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At least 793 records · Page 44

Effect of cerium on structure modifications of a hybrid sol–gel coating, its mechanical properties and anti-corrosion behavior

Highlights: ► New sol–gel routes to replace chromates for corrosion protection of aluminum. ► Effect of cerium concentration on the microstructure of xerogel. ► Electrochemical and mechanical performances of hybrid coating with different cerium contents. ► Good correlation between the different results with an optimal cerium content of 0.01 M. -- Abstract: An organic–inorganic hybrid coating was developed to improve the corrosion resistance of the aluminum alloy AA 2024-T3. Organic and inorganic coatings derived from glycidoxypropyl-trimethoxysilane (GPTMS) and aluminum tri-sec-butoxide Al(O{sup s}Bu){sub 3}, with different cerium contents, were deposited onto aluminum by dip-coating process. Corrosion resistance and mechanical properties were investigated by electrochemical impedance measurements and nano-indentation respectively. An optimal cerium concentration of 0.01 M was evidenced. To correlate and explain the hybrid coating performances in relation to the cerium content, NMR experiments were performed. It has been shown that when the cerium concentration in the hybrid is higher than 0.01 M there are important modifications in the hybrid structure that account for the mechanical properties and anti-corrosion behavior of the sol–gel coating.

36 MATERIALS SCIENCE↗

Development in corrosion resistance by microstructural refinement in Zr-16 SS 304 alloy using suction casting technique

Highlights: • Grain refinement was made in Zr–16 wt.% SS alloy while prepared by suction casting process. • Distribution of Laves phase, e.g., Zr{sub 2}(Fe, Cr) was raised in suction cast (SC) Zr–16 wt.% SS. • Corrosion resistance was improved in SC alloy compared to that of arc-melt-cast alloy. • Grain refinement in SC alloy assisted for an increase in its corrosion resistance. - Abstract: Zirconium (Zr)-stainless steel (SS) hybrid alloys are being considered as baseline alloys for developing metallic-waste-form (MWF) with the motivation of disposing of Zr and SS base nuclear metallic wastes. Zr–16 wt.% SS, a MWF alloy optimized from previous studies, exhibit significant grain refinement and changes in phase assemblages (soft phase: Zr{sub 2}(Fe, Cr)/α-Zr vs. hard phase: Zr{sub 3}(Fe, Ni)) when prepared by suction casting (SC) technique in comparison to arc-cast-melt (AMC) route. Variation in Cr-distribution among different phases are found to be low in suction cast alloy, which along with grain refinement restricted Cr-depletion at the Zr{sub 2}(Fe, Cr)/Zr interfaces, prone to localized attack. Hence, SC alloy, compared to AMC alloy, showed lower current density, higher potential at the breakdown of passivity and higher corrosion potential during polarization experiments (carried out under possible geological repository environments, viz., pH 8, 5 and 1) indicating its superior corrosion resistance.

36 MATERIALS SCIENCE↗

Considerations for realistic atmospheric environments: An application to corrosion testing

Measured salt compositions in dust collected over roughly the last decade from surfaces of in-service stainless-steel alloys at four locations around the United States are presented, along with the predicted brine compositions that would result from deliquescence of these salts. The salt compositions vary greatly from ASTM seawater and from laboratory salts (i.e., NaCl or MgCl 2 ) commonly used on corrosion testing. The salts contained relatively high amounts of sulfates and nitrates, evolved to basic pH values, and exhibited deliquescence relative humidity values (RH) higher than seawater. Additionally, inert dust in components were quantified and considerations for laboratory testing are presented. The observed dust compositions are discussed in terms of the potential corrosion behavior and are compared to commonly used accelerated testing protocols. Finally, ambient weather conditions and their influence on diurnal fluctuations in temperature (T) and RH on heated metal surfaces are evaluated and a relevant diurnal cycle for laboratory testing a heated surface has been developed. Suggestions for future accelerated tests are proposed that include exploration of the effects of inert dust particles on atmospheric corrosion, chemistry considerations, and realistic diurnal fluctuations in T and RH. Understanding mechanisms in both realistic and accelerated environments will allow development of a corrosion factor (i.e., scaling factor) for the extrapolation of laboratory-scale test results to real world applications.

54 ENVIRONMENTAL SCIENCES↗

Study of benzotriazole as corrosion inhibitors of carbon steel in chloride solution containing hydrogen sulfide using electrochemical impedance spectroscopy (EIS)

Corrosion and inhibition studies on API 5LX65 carbon steel in chloride solution containing various concentrations of benzotriazole has been conducted at temperature of 70°C using Electrochemical Impedance Spectroscopy (EIS). Corroded carbon steel surface with and without inhibitor have been observed using X-ray Diffraction (XRD), Scanning Electron Microscope (SEM), and Energy Dispersive Spectroscopy (EDS). The objectives of this research are to study the performance of benzotriazole as corrosion inhibitors. The experimental results of carbon steel corrosion in 3.5% NaCl solution containing 500 mg/l H{sub 2}S at different BTAH concentrations showed that corrosion rate of carbon steel decreases with increasing of BTAH concentrations from 0 to 10 mmol/l. The inhibition efficiency of BTAH was found to be affected by its concentration. The optimum efficiency obtained of BTAH is 93% at concentration of 5 mmol/l. The result of XRD and EDS analysis reveal the iron sulfide (FeS) formation on corroded carbon steel surface without inhibitor. The EDS spectrum show the Nitrogen (N) bond on carbon steel surface inhibited by BTAH.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Tannin bark Melalauca cajuputi powell (gelam) as green corrosion inhibitor of mild steel

Tannin was extracted from gelam bark and used to produce corrosion inhibitor for mild steel. Tannin was extracted from gelam bark using 70% aqueous acetone for 6 hour. Tannin powder was characterization using fourier transform infrared spectroscopy to analyse chemical component in tannin and Scanning electron microscope (SEM) for tannin physical structure. The tannin effect on the corrosion inhibition of mild steel has been investigated in 1Mol HCl solution for 6 hour followed ASTM. The weight loss method were applied to study the mild steel corrosion behavior in the present and absend of different concentration of tannin (250, 300, 350)ppm. Tannin act good inhibitor as corrosion inhibitor for mild steel in acid medium. Surface morphology of carbon steel with and without inhibitor was investigated by scanning electron microscopy.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

The effect of pH on the corrosion behavior of intermetallic compounds Ni{sub 3}(Si,Ti) and Ni{sub 3}(Si,Ti) + 2Mo in sodium chloride solutions

The corrosion behavior of the intermetallic compounds, Ni{sub 3}(Si,Ti) (L1{sub 2}: single phase) and Ni{sub 3}(Si,Ti) + 2Mo (L1{sub 2} and (L12 + Ni{sub ss}) mixture region), has been investigated using an immersion test, electrochemical method and surface analytical method (SEM; scanning electron microscope and EDAX: Energy Dispersive X-ray) in 0.5 kmol/m{sup 3} NaCl solutions at various pH. The corrosion behavior of nickel alloy C-276 was studied under the same experimental conditions as a reference. It was found that the uniform attack was observed on Ni{sub 3}(Si,Ti) for the immersion test at lower pH, while the pitting attack was observed on this compound for this test at neutral solution. Furthermore, Ni{sub 3}(Si,Ti)+2Mo had the preferential dissolution of L1{sub 2} compared to (L1{sub 2} + Ni{sub ss}) mixture region at lower pH, while pitting attack occurred in (L1{sub 2} + Ni{sub ss}) mixture region at neutral solution. For both intermetallic compounds, the magnitude of pitting and uniform attack decrease with increasing pH of solutions. From the immersion test and polarization curves, the corrosion resistance of Ni{sub 3}(Si,Ti)+2Mo is lower than that of Ni{sub 3}(Si,Ti), while the nickel alloy C-276 is the highest one at various pH of solutions. On the other hand, in the lower pH of solutions, the corrosion resistance of tested materials decreased significantly compared to those in neutral and higher pH of solutions.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Sputtered carbon as a corrosion barrier for x-ray detector windows

Sputtered amorphous carbon thin films were explored as corrosion resistant coatings on aluminum thin films to be incorporated into x-ray detector windows. The requirements for this application include high corrosion resistance, low intrinsic stress, high strains at failure, and high x-ray transmission. Low temperature sputtering was used because of its compatibility with the rest of the window fabrication process. Corrosion resistance was tested by exposure of carbon coated and uncoated Al thin films to humidity. Substrate curvature and bulge testing measurements were used to determine intrinsic stress and ultimate strain at failure. The composition and bonding of the carbon films were further characterized by electron energy loss spectroscopy, Raman spectroscopy, and carbon, hydrogen, and nitrogen elemental analyses. Samples had low compressive stress (down to.08 GPa), a high strain at failure (3%), and a low fraction of sp{sup 3} carbon–carbon bonds (less than 5%). The high breaking strain and excellent x-ray transmission of these sputtered carbon films indicate that they will work well as corrosion barriers in this application.

36 MATERIALS SCIENCE↗

Estimating Effects of Various Factors on Corrosion of Pipeline Grade Carbon Steel Under Disbonded Coating (Status Update)

This report provides description of the activities, associated data and results for a work focused on understanding corrosion of pipeline grade carbon steel under coating disbondment. Specifically, the work reported here was for a pipeline that was installed in 1968 with the following characteristics. The line was coated with polyethylene tape coat (brand Polyken), and the line joints were electric-flash welded. The line joints are 34-inch outer diameter, and made of API 5L X52 grade carbon steel. The line was initially operated at 55 °F, but subsequently the line temperature increased to 105 °F due to higher fluid flow rate inside the pipe. Due to age and type of the pipeline coating, coating disbondment has occurred at several locations. The increase in operating temperature, coupled with age of the coating, is likely to have resulted in migration in corrosive species from the soil underneath the coating. As a result, the pipeline is experiencing enhanced corrosion. The objective of this study was to evaluate whether the change in operating temperature has affected the corrosion rate of the pipeline external surfaces under areas of disbonded coating.

36 MATERIALS SCIENCE↗

FY24 Progress Report: SRNL Analysis of ICCWR LCM and WAMS data for Corrosion and Cracking

Algorithms for Machine Learning (ML) and data analysis for the 3013 Surveillance Program have been developed in an ongoing collaborative effort by the Savannah River National Laboratory (SRNL) and the University of South Carolina (USC). The objective of the algorithms is to automate the identification of corrosion and crack formation in the Inner Container Closure Weld Region (ICCWR) of the canister system used to store Pu-bearing material. Data for corrosion and cracking is collected from large binary files generated by a Laser Confocal Microscope (LCM), the Wide Area 3D Measurement System (WAMS), or,in a recent proposal, by a Scanning Electron Microscope (SEM). The ML software uses the physical attributes in the data files (e.g., one or more of: height, color, and 16-bit grayscale values as functions of position in a plane projection) to detect signs of surface corrosion and cracking after being trained on similar data, with the features to be detected. Although the initial scope included screening for broader indicators of corrosion, e.g., pitting, identification of potential cracks was prioritized for the past several years at the request of program leadership. Labeled training data is essential to developing the ML algorithm, and enhancements to data labeling capability have been developed to address this essential precursor to application of ML routines. Efficient labeling is particularly important in view of the large volume of data required to train ML algorithms and the relative rarity of cracks in the ICCWR data set. The updated program will read binary data from either LCM, WAMS or SEM files, interrogate data attributes, facilitate user labeling of data for training ML algorithms, execute ML algorithms, output parameters from trained ML algorithms, report ML model accuracy with respect to labeled data, and generate graphical representations for various analyses. In FY24, hourglass neural networks (HNNs) that were initiated in FY22 were further developed and tested using available LCM data, and their performance was tested against that of the alternative U-Net Neural Network algorithm structure. HNNs along with previously developed Convolutional Neural Networks (CNNs) and Deep Neural Networks (DNNs) comprise a suite of ML tools for identification of cracks in the ICCWR

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

FY25 Progress Report: SRNL Analysis of ICCWR LCM and WAMS data for Corrosion and Cracking

Algorithms for Machine Learning (ML) and image analysis for the 3013 Surveillance Program have been developed in an ongoing collaborative effort by the Savannah River National Laboratory (SRNL) and the University of South Carolina (USC). The objective of the algorithms is to automate the identification of corrosion and cracks in the Inner Container Closure Weld Region (ICCWR) of the canister system used to store Pu-bearing material. Data for corrosion and cracking is collected from large binary files generated by a Laser Confocal Microscope (LCM), the Wide Area 3D Measurement System (WAMS), or, in a recent proposal, by a Scanning Electron Microscope (SEM). The ML software uses the physical attributes in the data files (e.g., one or more of: height, color, and 16-bit grayscale values as functions of position in a plane projection) to detect signs of surface corrosion and cracking after being trained on similar data with the features to be detected. Although the initial scope included screening for broader indicators of corrosion, e.g., pitting, the identification of potential cracks was prioritized for the past several years at the request of program leadership.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Elevated-Temperature Tribo-Corrosion Response of Eutectic High-Entropy Alloy

The combination of elevated temperature and tribo-corrosion leads to the accelerated degradation of structural components used in many extreme environments. Recently developed high-entropy alloys (HEAs) with multiple principal elements have the potential for superior degradation resistance compared with presently used structural alloys. Here, we demonstrate the microstructural stability, pitting resistance, and superior tribo-corrosion degradation resistance of the AlCoCrFeNi 2.1 eutectic HEA in comparison with duplex stainless steel 2205 in deionized water (controlled low-ionic-strength electrolyte) at 25 °C, 50 °C and 100 °C. The AlCoCrFeNi 2.1 HEA showed excellent microstructural stability and tribo-corrosion resistance at all three temperatures, an order-of-magnitude lower wear rate, and a lower coefficient of friction compared with duplex 2205 steel. The lowest wear volume loss and wear rate for both AlCoCrFeNi 2.1 and duplex steel were recorded at 50 °C, which was attributed to temperature-assisted passivation and formation of a comparatively stable tribological surface condition. These results suggest superior performance of eutectic HEAs in tribo-corrosion applications compared with currently used dual-phase steels and motivate future evaluation in ion-containing industrial water chemistries.

36 MATERIALS SCIENCE↗

Surface Studies of Ultra Strength Drilling Steel after Corrosion Fatigue in Simulated Sour Environment

The Unites States predicted 60% growth in energy demand by 2030 makes oil and natural gas primary target fuels for energy generation. The fact that the peak of oil production from shallow wells (< 5000 m) is about to be reached, thereby pushing the oil and natural gas industry into deeper wells. However, drilling to depths greater than 5000 m requires increasing the strength-to weight ratio of the drill pipe materials. Grade UD-165 is one of the ultra- high yield strength carbon steels developed for ultra deep drilling (UDD) activities. Drilling UDD wells exposes the drill pipes to Cl{sup -}, HCO{sub 3}{sup -}/CO{sub 3}{sup 2-}, and H{sub 2}S-containig corrosive environments (i.e., sour environments) at higher pressures and temperatures compared to those found in conventional wells. Because of the lack of synergism within the service environment, operational stresses can result in catastrophic brittle failures characteristic for environmentally assisted cracking (EAC). Approximately 75% of all drill string failures are caused by fatigue or corrosion fatigue. Since there is no literature data on the corrosion fatigue performance of UD-165 in sour environments, research was initiated to better clarify the fatigue crack growth (FCGR) behavior of this alloy in UDD environments. The FCGR behavior of ultra-strength carbon steel, grade UD-165, was investigated by monitoring crack growth rate in deaerated 5%NaCl solution buffered with NaHCO{sub 3}/Na{sub 2}CO{sub 3} and in contact with H{sub 2}S. The partial pressure of H{sub 2}S (p{sub H2S}) was 0.83 kPa and pH of the solution was adjusted by NaOH to 12. The fatigue experiments were performed at 20 and 85 C in an autoclave with surface investigations augmented by scanning electron microscopy (SEM) and energy dispersive x-ray (EDX) spectroscopy. In this study, research focused on surface analyses supported by the fatigue crack growth rate measurements. Fig. 1 shows an SEM micrograph of the crack that propagated from the notch in the solution at 20 C. Accumulation of the corrosion products is visible along the crack. The EDX chemical analysis near the crack tip found iron, sulfur and oxygen in the passive layer. The surface of the sample after the fatigue test in the sour environment at 85{sup o}, Fig. 2, C looks different from that fatigued surface at 20 C. The crack propagates across the passive film that covers the surface fairly uniformly. Some spallation of the passive film is observed near the notch. The EDX chemical analysis of the passive film near the crack tip identified mainly iron, carbon and oxygen. It appears that temperature plays a very important role in formation of the passive film. This may be associated with different solubility of H{sub 2}S in the solution, which will be further studied.

03 NATURAL GAS↗

Investigations of Localized Corrosion of Stainless Steel after Exposure to Supercritical CO2

Severe localized corrosion of a 316 stainless steel autoclave occurred during investigating Type H Portland cement stability in 0.16 M CaCl{sub 2} + 0.02 M MgCl{sub 2} + 0.82 M NaCl brine in contact with supercritical CO{sub 2} containing 4% O{sub 2}. The system operated at 85 C and pressure of 29 MPa. However, no corrosion was observed in the same type of autoclave being exposed to the same environment, containing Type H Portland cement cylindrical samples, also operating at pressure of 29 MPa but at 50 C. The operation time for the 85 C autoclave was 53 days (1272 hours) while that for the 50 C autoclave was 66 days (1584 hours). Debris were collected from the base of both autoclaves and analyzed by X-ray diffraction (XRD). Corrosion products were only found in the debris from the 85 C autoclave. The cement samples were analyzed before and after the exposure by X-ray florescence (XRF) methods. Optical microscopy was used to estimate an extent of the 316 stainless steel corrosion degradation.

36 MATERIALS SCIENCE↗

The aqueous corrosion behavior of technetium - Alloy and composite materials

Metal waste forms are under study as possible disposal forms for technetium and other fission products. The alloying of Tc is desirable to reduce the melting point of the Tc-containing metal waste form and potentially improve its corrosion resistance. Technetium-nickel composites were made by mixing the two metal powders and pressing the mixture to make a pellet. The as-pressed composite materials were compared to sintered composites and alloys of identical composition in electrochemical corrosion tests. As-pressed samples were not robust enough for fine polishing and only a limited number of corrosion tests were performed. Alloys and composites with 10 wt% Tc appear to be more corrosion resistant at open circuit than the individual components based on linear polarization resistance and polarization data. The addition of 10 wt% Tc to Ni appears beneficial at open circuit, but detrimental upon anodic polarization. Qualitatively, the polarizations of 10 wt% Tc alloys and composites appear like crude addition of Tc plus Ni. The 1 wt% Tc alloys behave like pure Ni, but some effect of Tc is seen upon polarization. Cathodic polarization of Tc by Ni appears feasible based on open circuit potential measurements, however, zero resistance ammetry and solution measurements are necessary to confirm cathodic protection.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Progressing Zirconium-Alloy Corrosion Models Using Synchrotron XANES

The corrosion and hydrogen pickup of in-reactor zirconium-based cladding is currently limiting the maximum fuel burnup in light-water reactors. Since the oxidation rate and hydrogen pickup fraction of zirconium alloys vary significantly as a function of exposure time, burnup, and alloy composition, it is critical to better understand the underlying mechanisms to model and predict corrosion behavior. Following the analysis of ~500 autoclave coupons, a physically based zirconium-alloy corrosion model founded on first principles, named “Coupled Current Charge Compensation (C4)”, has been developed. The model reproduces the differences in oxidation kinetics and hydrogen pickup between different zirconium alloys, such as Zr-Nb and Zircaloy-4. Since oxidized solute elements affect the corrosion process through a space-charge compensation mechanism, synchrotron nano-beam X-ray Absorption Near-Edge Spectroscopy has been performed on multiple oxidized Zr-Nb alloys to determine the oxidation-state profile of niobium in the oxide layer. The results inform the C4 model and the associated hydrogen pickup fraction.

C4 Model↗

Effects of uranium metal carbon content on hydriding kinetics and corrosion blister number/area at sub-ambient pressures

Carbon is a common impurity in uranium metal, resulting in a number of uranium–carbon inclusion phases that contribute to an increase in metal defect density as carbon content increases. It is widely held that uranium hydride corrosion preferentially nucleates at these defect sites, and that an increase in carbon content will therefore represents an increase in uranium hydride corrosion sites on the metal surface. We hydrided six uranium sources with differing carbon contents to explore whether this assumption holds in a sub-ambient (~ 0.1 atm hydrogen), sealed environment, and report the resulting reaction kinetics and uranium hydride blister benchmarking data. We find that carbon content is not strongly correlated with reaction kinetics terms or the resulting hydride blister number and area, but that there is a tight relationship between corrosion blister number/area and kinetics as is expected. Further, we find that there is a strong trend of decreasing variance in the blister number, blister area, and induction time as carbon content increases (higher carbon content results in more reproducible blister populations). Additionally, we find a narrow band of uranium metal consumption at the end of the parabolic phase of reaction progress (beginning of linear growth phase) of 0.098 ± 0.011 w/w%, a fact that may be useful in assaying hydrogen corrosion of uranium metal within sealed environments generally.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

Effects of Heat Treatment on Phase Transformation and Corrosion Resistance of Boride Layer on Austenitic Stainless Steel AISI 304

The austenitic stainless steel AISI 304 was thermochemically surface treated using a powder-packed boronizing process at a temperature of 950 °C for about 4 hours. Double-phase boride layer (FeB and Fe{sub 2}B) was detected and then investigated for the corrosion resistance compared with the untreated one. Heat treatment was performed at a temperature range of 800 to 900 °C for 2 hours on the boronized austenitic stainless steel AISI 304 to diminish the double-phase boride layer. Afterward, corrosion tests were performed to clarify the effects of heat treatment as well as phase transformation on the corrosion resistance of the boronized austenitic stainless steel AISI 304. The results of this study showed that the formation of single-phase Fe{sub 2}B layer offers the best corrosion resistance.

36 MATERIALS SCIENCE↗

Elevated Temperature Corrosion Studies of AlCrN and TiAlN Coatings by PAPVD on T91 Boiler Steel

The present investigation discusses the hot corrosion behavior of AlCrN and TiAlN nano-coatings on T91 boiler steel by PAPVD process subjected to molten salt of Na{sub 2}SO{sub 4}-60%V{sub 2}O{sub 5} at 900 °C for 50 cycles. Surface and cross-sectional studies were performed by AFM, SEM/EDS and XRD techniques to understand the corrosion kinetics and mechanism. T91 bare boiler steel as well as TiAlN-coated specimen has shown higher internal oxidation as well as weight gain. The better corrosion resistance of AlCrN-coated specimen has been observed by virtue of higher availability of Cr and Al in the oxide scale as well as adherent and dense coating. The betterment of AlCrN coating can be attributed to low internal oxidation as well as movement of Cr and Al toward oxide scale to form protective corrosion barriers.

36 MATERIALS SCIENCE↗