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At least 1,135 records · Page 63

Passive Wireless Sensors for Realtime Temperature and Corrosion Monitoring of Coal Boiler Components Under Flexible Operation (Final Technical Report)

Researchers at West Virginia University (WVU) propose to demonstrate inexpensive wireless, high-temperature sensors for real-time monitoring of the temperature and corrosion of metal components, which are commonly used in coal-fired boilers. This study presents the development of cost-effective wireless high-temperature sensors for real-time temperature and corrosion monitoring in coal-fired boilers' metal components. The focus is on fabricating and evaluating chipless radio-frequency identification (RFID) sensors capable of operating between 25-1300 ºC. Efforts were directed towards designing passive RFID sensor and interrogator antenna with a broad frequency range, optimizing a microstrip patch antenna sensor integrated into a "peel-and-stick" format for efficient application to various metal specimens without altering their geometry. Additionally, this research aimed to assess the sensor responses under accelerated high-temperature conditions, correlating corrosion and cracking mechanisms with sensor data. An investigation of through-wall data acquisition techniques was also planned, facilitating unobtrusive monitoring of sensor responses housed within metal enclosures. Ultimately, this work sought to establish a robust passive wireless sensor system for the continuous health monitoring of metal components in operational settings, thereby contributing to enhanced safety and efficiency in coal-fired power plants.

20 FOSSIL-FUELED POWER PLANTS↗

Influence of Spatter on Porosity, Microstructure, and Corrosion of Additively Manufactured Stainless Steel Printed Using Different Island Size

Specimens of 316 L stainless steel were printed using laser powder bed fusion (LPBF), a popular metal additive manufacturing (AM) technique, with varying island sizes. Not many researchers have considered the impact of spatter while optimizing LPBF printing parameters. In this research, the influence of spatter was considered while also investigating the effect of varied island size on the microstructure, surface roughness, microhardness, and corrosion resistance of LPBF-316 L. No correlation was observed between surface roughness or microhardness and minor variations in island size. However, a correlation was drawn between varied island sizes and porosity in LPBF-316 L. The specimens associated with larger island sizes showed significantly enhanced corrosion resistance due to fewer manufacturing defects and reduced porosity, attributed to the minimal influence of the spatter. Based on analysis, the LPBF parameters were revised, which lead to superior corrosion resistance of LPBF-316 L, attributed to high density and reduced porosity.

36 MATERIALS SCIENCE↗

Corrosion Compatibility of Stainless Steels and Nickel in Pyrolysis Biomass-Derived Oil at Elevated Storage Temperatures

Corrosion compatibility of stainless steels and nickel (Ni200) was assessed in fast pyrolysis bio-oil produced from pyrolysis of high ash and high moisture forest residue biomass. Sample mass change, ICP-MS and post-exposure electron microscopy characterization was used to investigate the extent of corrosion. Among the tested samples, type 430F and type 316 stainless steels (SS430F and SS316) and Ni200 (~98.5% Ni) showed minimal mass changes (less than 2 mg∙cm−2) after the bio-oil exposures at 50 and 80 °C for up to 168 h. SS304 was also considered to be compatible in the bio-oil due to its relatively low mass change (1.6 mg∙cm−2 or lower). SS410 samples showed greater mass loss values even after exposures at a relatively low temperature of 35 °C. Fe/Cr values from ICP-MS data implied that Cr enrichment in stainless steels would result in a protective oxide layer associated with corrosion resistance against the bio-oil. Post exposure characterization showed continuous and uniform Cr distribution in the surface oxide layer of SS430F, which showed a minimal mass change, but no oxide layer on a SS430 sample, which exhibited a significant mass loss.

09 BIOMASS FUELS↗

High-temperature corrosion of UNS N10003 in molten Li 2 BeF 4 (FLiBe) salt

Here, corrosion testing of Hastelloy N in molten fluoride salt was performed in purified molten 2 7 LiF-BeF 2 (66-34mol%) (FLiBe) salt at 700°C for 1000 hours, in pure nickel and graphite capsules. In the nickel capsule tests, the near-surface region of the alloy exhibited an about 200 nm porous structure, an approximately 3.5 μm chromium depleted region, and MoSi 2 precipitates. In tests performed in graphite capsules, the alloy samples gained weight due to the formation of a variety of Cr 3 C 2 , Cr 7 C 3 , Mo 2 C and Cr 23 C 6 , carbide phases on the surface and in the subsurface regions of the alloy. A Cr depleted region was observed in the near-surface region where Mo thermally diffused toward either surface or grain boundary, which induced approximately 1.4 μm Ni 3 Fe alloy layer in this region. The carbide containing layer extended to about 7 μm underneath the Ni 3 Fe layer. The presence of graphite dramatically changes the mechanisms of corrosion attack in Hastelloy N in molten FLiBe salt. Evaluated by in terms of the depth of attack, graphite clearly accelerates corrosion, but the results appear to indicate that the formation of Cr 23 C 6 phase might stabilize the Cr and mitigate its dissolution in molten FLiBe salt.

36 MATERIALS SCIENCE↗

Cyclic Oxidation and Hot Corrosion of NiCrY-Coated Disk Superalloy

Powder metallurgy disk superalloys have been designed for higher engine operating temperatures through improvement of their strength and creep resistance. Yet, increasing disk application temperatures to 704 C and higher could enhance oxidation and activate hot corrosion in harmful environments. Protective coatings could be necessary to mitigate such attack. Cylindrical coated specimens of disk superalloys LSHR and ME3 were subjected to thermal cycling to produce cyclic oxidation in air at a maximum temperature of 760 C. The effects of substrate roughness and coating thickness on coating integrity after cyclic oxidation were considered. Selected coated samples that had cyclic oxidation were then subjected to accelerated hot corrosion tests. The effects of this cyclic oxidation on resistance to subsequent hot corrosion attack were examined.

Hot corrosion↗

Corrosion Failure in Electronic Devices for Aerospace Application

Corrosion of complex electronic systems is a growing and expensive concern. New materials and technology are constantly being introduced to increase performance of devices. There are many factors that can induce a corrosive environment during the various stages of manufacturing, processing, transport, and storage of these devices. The scope of this paper was to identify potential causes for the corrosion failure of optocoupler batches being used in launch applications. Optical microscope with surface profile measurements, scanning electron microscopy (SEM), energy-dispersive X-ray spectrometry (EDS), and X-ray photoelectron spectroscopy (XPS) were used to identify and analyze the source of these failure. These studies revealed that the loss of adhesion between the electrolytic plated gold and nickel layers is the critical area that traps impurity ions into the chip allowing for blisters to form along the pins of the optocoupler.

Corrosion↗

Pre-Demonstration Development of Controlled-Release Corrosion Inhibitors and Healing Agents as Alternatives to Hexavalent Chromium

This Limited Scope Study was directed to achieve the following objectives: (1) Scale-up of materials that can meet MIL-PRF-23377 (solvent-based primer). (2) Provide evidence of resistance to aircraft alkaline cleaners and deicing fluids. (3) Provide formulation for initial ecological and toxicity screening. (4) Submit an interim report that will provide the basis for a future ESTCP demonstration effort. The encapsulation procedure for two corrosion inhibitors was scaled up from lab scale to 2.0 kg. This scale will accommodate high volume production of coatings with encapsulated corrosion inhibitors for large surface areas during a follow on ESTCP demonstration effort. Test results provided evidence of resistance to alkaline cleaners and aircraft deicing fluids and compliance with MIL-PRF-23377. All the MIL-PRF-23377 requirements were met with the exception of the adhesion requirement, in top coated panels, and the flexibility requirement. Work on solving these two problems will be done prior to validation and demonstration of the technology. An initial ecological and toxicity screening identified several factors that were not critical to the acceptance of the encapsulated corrosion inhibitor. This new technology will lead to environmentally friendly alternatives to hexavalent chromium that will enable DoD to protect its assets. Field demonstration, licensing, qualification, and commercialization will allow its real world utilization.

Alternatives to Hexavalent Chromium↗

Surface Studies of HSLA [high strength low alloy] Steel after Electrochemical Corrosion in Supercritical CO{sub 2}-H{sub 2}O Environment

Corrosion resistance of pipeline materials for transporting coal combustion produced supercritical CO{sub 2} from power plants to sequestration sites has not been fully determined. Although pipeline materials are resistant to corrosion in pure supercritical CO{sub 2}, cleaning costs of combustion produced CO{sub 2} streams from impurities such as H{sub 2}O, O{sub 2}, SO{sub 2} are too high, making sequestration of pure CO{sub 2} streams unfeasible. Impacts of the H{sub 2}O, O{sub 2}, SO{sub 2} impurities on pipeline corrosion must be determined. Filling Up This Technological Gap requires studying effects of H{sub 2}O, O{sub 2}, SO{sub 2} concentrations on pipeline.

20 FOSSIL-FUELED POWER PLANTS↗

Superheater Corrosion Produced By Biomass Fuels

About 90% of the world's bioenergy is produced by burning renewable biomass fuels. Low-cost biomass fuels such as agricultural wastes typically contain more alkali metals and chlorine than conventional fuels. Although the efficiency of a boiler's steam cycle can be increased by raising its maximum steam temperature, alkali metals and chlorine released in biofuel boilers cause accelerated corrosion and fouling at high superheater steam temperatures. Most alloys that resist high temperature corrosion protect themselves with a surface layer of Cr{sub 2}O{sub 3}. However, this Cr{sub 2}O{sub 3} can be fluxed away by reactions that form alkali chromates or volatilized as chromic acid. This paper reviews recent research on superheater corrosion mechanisms and superheater alloy performance in biomass boilers firing black liquor, biomass fuels, blends of biomass with fossil fuels and municipal waste.

09 BIOMASS FUELS↗

Fireside Corrosion in Oxy-fuel Combustion of Coal

Oxy-fuel combustion is burning a fuel in oxygen rather than air. The low nitrogen flue gas that results is relatively easy to capture CO{sub 2} from for reuse or sequestration. Corrosion issues associated with the environment change (replacement of much of the N{sub 2} with CO{sub 2} and higher sulfur levels) from air- to oxy-firing were examined. Alloys studied included model Fe-Cr alloys and commercial ferritic steels, austenitic steels, and nickel base superalloys. The corrosion behavior is described in terms of corrosion rates, scale morphologies, and scale/ash interactions for the different environmental conditions.

01 COAL, LIGNITE, AND PEAT↗

Air- and Oxy-Fired Fireside Corrosion

The primary goal of this work was to examine the corrosion effects from flue gas composition changes arising from oxy-combustion. At 700°C, increased SO{sub X}, CO{sub 2}, and H{sub 2}O contents in the gas phase arising from various oxy-combustion flue gas recirculation scenarios, while maintaining constant ash deposit chemistry, do not increase corrosion in superheater or reheater tubing. At 400°C, for both oxidative and reducing conditions, the corrosion rates were lower than at 700°C.

36 MATERIALS SCIENCE↗

In-Situ Proton Irradiation-Corrosion Study of ATF Candidate Alloys in Simulated PWR Primary Water

Irradiation enhanced corrosion behavior of Accident Tolerant Fuel candidate alloys T91 and Fe15Cr4Al were evaluated using in-situ proton irradiation-corrosion experiments in hydrogenated pure water (at 320 °C, 3 wppm H2) with a 5.4 MeV proton beam. The thin sample acted as a “window” to allow protons to fully penetrate the sample while maintaining system pressure. The area of the samples exposed to the proton beam experienced effects from displacement damage and radiolysis products. The aim of the study was to characterize the effect of radiation on the kinetics and character of oxidation caused by accelerated waterside corrosion under irradiation. Samples irradiated with protons for total displacement damage of *0.1 dpa (dose rate in water, 400 kGy/s) at an exposure time of 24 h were compared. Oxide morphology, phase structure, and composition of the oxide, metal and the metal/oxide interface were investigated using TEM and EDS and are related to the test conditions. The oxidation rate or resulting oxide thickness is dependent on the alloy Cr content; the oxidation rate increased as the Cr content decreased. The resulting oxide consists of an inner layer of Cr-rich spinel oxide and outer magnetite crystals in the unirradiated region; while the irradiated region consists of Cr-rich inner oxide spinel that was partially dissolved and coverage of outer non-faceted hematite precipitates.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗

Development of an Electrochemical Impedance Instrument for Monitoring Corrosion Formation (Oxide and Hydride) on Cladding Materials

The objective of this work package is to develop electrochemical impedance spectroscopic (EIS) techniques for the in pile measurement of changes in cladding materials in coupling with model simulation and material characterization. This work package will involve the initial development of electrochemical sensing technologies for measuring spatial and time resolved changes in cladding chemistry. Specific attention will be paid to monitoring changes in monitor cladding corrosion including oxide and hydride formation and deformation. The planned work during this period was focused on cladding material zirconium alloy corrosion, oxide and hydride development, and to characterize samples using EIS under controlled gas atmosphere, atom probe tomography (APT), Raman Spectroscopy, and Synchrotron X-ray diffraction (XRD). The corrosion, including oxide and hydride of zirconium alloy samples, was tested in this study. The samples were treated at a gas environment containing 3% H2 (vol%) balanced with N2 gas at various temperatures (100 – 500°C) and different times (up to 60 hours) and were characterized by in situ EIS. After treatment, various characterization techniques were applied to measure the samples, including TGA, Ramen, XRD, and APT. This study found that impedance spectra can be affected significantly with (furnace/environment) temperature. Higher temperature resulted in higher overall impedance, and longer exposure time exerted similar effects. Proof of concept characterization of oxidized samples, including TGA, Raman, XRD, and APT, were accomplished on samples exposed to 700 oC gas environment containing 20% O2 and 80% N2. TGA provides observable breakaway and bulk oxide growth measurements. High-temperature, in-situ Raman provides observation of oxidation stress at the surface of the oxide. Additionally, a transition from tetragonal to monoclinic zirconia can be seen early in the oxidation experiment. Specifically, tetragonal-rich zirconia is seen at the metal/oxide interface, where a transition to monoclinic-rich zirconia is seen in the bulk of the oxide. It has also been confirmed that highly compressive residual stresses are seen near the metal/oxide interface. It is concluded that the transition from tetragonal to monoclinic zirconia is induced by massive shifts in stress as the oxide grows. APT has supplied evident differences in the distribution of zirconium and oxygen at the metal/oxide interface. On the pre-breakaway sample, the metastable Zr(O) region at the boundary is relatively thin, interfaced by Zr-rich (i.e., metal) and O-rich (i.e., ZrO2) on either side. In contrast, it has been seen on a post-breakaway sample that the Zr(O) metastable region is much greater in thickness, with evidence of four “zones” showing slightly contrasting composition between 49-54% Zr. In addition, it can be seen from the Zr-2.65Nb post-breakaway sample that secondary element concentrations are considerably different than bulk composition measurements show. Specifically, Nb concentration is much lower than expected, whereas Fe concentration is much higher than expected. These differences could play a role in each element’s contribution to oxide growth mechanisms, as well as causation for breakaway. Future work is focused on analyzing EIS spectra of hydride and its correlation with characterization features, finite element (FE) modeling of cladding materials, electrochemical sensor development, targeting cladding oxides/hydrides under thermodynamic equilibria, during transients and under irradiation.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Novel Magnesium Pretreatment Coatings Offering Excellent Corrosion Protection

There is a growing interest in using magnesium alloys for automotive, industrial, and aerospace applications due to their low density, high strength-to-weight ratio, good machinability, and low cost. These alloys have the potential to lighten cars and aircraft, reducing fuel consumption and emissions. A major drawback to the use of magnesium alloys is their highly reactive nature, which can result in corrosion; as a result, most existing pretreatment systems for these alloys require the use of chromium, which is increasingly coming under regulatory pressures, as a corrosion inhibitor. Through a project funded by the Department of Energy and administered by the U.S. Automotive Materials Partnership (USAMP), PPG developed chromium-free metal pretreatment solutions for ZEK-100 and AZ21 magnesium alloys. In a major technical advance, several chromium-free cleaning and pretreatment processes were developed that offer excellent corrosion protection when compared to a typical automotive pretreatment systems. To expand the use cases for these systems beyond single-alloy substrates to broader multi-metal assemblies, these pretreatment solutions were also optimized for use in multi-metal applications: compatibility with magnesium and other metals was demonstrated without the need for additional process steps.

36 MATERIALS SCIENCE↗

Development of a Thermodynamic Database for Corrosion in Chloride MSRs

Control of the salt redox condition is the salient method for corrosion inhibition in molten salts. For chloride salt-fueled molten salt reactors of primary concern is the U(IV)/U(III) ratio, influenced directly by the Cl2 activity in the salt. Although thermodynamic assessments of MSR-relevant salts abound, none have included consideration of UCl4 which is essential to correctly describe the salt redox condition. This work reports the assessment of the NaCl-KCl-MgCl2 base salt with UCl3-UCl4 and corrosion chlorides involving Cr, Fe, and Ni as minor components and the resultant thermodynamic models. The effort utilized available thermodynamic measurements and phase equilibria complemented by differential scanning calorimetry determinations of phase equilibria. Example calculations explore the temperature and composition space to understand its influence on corrosion. The foregoing models are incorporated into an update of the Molten Salt Thermal Properties Database – Thermochemical which is publicly available.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Chemistry control and corrosion mitigation of heat transfer salts for the fluoride salt reactor (FHR)

The Molten Salt Reactor Experiment (MSRE) was a prototype nuclear reactor which operated from 1965 to 1969 at Oak Ridge National Laboratory. The MSRE used liquid fluoride salts as a heat transfer fluid and solvent for fluoride based {sup 235}U and {sup 233}U fuel. Extensive research was performed in order to optimize the removal of oxide and metal impurities from the reactor's heat transfer salt, 2LiF-BeF{sub 2} (FLiBe). This was done by sparging a mixture of anhydrous hydrofluoric acid and hydrogen gas through the FLiBe at elevated temperatures. The hydrofluoric acid reacted with oxides and hydroxides, fluorinating them while simultaneously releasing water vapor. Metal impurities such as iron and chromium were reduced by hydrogen gas and filtered out of the salt. By removing these impurities, the corrosion of reactor components was minimized. The Univ. of Wisconsin - Madison is currently researching a new chemical purification process for fluoride salts that make use of a less dangerous cleaning gas, nitrogen trifluoride. Nitrogen trifluoride has been predicted as a superior fluorinating agent for fluoride salts. These purified salts will subsequently be used for static and loop corrosion tests on a variety of reactor materials to ensure materials compatibility for the new FHR designs. Demonstration of chemistry control methodologies along with potential reduction in corrosion is essential for the use of a fluoride salts in a next generator nuclear reactor system. (authors)

21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗

Corrosion resistant coatings for zirconium-alloy cladding with improved accident tolerance

The Westinghouse-led accident tolerant fuel (ATF) program is evaluating Accident Tolerant Fuel (ATF) coatings of MAX phase (Ti{sub 2}AlC) and multi-layer Ti{sub x}Al{sub 1-x}N/TiN to enhance the oxidation resistance of zirconium alloy fuel cladding in both normal operation and beyond design-based conditions of light water reactors. A variety of coating technologies have been applied to deposit these coating materials onto Zircaloy-4 or Zirlo sheets and tubes, including cold spray and cathodic arc-physical vapor deposition (CA-PVD). Neutronic analysis using the elemental compositions of the coating materials showed that the coating thicknesses should be less than 30 μm for most coating materials to avoid non-negligible economic penalty. The coated samples were autoclave tested in water at 360 Celsius degrees and 150 bar or in steam at 427 Celsius and 103 bar for corrosion resistance evaluation. The initial Ti{sub 2}AlC coating made by using large particle size MAX phase powder and cold spray deposition did not provide the desired corrosion resistance due to un-optimized microstructure and porosity. Subsequent optimization including reduction in particle size and tuning of cold spray deposition parameters resulted in denser coatings less than 30 microns in thickness. Optimization of process conditions resulted in reduced oxidation kinetics and showed that the coating acts as an effective barrier to prevent the zirconium substrate from oxidizing in accident condition temperatures. High purity Ti{sub 2}AlC powder is needed to further improve oxidation resistance of the Ti{sub 2}AlC coating. The oxidation resistance of pure monolithic MAX phase compound was also found to be remarkable, and the weight gain was only 1.85 mg/cm{sup 2} for 96 hours exposure in 1200 C. degrees steam, which is consistent with the literature. The corrosion resistance of the TiAlN/TiN multilayer coating was excellent. The weight gain was negligible and no oxidation was observed on the surface of zirconium-alloy at the coating-substrate interface. (authors)

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗