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At least 91 records · Page 5

Marine Atmospheric Corrosion of Additively Manufactured Stainless Steels

Additively manufactured (AM) stainless steels exhibit numerous microstructural differences compared to their wrought counterparts, such as Cr enriched dislocation cell structures. The influence these unique features have on a SSs corrosion resistance are still under investigation with most current works limited to laboratory experiments. The work herein shows the first documented study of AM 304L and 316L exposed to a severe marine environment on the eastern coast of Florida with comparisons made to wrought counterparts. Coupons were exposed for 21 months and resulted in significant pitting corrosion to initiate after 1 month of exposure for all conditions. At all times, the AM coupons exhibited lower average and maximum pit depths than their wrought counterparts. After 21 months, pits on average were 4 μm deep for AM 316L specimen and 8 μm deep for wrought specimen. Pits on the wrought samples tended to be nearly hemispherical and polished with some pits showing crystallographic attack while pits on AM coupons exhibited preferential attack at melt pool boundaries and the cellular microstructure.

36 MATERIALS SCIENCE↗

Corrosion and corrosion fatigue of airframe aluminum alloys

Localized corrosion and corrosion fatigue crack nucleation and growth are recognized as degradation mechanisms that effect the durability and integrity of commercial transport aircraft. Mechanically based understanding is needed to aid the development of effective methodologies for assessing durability and integrity of airframe components. As a part of the methodology development, experiments on pitting corrosion, and on corrosion fatigue crack nucleation and early growth from these pits were conducted. Pitting was found to be associated with constituent particles in the alloys and pit growth often involved coalescence of individual particle-nucleated pits, both laterally and in depth. Fatigue cracks typically nucleated from one of the larger pits that formed by a cluster of particles. The size of pit at which fatigue crack nucleates is a function of stress level and fatigue loading frequency. The experimental results are summarized, and their implications on service performance and life prediction are discussed.

Chen, G. S.↗

Refinement of Salt Dissolution Inhibitor Requirements (Interim Report)

At Savannah River Site, High-Level Waste is stored in below-grade carbon steel tanks. This waste in part consists of sludge, salt cake, and/or supernate. Preparation of this waste for future processing involves dissolution of the salt cake layer. The salt dissolution process can create conditions that leave the carbon steel tanks susceptible to localized corrosion. The salt to be dissolved contains high concentrations of nitrate, that once released, create an environment that may be conducive to pitting corrosion or stress corrosion cracking (SCC) of carbon steel. The salt dissolution process also liberates interstitial liquid trapped between the salt crystals. This liquid is initially high in nitrite and hydroxide concentration. High pH and greater ratios of nitrite to nitrate act as inhibitors to minimize corrosion of carbon steel in high nitrate environments. However, as dissolution proceeds, the concentration of nitrate increases while the hydroxide and nitrite concentration of the interstitial liquid depletes and becomes insufficient to prevent the onset of corrosion attack. While tank blending and the addition of inhibitors are used to ensure adequate concentrations of hydroxide and nitrite during normal operation, this is not desirable during salt dissolution as it can reduce process efficiency and increase the amount of waste that needs processed.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Effects of service environments on aluminum-brazed titanium (ABTi)

Aluminum brazed titanium (ABTi) structures were evaluated during prolonged exposure to extreme environments: elevated temperature exposure to airline service fluids, hydraulic fluid, and seawater, followed by laboratory corrosion tests. Solid-face and perforated face honeycomb sandwich panel specimens, stressed panel assemblies, and faying surface brazed joints were tested. The corrosion resistance of ABTi is satisfactory for commercial airline service. Unprotected ABTi proved inherently resistant to attack by all of the extreme service aircraft environments except: seawater at 700 K (800 F) and above, dripping phosphate ester hydraulic fluid at 505 K (450 F), and a marine environment at ambient temperature. The natural oxides and deposits present on titanium surfaces in airline service provide protection against hot salt corrosion pitting. Coatings are required to protect titanium dripping phosphate ester fluid at elevated temperatures and to protect exposed acoustic honeycomb parts against corrosion in a marine environment.

Cotton, W. L.↗

Long-term corrosion evaluation of stainless steels in Space Shuttle iodinated resin and water

The effects of stainless steel exposure to iodinated water is a concern in developing the Integrated Water System (IWS) for Space Station Freedom. The IWS has a life requirement of 30 years, but the effects of general and localized corrosion over such a long period have not been determined for the candidate materials. In 1978, Umpqua Research Center immersed stainless steel 316L, 321, and 347 specimens in a solution of deionized water and the Space Shuttle microbial check valve resin. In April 1990, the solution was chemically analyzed to determine the level of corrosion formed, and the surface of each specimen was examined with scanning electron microscopy and metallography to determine the extent of general and pitting corrosion. This examination showed that the attack on the stainless steels was negligible and never penetrated past the first grain boundary layer. Of the three alloys, 316L performed the best; however, all three materials proved to be compatible with an aqueous iodine environment. In addition to the specimens exposed to aqueous iodine, a stainless steel specimen (unspecified alloy) was exposed to moist microbial check valve resin and air for a comparable period. This environment allowed contact of the metal to the resin as well as to the iodine vapor. Since the particular stainless steel alloy was not known, energy dispersive spectroscopy was used to determine that this alloy was stainless steel 301. The intergranular corrosion found on the specimen was limited to the first grain boundary layer.

Krohn, Douglas D.↗

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↗

Laser Confocal Microscopy Uncertainty Quantification Study

At Los Alamos National Laboratory (LANL), the Storage Safety and Engineering (SSE) team completes annual surveillance on a subset of in-use interim nuclear material storage containers in fulfilment of requirements outlined in DOE Manual M 441.1-1. The containers are selected through several methods, such as subject matter expert judgement, random selection, and trending items. Following these selections, the SSE team has the capacity to complete surveillance on 15-20 containers each fiscal year, composed of a combination of SAVY-4000 and Hagan storage containers. Through previous work, the stainless-steel components of the containers have been identified as life limiting components, with an emphasis on the thin-walled bodies. The team is focused on understanding the extent of general and pitting corrosion, due to observations of extensive corrosion from stored contents and bag-out-bag degradation. Quantifying corrosion effects on the thin-walled stainless steel container bodies, and understanding potential impacts to the respective design release rates and design qualification release rates is paramount to the team. To date, destructive examination (DE) has proven to be the most insightful method for developing an understanding on the extent of corrosion on used containers. To standardize this process, the SSE team developed a destructive examination guide for analyzing stainless steel components of the containers. Corroded containers of interest are identified during surveillance activities and set aside for sectioning and characterization. Following sectioning, a major step in the DE workflow is the utilization of laser confocal microscopy for scanning corroded samples of interest and extracting data on pits, such as count, depth, and equivalent diameter. Adhering to the techniques outlined in the DE guide, analysis has been completed on two Hagans and one SAVY-4000 container, with the maximum pit depth recorded as 139.1 ± 22.82 μm on a 17.5 year old Hagan. The findings from the completed destructive examinations will be utilized to support lifetime extension efforts of the SAVY-4000 as the team can better estimate corrosion rates and effects over time based on stored contents and age. Due to the implications of observing extreme pit depths that approach the nominal container body thickness of .0299 inches (0.759 mm) or minimum container thickness of 0.236” (0.6 mm), high confidence in the LCM measurements is desired. Through testing outlined in, it was concluded that the total error ascribed to the 20x objective when conducting large image mapping on the Keyence VK-X3050 laser confocal microscope (LCM) relative to a 50x objective (reference) is 16.4% (± 8.73%). For shallow features on the order of pristine SAVY surface defects (i.e. 5 μm), this uncertainty is appropriate. However, this conservative estimate of total error poses a fundamental concern for pit depths that approach the thickness of the measured samples. That is, with the measurement uncertainty currently employed on all measurements, the LCM would be unable to resolve if a pit with a depth of 515 μm is through wall. Standard step height samples were procured and used in the present study to assess the resolution and repeatability of height measurements. Understanding the resolution and repeatability of height measurements was the first focus of the team as it relates directly to pit depth, which is of primary concern. Calibration gratings were procured to evaluate the resolution and repeatability of measurements in the X and Y axes of the LCM stage. The results of the depth uncertainty study were conducted first and presented in the subsequent sections. The planar uncertainty study is appended to the depth study with conclusions from both summarized at the end of the report.

36 MATERIALS SCIENCE↗

Effect of Drying on Corrosion Mitigation of Hanford Transfer Lines

Radioactive waste is stored in underground, carbon-steel double-shell tanks at the Department of Energy Hanford site. The waste is transferred between the tanks and other assets using the transfer lines spanning throughout the various tank farms at Hanford. The transfer lines consist of a pipe-in-pipe design, small diameter pipes, and are not piggable. Recent inspection data of the transfer lines have shown areas with corrosion on both interior of the encasements and exterior of the primary pipes, with nearly 50 percent wall loss on the primary pipes and nearly 25% wall loss on the encasement pipes due to pitting corrosion. The visual inspections of the transfer lines have shown presence of corrosion products near the pipeline risers and beyond. It has been hypothesized that the corrosion is predominantly due to the high humidity conditions and in some cases is driven by the presence of residual hydrotest water in the encasement and the associated contact with the safety significant primary pipe. Therefore, drying of the transfer lines could lead to corrosion mitigation. Experimental studies are being conducted to understand the effect of environmental conditions, especially, relative humidity and temperature, on transfer line grade carbon steel corrosion and on mitigating corrosion. The experimental conditions are selected based on the seasonal temperature changes, and relative humidity conditions ranging from 30 to 100 percent. The experimental data will be used as guidance for maintaining a dry environment that will help mitigate the transfer-line corrosion caused by the high humidity conditions.

Shukla, Pavan K.↗

An anode-free Li metal cell with replenishable Li designed for long cycle life

Pit corrosion of Li during stripping is an important factor responsible for poor Li cycling efficiency, a metric that determines its cycling life. When excess Li is present, it has been observed that Li tends to strip in a non-uniform fashion, forming pits that extend well past the theoretical Li depth that inevitably lead to the formation of electronically isolated “dead” Li particles. In this work, a novel cell with replenishable Li is shown to inherently mitigate the formation of this “dead” Li, as a direct result of a design in which the intrinsically more homogenous stripping behavior of anode-free cells are combined with a replenishable limited Li reservoir. These novel cells (Li|Cu||LiFePO 4 ) exhibit 25% and 34% higher cumulative capacities than the conventional cells (Cu|Li||LiFePO 4 ) in carbonate and ether electrolytes, respectively, enabling a significant increase in cycle life without impacting energy density. This improvement strategy represents a new direction in Li metal battery improvement, in which improved cycling can be achieved regardless of electrolyte chemistry.

Long cycle life↗

Electrochemical Impedance Spectroscopy of Alloys in a Simulated Space Shuttle Launch Environment

Type 304L stainless steel (304L SS) tubing is currently used in various supply lines that service the Orbiter at NASA's John F. Kennedy Space Center Launch Pads in Florida (USA). The atmosphere at the Space Shuffle launch site is very corrosive due to a combination of factors, such as the proximity of the Atlantic Ocean and the concentrated hydrochloric acid produced by the fuel combustion reaction in the solid rocket boosters. The acidic chloride environment is aggressive to most metals and causes severe pitting in many of the common stainless steel alloys such as 304L SS. Stainless steel tubing is susceptible to pitting corrosion that can cause cracking and rupture of both high-pressure gas and fluid systems. Outages in the systems where failures occur can impact the normal operation of the shuttle and launch schedules. The use of a more corrosion resistant tubing alloy for launch pad applications would greatly reduce the probability of failure, improve safety, lessen maintenance costs, and reduce downtime. A study which included ten alloys was undertaken to find a more corrosion resistant material to replace the existing 304L SS tubing. The study included atmospheric exposure at NASA's John F. Kennedy Space Center outdoor corrosion test site near the launch pads and electrochemical measurements in the laboratory which included DC techniques and electrochemical impedance spectroscopy (EIS). This paper presents the results from EIS measurements on three of the alloys: AL6XN (UN N08367), 254SMO (UNS S32l54), and 304L SS (UNS S30403). Type 304L SS was included in the study as a control. The alloys were tested in three electrolyte solutions which consisted of neutral 3.55% NaC1, 3.55% NaCl in O.1N HC1, and 3.55% NaCl in 1.ON HC1. The solutions were chosen to simulate environments that were expected to be less, similar, and more aggressive, respectively, than those present at the Space Shuttle launch pads. The results from the EIS measurements were analyzed to evaluate the corrosion susceptibility of the alloys and to predict the long-term corrosion performance of the subject materials. The results from the EIS measurements for the three alloys indicated that the higher-alloyed 254SMO and AL6XN exhibited a significantly improved resistance to corrosion than the 304L SS as the concentration of hydrochloric acid in the 3.55% NaC1 solution was increased. The polarization resistance values obtained from the EIS measurements were consistent with those from linear polarization measurements, and were indicative of the actual long-term corrosion performance of the alloys during a two-year atmospheric exposure study.

Calle, L. M.↗

Characterization and Electrochemical Analysis of Acidic Condensate-Induced Corrosion on Aluminized Coating on Steel in Residential Heaters

Condensing furnace residential heaters are starting to replace outdated and less efficient non-condensing units in homes across the US. However, the burning of natural gas in these new units produces acidic gases, which can form acid droplets (H 2 SO 4 , HNO 3 , H 2 CO 3 , etc.) that are corrosive to low-grade heat exchanger metallic materials. Type-1 aluminized steel has been used in industrial applications, such as marine, heating, and automobile parts, due to its resistance to oxidation at elevated temperature. Many components of the condensing furnaces, including heat exchangers, are made from type-1 aluminized steel. We investigated the interaction of type-1 aluminized steel substrates with two acidic condensate liquids by 500 h corrosion exposures as well as short-term electrochemical impedance measurements. SEM plan and cross-sectional view images revealed damage to the Al-Si rich layer and exposure of the steel substrate. The non-uniform damage in the Al-Si rich layer was likely attributed to a pitting corrosion mechanism and induced by high acidity of the condensate liquid. Electrochemical impedance measurements in an acidic condensate revealed lower corrosion resistance of the aluminized steel surface with a weld line, identifying welded sections as preferential corrosion initiation sites.

36 MATERIALS SCIENCE↗

Residual Stresses in a NiCrY-Coated Powder Metallurgy Disk Superalloy

Protective ductile coatings will be necessary to mitigate oxidation and corrosion attack on superalloy disks exposed to increasing operating temperatures in some turbine engine environments. However, such coatings must be resistant to harmful surface cracking during service. The objective of this study was to investigate how residual stresses evolve in such coatings. Cylindrical gage fatigue specimens of powder metallurgy-processed disk superalloy LSHR were coated with a NiCrY coating, shot peened, and then subjected to fatigue in air at room and high temperatures. The effects of shot peening and fatigue cycling on average residual stresses and other aspects of the coating were assessed. Shot peening did induce beneficial compressive residual stresses in the coating and substrate. However, these stresses became more tensile in the coating with subsequent heating and contributed to cracking of the coating in long intervals of cycling at 760 C. Substantial compressive residual stresses remained in the substrate adjacent to the coating, sufficient to suppress fatigue cracking. The coating continued to protect the substrate from hot corrosion pitting, even after fatigue cracks initiated in the coating.

superalloy↗

LCF Life of As-Deposited and Annealed NiCr-Y Coatings for Oxidation and Hot Corrosion Protection of Disk Alloys

Increasing temperatures in aero gas turbines is resulting in oxidation and hot corrosion attack of turbine disks. Since disks are sensitive to low cycle fatigue (LCF), any environmental attack, and especially hot corrosion pitting, can seriously degrade the life of the disk. Application of metallic coatings is one means of protecting disk alloys from this environmental attack. However, the presence of a metallic coating can degrade the LCF life of a disk alloy. Therefore, coatings must be designed which are not only resistant to oxidation and corrosion attack, but do not significantly degrade the LCF life of the alloy.Three different NiCr-Y coating compositions (29, 35.5, 44 wt.% Cr, all with 0.1 wt.% Y) were applied at two thicknesses by Plasma Enhanced Magnetron Sputtering (PEMS) to two similar Ni-based disk alloys. One Ni-35.5Cr-0.1Y coating also received a thin ZrO2 overcoat. The coated samples were also given a short thermal anneal in a low PO2 environment to encourage bonding of the coating and substrate as well as initiating formation of a chromia scale. Without further environmental exposure, the LCF life of coated and uncoated samples was evaluated at 760°C in air. The LCF lifetime of all coated samples was less than that of uncoated samples. The LCF life scaled with the Cr content and the high-Cr, thin coating showed the highest LCF life. Pre and post-test characterization of the various coatings, including identification of crack initiation sites, will be presented and the effect of the coating on the LCF life discussed.

low cycle fatigue↗

The effects of pitting on fatigue crack nucleation in 7075-T6 aluminum alloy

A high-strength aluminum alloy, 7075-T6, was studied to quantitatively evaluate chemical pitting effects of its corrosion fatigue life. The study focused on pit nucleation, pit growth, and fatigue crack nucleation. Pitting corrosion fatigue experiments were conducted in 3.5 percent NaCl aqueous solution under constant amplitude sinusoidal loading at two frequencies, 5 and 20 Hz. Smooth and unnotched specimens were used in this investigation. A video recording system was developed to allow in situ observation of the surface changes of the specimens during testing. The results indicated that pitting corrosion considerably reduces the fatigue strength by accelerating fatigue crack nucleation. A metallographic examination was conducted on the specimens to evaluate the nature of corrosion pits. First, the actual shapes of the corrosion pits were evaluated by cross-sectioning the pits. Secondly, the relation between corrosion pits and microstructure was also investigated. Finally, the possibility of another corrosion mechanism that might be involved in pitting was explored in this investigation. The fractography of the tested specimens showed that corner corrosion pits were responsible for fatigue crack nucleation in the material due to the associated stress concentration. The pits exhibited variance of morphology. Fatigue life for the experimental conditions appeared to be strongly dependent on pitting kinetics and the crack nucleation stage.

Ma, LI↗

The corrosion behavior of borosilicate glass in the presence of cementitious waste forms

Borosilicate glasses are widely used for radioactive waste disposal due to their ability to incorporate a variety of contaminants and radionuclides while exhibiting high durability in various disposal scenarios. This research evaluated the dissolution of borosilicate glass using both single-pass-flow-through (ASTM C1662-18) and product consistency test (ASTM C1285-21) methods with different solutions, including a cementitious-contacted water (called grout-contacted, GC, from this point) and solutions with varying levels of dissolved cementitious species such as Si, Ca, Al. Here, the results indicated that the presence of Ca plays a crucial role in suppressing glass corrosion, as evidenced by the slower normalized dissolution rates, which were one order of magnitude lower for boron and two orders of magnitude lower for rhenium, observed in both Ca-amended and GC solutions compared to the pH 12 buffer solution. This effect is attributed to the formation of a dense, low-porosity, and strongly bonded calcium silicate hydrate (CSH) layer on the glass surface, which implies that a glass corrosion process is influenced by ion exchange involving alkali ions Na + , K + , Ca 2+ , and hydrogen-containing species. A small number of glass particles treated in the GC solution showed minor corrosion pits in the form of shallow craters with an average diameter of approximately 500 μm. This observation is correlated with a significant reduction, 2000 to 3000 times lower, in the cumulative volume of glass pores, indicating that smaller pore voids were “sealed” in the presence of Ca 2+ ions, likely attributed to the formation of CSH precipitation or other corrosion products such as calcium carbonate saturated from the grout solution. These findings suggest that the presence of dissolved Ca in the GC solution can slow down the dissolution of borosilicate glass, contrary to the expected trend of higher dissolution rates resulting from exposure to high alkaline and thus higher pH solutions.

36 MATERIALS SCIENCE↗

Coatings for Oxidation and Hot Corrosion Protection of Disk Alloys

Increasing temperatures in aero gas turbines is resulting in oxidation and hot corrosion attack of turbine disks. Since disks are sensitive to low cycle fatigue (LCF), any environmental attack, and especially hot corrosion pitting, can potentially seriously degrade the life of the disk. Application of metallic coatings are one means of protecting disk alloys from this environmental attack. However, simply the presence of a metallic coating, even without environmental exposure, can degrade the LCF life of a disk alloy. Therefore, coatings must be designed which are not only resistant to oxidation and corrosion attack, but must not significantly degrade the LCF life of the alloy. Three different Ni-Cr coating compositions (29, 35.5, 45wt. Cr) were applied at two thicknesses by Plasma Enhanced Magnetron Sputtering (PEMS) to two similar Ni-based disk alloys. One coating also received a thin ZrO2 overcoat. The coated samples were also given a short oxidation exposure in a low PO2 environment to encourage chromia scale formation. Without further environmental exposure, the LCF life of the coated samples, evaluated at 760C, was less than that of uncoated samples. Hence, application of the coating alone degraded the LCF life of the disk alloy. Since shot peening is commonly employed to improve LCF life, the effect of shot peening the coated and uncoated surface was also evaluated. For all cases, shot peening improved the LCF life of the coated samples. Coated and uncoated samples were shot peened and given environmental exposures consisting of 500 hrs of oxidation followed by 50 hrs of hot corrosion, both at 760C). The high-Cr coating showed the best LCF life after the environmental exposures. Results of the LCF testing and post-test characterization of the various coatings will be presented and future research directions discussed.

LCF life↗

Numerical investigation of micro-galvanic corrosion in Mg alloys: Role of the cathodic intermetallic phase size and spatial distributions

Magnesium alloys are of increasing interest in structural applications due to their low-density, moderate specific strength and stiffness, recyclability, and high damping among other properties. However, the wide-scale applicability of magnesium alloys in structural applications has been limited due to many factors including its poor corrosion resistance. In this work, a numerical investigation to simulate the micro-galvanic corrosion behavior was performed to examine the influence of size and distribution of cathodic intermetallic phase (ß-Mg17Al12) in a Mg matrix. The ratio of cathodic to anodic surface area was kept constant in each simulation condition to understand the effect of size and spacing distributions. In general, fragmentation of a larger intermetallic particle into smaller ones was found to enhance the localized current density. However, the uniform distribution of this small intermetallic phase throughout the matrix was found to reduce the overall dissolution current density and hence, pitting corrosion severity.

Beura, Vikrant↗

Hot corrosion of Co-Cr, Co-Cr-Al, and Ni-Cr alloys in the temperature range of 700-750 deg C

The effect of SO3 pressure in the gas phase on the Na2SO4 induced hot corrosion of Co-Cr, Ni-Cr, and Co-Cr-Al alloys was studied in the temperature range 700 to 750 C. The degradation of the Co-Cr and Ni-Cr alloys was found to be associated with the formation of liquid mixed sulfates (CoSO4-Na2SO4 or NiSO4-Na2SO4) which provided a selective dissolution of the Co or Ni and a subsequent sulfidation oxidation mode of attack which prevented the maintenance of a protective Cr2O3 film. A clear mechanism was not developed for the degradation of Co-Cr-Al alloys. A pitting corrosion morphology was induced by a number of different mechanisms.

Chiang, K. T.↗