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Pint, B. A.

Publications and source records attributed to Pint, B. A..

At least 19 records

Understanding Environmental Barrier Coating Lifetimes and Performance for Industrial Gas Turbines

Hydrogen or hydrogen blend fuels are expected to replace natural gas in land-based industrial gas turbines (IGTs) to support a greener power economy. Silicon carbide (SiC) base ceramic matrix composites (CMCs) are considered for replacement of Ni-based superalloys to facilitate future efficiency improvements. SiC CMCs require environmental barrier coatings (EBCs) to mitigate volatilization from high-temperature steam, thus making the EBC lifetime critical information for identifying CMC component lifetimes. Here, the goal of this project is to determine the maximum bond coating temperature underneath the EBC for achieving an IGT component lifetime goal of 25,000 h, which is far greater than current CMC component lifetime requirements for aeroturbine applications. To provide data for the lifetime model, laboratory testing used atmospheric plasma-sprayed rare-earth silicate EBCs on monolithic SiC substrates with an intermediate Si bond coating. Specimens exposed to 1-h thermal cycles in flowing air–steam environments and reaction kinetics were assessed from 700 °C to 1350 °C by measuring the thickness of the thermally grown silica scales. The silica growth and phase transformation appear critical in predicting EBC lifetime and several strategies have been explored to reduce the oxide growth rate and improve EBC durability at elevated temperatures. Advanced characterization using Raman spectroscopy has helped clarify this system.

08 HYDROGEN↗

Measure the effect of molten halide salt exposure on creep rupture lifetime

Recent resurgence in the research and commercial interests in molten salt reactors (MSRs) as a viable advanced reactor concept to achieve the short- and long-term climate goals has resulted in ongoing efforts to demonstrate their commercial potential. These are relying on a combination of the extensive legacy knowledge from the molten salt reactor experiment (MSRE) and relatively recent data on materials compatibility of structural materials of interest such as 316H in molten salts environments. However, there is a critical lack of data on the mechanical behavior of alloys of interest for MSRS such as 316H, 617 and 709 in molten fluoride (FLiNaK or FLiBe) or chloride (NaCl-MgCl 2 ) salts. Limited legacy data from the molten salt reactor experiment (MSRE) program showed a significant reduction in creep rupture strength of a Ni-base alloy (Ni-15Cr-7Fe wt.%) in the molten fluoride NaF-ZrF4-UF4 (50-46-4 mol.%) salt. With ongoing efforts to commercialize different molten salt reactor concepts, the industry can considerably benefit from quantitative information on the impact of molten halide salts on the engineering properties such as creep and fatigue strength of materials of interest. Creep tests for 316H were conducted with fluoride (FLiNaK) and chloride (NaCl-MgCl 2 ) salts tat 650°C/150 MPa while alloys 709 and 617 were tested with FLiNaK at 700C/158 MPa and 750C.146 MPa respectively. Baseline tests were conducted in air to assess the impact of the molten salts on the creep behavior.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗

Exploring Fission–Fusion Synergies to Accelerate Compatibility Understanding

To address the significant commercial interest in fusion energy, it will be necessary to accelerate the compatibility research associated with liquid breeders including Li, eutectic Pb–Li and LiF-BeF 2 (FLiBe) molten salt. Particularly for FLiBe, compatibility understanding is limited especially for fusion relevant materials such as reduced activation ferritic-martensitic steels, SiC and V alloys. The historical knowledge associated with molten salt reactors (MSRs) and recent work to commercialize MSRs can benefit fusion research. Recent experimental and modeling work has improved understanding and this knowledge can be applied to fusion relevant materials. For liquid metals (LMs), the comparisons to Li and Pb–Li are less direct but nevertheless can help guide the pathway toward commercialization. For Pb–Li, Al-rich coatings have been shown to inhibit dissolution and potentially increase operating temperatures. For commercialization, the experience with sensors and on-line cleanup can help guide future developments. Thus, it is worth considering the potential for fission-related research with LMs and molten salts to help accelerate fusion research.

36 MATERIALS SCIENCE↗

Liquid metal compatibility of pre-oxidized FeCrAl in flowing Sn

Here, a flowing Sn thermal convection loop (TCL) experiment was conducted in FeCrAlMo (Kanthal alloy APMT) tubing for 1000 h with a peak temperature of 400 °C. Oxide dispersion strengthened (ODS) Fe-(10–12)Cr-6Al and APMT specimens were exposed and all were pre-oxidized to form an external alumina scale. Unlike static exposures at 400° and 500 °C where pre-oxidation prevented dissolution, large mass losses were observed in the TCL hot leg after the specimens were cleaned in Li. The observed pitting suggests that localized failure of the pre-formed alumina surface oxide caused significant metal loss. Specimen mass gains were not observed on the cold leg implying that mass transfer did not occur and the small levels of Fe and Cr in the Sn after the experiment implies that Sn-rich phases may have formed. Post exposure room temperature tensile testing showed limited impact of the Sn exposure on the 12Cr ODS FeCrAl alloy, comparable to a 1000 h anneal in Ar at 400 °C. These results suggest that pre-oxidation is not sufficient to protect FeCrAl alloys in contact with flowing liquid Sn at 350°-400 °C.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Compatibility of Fe-Cr-Al and Fe-Cr-Al-Mo oxide dispersion strengthened steels with static liquid sodium at 700 °C

We report the corrosion behavior and tensile properties of oxide dispersion strengthened (ODS) FeCr, FeCrAl, FeCrAlMo steels and 316H stainless steel were evaluated after 1000 h at 700 °C in static sodium with and without an oxygen getter (Zr foil). Without Zr foil to getter the dissolved oxygen in the liquid sodium, combined oxidation (formation of Cr, Fe-rich or Al-rich oxides) and dissolution of the studied materials was observed. For the ODS FeCr, Cr- and Fe-rich oxide formation and dissolution induced Cr depletion in the underlying alloy and led to the formation of laves phases that were observed to be detrimental to the room temperature tensile properties. For ODS FeCrAlMo and FeCrAl Al-rich oxide formation and dissolution resulted in Al depletion in the underlying alloys but did not impact tensile properties at room temperature. For 316H temperature induced sensitization combined with oxidation decreased room temperature tensile properties. With Zr foil added as oxygen getter, roughened surfaces and Al depletion profiles suggested the dissolution of ODS FeCr and FeCrAl into the liquid sodium while limited dissolution was observed for ODS FeCrAlMo and 316H. For the 316H and ODS FeCrAlMo steels, precipitates were formed at the grain boundaries after exposure. Tensile properties of ODS FeCr, FeCrAl and FeCrAlMo were not affected by the 1000 h corrosion exposure with Zr foil added to the sodium but for 316H temperature-induced grain boundary sensitization negatively affected the tensile properties.

36 MATERIALS SCIENCE↗

Burst and oxidation behavior of Cr-coated Zirlo during simulated LOCA testing

We report Cr-coated Zr-alloys are a near-term cladding concept to improve reactor safety during accident scenarios. Burst and steam oxidation behavior of bare and Cr-coated Zirlo claddings were examined under simulated loss-of-coolant accident conditions. The 4.4 µm coating had no substantial effect on ballooning or opening geometry but did increase burst temperatures at higher pressures. The coating reduced steam oxidation of the cladding compared to bare specimens, but in regions of high strain, the coating developed through-cracks allowing rapid underlying zirconia formation.

36 MATERIALS SCIENCE↗

Steam oxidation of chromium corrosion barrier coatings for sic-based accident tolerant fuel cladding

SiC-based materials are currently being considered for accident tolerant fuel (ATF) cladding, however, there are concerns regarding hydrothermal corrosion rates and hermeticity. These issues may be addressed with the utilization of a Cr corrosion barrier coating (CBC) but the interaction of Cr with SiC under loss of coolant accident (LOCA) conditions needs to be investigated. In the present work, Cr coatings were deposited onto chemically vapor deposited (CVD) SiC with either high power impulse magnetron sputtering (HiPIMS), cathodic arc (CA), or a combination of both. Annealing and steam thermogravimetric analysis (TGA) was used to study reaction product formation with and without oxidation. Additionally, after 1200 °C annealing, formation of a Cr x C y carbide layer at the ambient interface and a Cr x Si y C z silicide layer at the SiC interface was observed. After 1200 °C TGA exposure, similar carbide and silicide layers were observed but with a Cr 2 O 3 outer reaction layer and a Si and O rich interfacial layer forming between the carbide and silicide layers. Initial mass gain of the coatings during the 1200 °C TGA exposure was parabolic and were similar to reported rates of chromia formation. Mass gain behavior and observed transitions in chromia microstructure indicate that metallic Cr may be consumed within the first ~1 h at 1200 °C and that subsequent chromia formation occurs at the expense of the underlying Cr carbide layer. Overall, the results show no detrimental impact of Cr coatings on the steam oxidation resistance of SiC up to 4 h at 1200 °C.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Effect of Water Vapor on Lifetime of 625 and 120 Foils During Oxidation Between 650 and 800 °C

In this work, the oxidation behavior of alloy 625 and 120 foils was studied at 650, 700 and 800 °C in dry air and flowing air + 10% H 2 O up to 10,000 h (alloy 625) or 30,000 h (alloy 120). The effect of water vapor on Cr loss was investigated. Manganese and iron in the 120 foil induced faster Cr depletion in the foil and breakdown of the Cr 2 O 3 scale into Fe and Cr-rich oxide compared to the alloy 625 foil. In the latter case, the presence of Nb led to the formation of Nb and Cr-rich oxide after breakdown of the Cr 2 O 3 scale. Simultaneous Cr loss due to oxidation and volatilization of the Cr 2 O 3 oxide scale was predicted and compared to experimental Cr loss measurements for exposures up to 30,000 h.

36 MATERIALS SCIENCE↗

Additive Manufacturing of Corrosion Resistant UHTC Materials for Chloride Salt-to-sCO2 Brayton Cycle Heat Exchangers

The objectives of the project include: (1) screen high-purity, high density ultra-high-temperature ceramics (UHTCs) for chloride salt corrosion resistance, (2) develop binder-jet additive manufacturing and sintering for ZrB 2 -MoSi 2 blends using literature and experiments to demonstrate feasibility, and (3) evaluate chloride salt corrosion resistance of additively manufactured ZrB 2 -MoSi 2 . These initial objectives support the development of a durable and reliable ultra-compact high-efficiency salt-to-sCO 2 heat exchanger for closed-loop Brayton power cycles based on corrosion resistant, high-strength, thermally conductive UHTC materials and novel designs enabled by additive manufacturing. The UHTC materials are also abrasion resistant so that they could be applicable to all three thermal carrier media pathways identified in the CSP Gen3 Roadmap.

36 MATERIALS SCIENCE↗

The Effect of CO 2 Pressure on Chromia Scale Microstructure at 750°C

To understand and model performance in supercritical CO 2 (sCO 2 ) for high-efficiency, concentrating solar power (CSP) and fossil energy power cycles, reaction rates are compared at 750°C in 0.1 MPa CO 2 and 30 MPa sCO 2 as well as laboratory air as a baseline on structural materials such as Ni-based alloy 625. Due to the thin reaction products formed even after 5000 h, scanning transmission electron microscopy was used to study the Cr-rich surface oxide scale. The scales formed in CO 2 and sCO 2 had a much finer grain size with more voids observed in CO 2 . However, the observations on alloy 625 were complicated by Mo and Nb-rich precipitates in the adjacent substrate and Al internal oxidation. To simplify the system, a binary Ni-22Cr alloy was exposed for 1000 h in similar environments. After exposure in sCO 2 , there was an indication of carbon segregation detected on the Cr 2 O 3 grain boundaries. After exposure in air, metallic Ni precipitates were observed in the scale that were not observed in the scale formed on alloy 625. The scale formed in air on a second Ni-22Cr model alloy with Mn and Si additions did not contain Ni precipitates, suggesting caution when drawing conclusions from model alloys.

36 MATERIALS SCIENCE↗

Development of 1100 °C Capable Alumina-Forming Austenitic Alloys

Recently dalumina-forming austenitic (AFA) alloys based on ~12–32 weight % (wt%) Ni have been developed and offer an attractive combination of oxidation resistance and creep resistance at relatively low alloy cost. But, they exhibit a transition to internal oxidation and nitridation of Al above ~750–950 °C depending on composition and exposure environment. In order to identify AFA compositions capable of higher-temperature operation for applications such as ethylene cracking, the oxidation behavior of a series of developmental, as-cast nominal Fe–(25–45)Ni–(10–25)Cr–(4–5)Al–1Si–0.15Hf–0.07Y–0.01B wt% base alloys with and without Nb, Ti, and C additions was evaluated at 1100 °C in air with 10% water vapor. Furthermore, we observed protective alumina scale formation at levels of 35Ni, 25Cr, and 4Al with additions of Nb and C, indicating promise for 1100°C capable cast AFA alloys.

36 MATERIALS SCIENCE↗

Overview of the multifaceted activities towards development and deployment of nuclear-grade FeCrAl alloys

A large effort is underway under the leadership of US DOE Fuel Cycle Research program to develop advanced FeCrAl alloys as accident tolerant fuel (ATF) cladding to replace Zr-based alloys in light water reactors. The primary motivation is the excellent oxidation resistance of these alloys in high-temperature steam environments right up to their melting point (roughly three orders of magnitude slower oxidation kinetics than zirconium). A multifaceted effort is ongoing to rapidly advance FeCrAl alloys as a mature ATF concept. The activities span the broad spectrum of alloy development, environmental testing (high-temperature high-pressure water and elevated temperature steam), detailed mechanical characterization, material property database development, neutron irradiation, thin tube production, and multiple integral fuel test campaigns. Instead of off-the-shelf commercial alloys that might not prove optimal for the LWR fuel cladding application, a large amount of effort has been placed on the alloy development to identify the most optimum composition and microstructure for this application. The development program is targeting a cladding that offers performance comparable to or better than modern Zr-based alloys under normal operating and off-normal conditions. This paper provides a comprehensive overview of the systematic effort to advance nuclear-grade FeCrAl alloys as an ATF cladding in commercial LWRs. (authors)

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Uniform corrosion of FeCrAl alloys in LWR coolant environments

The corrosion behavior of commercial and model FeCrAl alloys and type 310 stainless steel was examined by autoclave tests and compared to Zircaloy-4, the reference cladding materials in light water reactors. The corrosion studies were carried out in three distinct water chemistry environments found in pressurized and boiling water reactor primary coolant loop conditions for up to one year. The structure and morphology of the oxides formed on the surface of these alloys was consistent with thermodynamic predictions. Spinel-type oxides were found to be present after hydrogen water chemistry exposures, while the oxygenated water tests resulted in the formation of very thin and protective hematite-type oxides. Unlike the alloys exposed to oxygenated water tests, the alloys tested in hydrogen water chemistry conditions experienced mass loss as a function of time. This mass loss was the result of net sum of mass gain due to parabolic oxidation and mass loss due to dissolution that also exhibits parabolic kinetics. Finally, the maximum thickness loss after one year of LWR water corrosion in the absence of irradiation was ~2 μm, which is inconsequential for a ~300–500 μm thick cladding.

36 MATERIALS SCIENCE↗

Current Thoughts on Reactive Element Effects in Alumina-Forming Systems: In Memory of John Stringer

In memory of John Stringer (1934–2014), one of the leaders in studying the reactive element (RE) effects, this paper reviews the current status of understanding of the effect of RE dopants on high-temperature oxidation behavior, with an emphasis on recent research related to deploying alumina-forming alloys and coatings with optimal performance in commercial systems. Additionally, to the well-known interaction between indigenous sulfur and RE additions, effects have been observed with C, N, and O found in commercial alloys and coatings. While there are many similarities between alumina-forming alloys and coatings, the latter bring additional complicating factors such as the effects of O incorporation during thermal spraying MCrAlY coatings, coating roughness, and heat treatments that must be considered in optimizing the beneficial dopant addition. We can see analogies between RE effects in alloys and in the substrates beneath diffusion M–Al coatings. Recently, there has been more interest in the influence of mixed oxidant environments, since these may modify the manifestation of the RE effect. Some thoughts are provided on optimizing the RE benefit and modeling oxidation of RE-doped alloys.

36 MATERIALS SCIENCE↗

Effect of Specimen Thickness on Microstructural Changes During Oxidation of the NiCrW Alloy 230 at 950–1050°C

An accurate procedure for predicting oxidation-induced damage and lifetime limits is crucial for the reliable operation of high-temperature metallic components in practical applications. In order to develop a predictive oxidation lifetime model for Ni–Cr alloys, specimens of wrought NiCrW alloy 230 with different thicknesses were cyclically oxidized in air at 950–1050°C for up to 3000 h. After prolonged exposure, two types of carbides as well as a Cr-rich nitride (π-phase) precipitated in the γ-Ni matrix. In the case of oxidation-induced loss of Cr from the alloy resulted in the formation of subscale zones, which were free of the Cr-rich carbide and nitride but also of the Ni-W rich M 6 C. The width of the M 6 C-free zone was smaller than that free of the Cr-rich precipitates. Thermodynamic and diffusion calculations of the observed time- and temperature-dependent Cr depletion processes identified that back diffusion of C occurred which resulted in an increased volume fraction of M 23 C 6 in the specimen core. Moreover, with increasing time and temperature, the amount of π-phase in the specimen core increased. The subscale depletion of the initially present Cr-nitrides and the formation of Cr-nitrides in the specimen center is believed to be related to a mechanism which is qualitatively similar to that described for the Cr carbide enrichment. However, with increasing time and decreasing specimen thickness, N uptake from the atmosphere becomes apparent. As a result, the precipitates present in the specimen center eventually consisted almost exclusively of nitrides.

36 MATERIALS SCIENCE↗

Initial assessment of Ni-base alloy performance in 0.1 MPa and supercritical CO 2

There is considerable interest in increasing the working temperature of both open and closed supercritical CO 2 (sCO 2 ) cycles to ≥700 °C. At these temperatures, it is unlikely that any Fe-base alloys have suitable strength and therefore the focus is on Ni-base alloys for this application. To begin addressing the lack of compatibility data under these conditions, initial work exposed a wide range of candidate alloys in 500-h exposures at 20 MPa (200 bar) CO 2 at 650 -750 °C in high purity CO 2 . In general, the reaction products were thin and protective in these exposures. A smaller group of alloy coupons focusing on chromia- and alumina-forming alloys was exposed for 500h in 0.1 MPa (1bar) air, CO 2 , CO 2 +O 2 and CO 2 +H 2 O for comparison. Thus, the thin surface oxides formed were very similar to those formed at high pressure and no clear detrimental effect of CO 2 oxidation or O 2 or H 2 O impurities could be observed in these exposures.

36 MATERIALS SCIENCE↗