reduction (redox) sensor pair, an electrical sensor, an array of eight galvanic cells, and eight ion-specific electrodes.

Buehler, Martin↗

Field Testing of Self-Healing Metallic Coatings for Internal Corrosion Protection of Natural Gas Pipelines

Internal corrosion occurs in natural gas pipelines primarily due to the presence of water, carbon dioxide, and hydrogen sulfide. Internal corrosion can eventually result in leakage, cracks, and rupture of the pipeline. The objective of this work is to mitigate internal corrosion in steel pipelines transporting natural gas using cold spray coatings. The corrosion behavior of carbon steel coated with self-healing zinc chromium (ZnCr) and zinc niobium (ZnNb) cold spray coatings was investigated in a natural gas environment. For comparison purposes, hot-dip galvanized steel (HDGS) was tested under the same conditions as cold spray coatings. The field test was performed at the NW Natural gas storage facility in Mist, Oregon. The field test was conducted in a 6-inch diameter pipe transporting wet natural gas out of an underground storage well at 500 psi and 4.4 °C. The coupons were tested for 15 and 32 days under stagnant and flow conditions, respectively. Weight loss method was used to measure the corrosion rate of metallic coatings. Post-corrosion surface characterization was performed on the specimen using a scanning electron microscopy (SEM) equipped with energy dispersive X-ray spectroscopy (EDS). Crystalline phases were determined by X-ray diffraction (XRD). The field-test results confirmed that the metallic coatings provided corrosion protection of carbon steel exposed to wet natural gas under stagnant and flow conditions. The formation of the ZnCO 3 layer on top of ZnNb and ZnCr coatings led to passivation of the coatings which helps to reduce the self-corrosion. These layers form a barrier for diffusion of corrosive species to the surface.

03 NATURAL GAS↗

Accelerating FEM-Based Corrosion Predictions Using Machine Learning

Atmospheric corrosion of metallic parts is a widespread materials degradation phenomena that is challenging to predict given its dependence on many factors (e.g. environmental, physiochemical, and part geometry). For materials with long expected service lives, accurately predicting the degree to which corrosion will degrade part performance is especially difficult due to the stochastic nature of corrosion damage spread across years or decades of service. The Finite Element Method (FEM) is a computational technique capable of providing accurate estimates of corrosion rate by numerically solving complex differential Eqs. characterizing this phenomena. Nevertheless, given the iterative nature of FEM and the computational expense required to solve these complex equations, FEM is ill-equipped for an efficient exploration of the design space to identify factors that accelerate or deter corrosion, despite its accuracy. In this work, a machine learning based surrogate model capable of providing accurate predictions of corrosion with significant computational savings is introduced. Specifically, this work leverages AdaBoosted Decision trees to provide an accurate estimate of corrosion current per width given different values of temperature, water layer thickness, molarity of the solution, and the length of the cathode for a galvanic couple of aluminum and stainless steel.

36 MATERIALS SCIENCE↗

Localized corrosion at nm-scale hardening precipitates in Al-Cu-Li alloys

The localized corrosion of Li-containing nm hardening precipitates in the 3rd generation of Al-Cu-Li alloys was investigated based on a quasi in situ approach by sequentially exposing the material to NaCl solution and characterizing the structural, chemical, and electrochemical evolution at atomic scale using electron microscopy, spectroscopy, 3D tomography, electrochemical measurements, and DFT calculations. Localized corrosion of Al 7.5 Cu 4 Li (TB phase) initiated along {001} family of planes through the dealloying of Al and Li due to a low surface work function. Cu was enriched along the Cu (110) // T B (011) // Al (100) orientations on and around corroded T B precipitates. No strong galvanic interactions were observed at the T B and Al matrix interface due to the formation of a Li-C-O rich passivation layer during electrolyte exposure. Similarities and differences between T B and other common Al-Cu-Li precipitates (Al 2 CuLi, Al 6 CuLi 3 , and Al 3 Li) with respect to corrosion are discussed. Overall, the reported corrosion mechanism can assist in the assessment of the localized corrosion susceptibility of precipitation-hardened Al alloys and assist in the design of new alloys.

36 MATERIALS SCIENCE↗

Electrochemical noise studies on localized corrosion of Ni and Ni-20Cr in molten ZnCl 2

The electrochemical noise (ECN) technique was employed to study corrosion of two model systems, i.e. pure Ni and a binary Ni-20 wt%Cr (Ni20Cr) alloy in molten ZnCl 2 at 623 K. Here we measured ECN transients in current and open-circuit potential from two nominally identical Ni-Ni and Ni20Cr-Ni20Cr electrodes and one galvanic Ni-Ni20Cr electrode pair. The behavior of ECN is quite distinct among the three-electrode systems, and it is correlated with the various microscopic observations of micro- and nano-scale morphological features. Based on the ECN study coupled with the microstructural analysis, the origins of ECN in the molten salt environment as well as the mechanisms of localized corrosion in the three systems are discussed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Evaluation of inorganic zinc-rich primers using Electrochemical Impedance Spectroscopy (EIS)

This investigation explores the use of Electrochemical Impedance Spectroscopy (EIS) in combination with beach exposure as a short term method for analyzing the performance of twenty-one zinc-rich primers. The twenty-one zinc-rich primers were: Carboline CZ-11, Ameron Devoe-Marine Catha-Coat 304, Briner V-65, Ameron D-21-9, Sherwin Williams Zinc Clad II, Carboline CZ-D7, Ameron D-4, Dupont Ganicin 347WB, Porter TQ-4374H, Inorganic Coatings IC-531, Subox Galvanox IV, Southern Coatings Chemtec 600, Glidden Glidzinc 5530, Byco SP-101, Tnemec 90E-75, Devoe Catha-Coat 302H, Glidden Glidzinc 5536, Koppers 701, Ameron D-21-5, Coronado 935-152, and Subox Galvanoz V. Data were also collected on galvanized steel for comparison purposes. A library of Bode magnitude plots was generated for each coating including curves for the initial time and after each week of atmospheric exposure as Beach Corrosion Test Site near the Space Shuttle launch pad at the Kennedy Space Center for up to three weeks. An examination of the variation of the Bode magnitude plots with atmospheric exposure revealed no clearly identifiable trend at this point that could distinguish between the good and the poor coatings. The test will be continued by including EIS measurements after six months and one year of atmospheric exposure.

Calle, Luz M.↗

Friction and wear of iron in sulfuric acid

Elemental iron sliding on aluminum oxide in aerated sulfuric acid concentrations ranging from very dilute (0.000007 N; i.e., 4 ppm) to very concentrated (96 percent acid) was studied. Load and reciprocating sliding speeds were kept constant. With the most dilute acid of 0.7 to 0.0002 N, a complex corrosion product formed that was friable and often increased friction and wear. At concentrations of 0.001 N, metal losses were essentially by wear alone. Because no buildup of corrosion products occurred, this acid concentration became the standard from which to separate metal loss from direct corrosion and mechanical wear losses. When the acid concentration was increased to 5 percent, the high corrosion rate of iron in sulfuric acid strongly dominated the total wear loss. This strong corrosion increased to 30 percent acid, and decreased somewhat at 50 percent in accordance with expectations. However, the low corrosion of iron expected at acid concentrations of 65 to 96 percent was not observed in the wear area. It is apparent that the normal passivating film was being worn away and a galvanic cell established which rapidly attached to the wear area.

Rengstorff, G. W. P.↗

Galvanic Protected Anode Materials for Molten Regolith Electrolysis

This effort aimed to explore the use of refractory alloys as long-lifetime electrode materials for use in a molten regolith electrolysis (MRE) reactor, a technology that can produce oxygen (O2) from regolith. To find a material capable of withstanding the high temperatures and corrosive nature of molten regolith, first-principles thermodynamic calculations were performed on platinum group metals in the presence of iron (Fe) and silicon (Si) to determine favorable compositions for resisting unwanted secondary phases that could form on the surface of the material. As a result of these first-principles calculations, the kinetic properties of elements such as aluminum (Al), Fe, and Si can be more easily derived, which would provide insight into the longevity of such a material when used in an MRE reactor. The effort funded by this CIF project mapped the entire phase diagram of platinum group metals, which is beneficial not only to MRE where high temperatures and molten material are present, but also aerospace applications like turbine materials, terrestrial metal processing techniques, and energy storage applications. This project narrowed a broad spectrum of refractory metals down to a small list of alloys that would be able to survive not only the high temperatures of an MRE reactor, but also the thermodynamic forces that would cause inferior alloys to form secondary phases, which would ultimately consume the electrodes of the reactor. This research needs to be followed up with experimental demonstrations of these alloys in an MRE environment.

Kevin Grossman↗

ZnCr and ZnNb Cold Spray Coatings

Novel cold spray zinc-based alloy coatings have been investigated for corrosion protection of API 5L low carbon steel pipelines used in transporting natural gas. These different zinc alloy coatings are designed for use to help prevent internal corrosion and improve the lifespan of steel pipelines via sacrificial anodic protection. The corrosion behavior of these cold deposited zinc alloy coatings was investigated in CO2 saturated 3.5 wt.% NaCl solutions under simulated natural gas pipeline conditions. Electrochemical tests were conducted at 25 and 40 °C to determine the polarization resistance and galvanic current between each coating and the steel substrate in the galvanic couple. Tests were conducted at atmospheric, 1 bar, pressure. The results indicate that use of these coatings has the potential to increase the lifespan of steel pipelines above what a zinc coating alone could provide.

Teeter, Lucas↗

Failure modes of protection layers produced by atomic layer deposition of amorphous TiO 2 on GaAs anodes

Amorphous titanium dioxide (a-TiO 2 ) films formed by atomic layer deposition can serve as protective coatings for semiconducting photoanodes in water-splitting cells using strongly alkaline aqueous electrolytes. Herein, we experimentally examine the mechanisms of failure for p + -GaAs anodes coated with a-TiO 2 films (GaAs/a-TiO 2 ). Galvanic displacement of exposed GaAs by Au allowed imaging of pinholes in the a-TiO 2 coatings, and enabled collection of quantitative and statistical data associated with pinhole defects. A combination of imaging, electrochemical measurements, and quantitative analyses of corrosion products indicated that extrinsic pinholes were present in the a-TiO 2 films before electrochemical operation. During electrochemical operation these pinholes led to pitting corrosion of the underlying GaAs substrate. The dominant source of pinholes was the presence of atmospheric particulate matter on the GaAs surface during deposition of the a-TiO 2 layer. The pinhole density decreased substantially when the thickness of the a-TiO 2 coating increased beyond 45 nm, and approached zero when the thickness of the film exceeded 112 nm. The density of pinholes in films thinner than 45 nm decreased when the a-TiO 2 coating was deposited in an environmentally controlled cleanroom. Pinhole-free GaAs/a-TiO 2 devices were also tested via chronoamperometry to quantify the rate of pinhole formation during electrochemistry. The time-to-failure increased with thickness, suggesting that the failure mechanism may involve diffusion or migration through the film. However, other mechanisms may also contribute to the degradation of thicker films (>112 nm). Nevertheless, as previously hypothesized, extrinsic pinhole defects formed during deposition and testing control the short-term protective performance of the a-TiO 2 film for GaAs anodes evolving O 2 from water.

25 ENERGY STORAGE↗