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Corrosion Issues for Ceramics in Gas Turbines

The requirements for hot-gas-path materials in gas turbine engines are demanding. These materials must maintain high strength and creep resistance in a particularly aggressive environment. A typical gas turbine environment involves high temperatures, rapid gas flow rates, high pressures, and a complex mixture of aggressive gases. Figure 26.1 illustrates the requirements for components of an aircraft engine and critical issues [1]. Currently, heat engines are constructed of metal alloys, which meet these requirements within strict temperature limits. In order to extend these temperature limits, ceramic materials have been considered as potential engine materials, due to their high melting points and stability at high temperatures. These materials include oxides, carbides, borides, and nitrides. Interest in using these materials in engines appears to have begun in the 1940s with BeO-based porcelains [2]. During the 1950s, the efforts shifted to cermets. These were carbide-based materials intended to exploit the best properties of metals and ceramics. During the 1960s and 1970s, the silicon-based ceramics silicon carbide (SiC) and silicon nitride (Si3N4) were extensively developed. Although the desirable high-temperature properties of SiC and Si3N4 had long been known, consolidation of powders into component-sized bodies required the development of a series of specialized processing routes [3]. For SiC, the major consolidation routes are reaction bonding, hot-pressing, and sintering. The use of boron and carbon as additives which enable sintering was a particularly noteworthy advance [4]. For Si3N4 the major consolidation routes are reaction bonding and hot pressing [5]. Reaction-bonding involves nitridation of silicon powder. Hot pressing involves addition of various refractory oxides, such as magnesia (MgO), alumina (Al2O3), and yttria (y2O3). Variations on these processes include a number of routes including Hot Isostatic Pressing (HIP), gas-pressure sintering, sinter-HIPing, and Encapsulation-HIPing. It is important to note that each process involves the addition of secondary elements, which later were shown to dramatically influence oxidation and corrosion behavior. As dense bodies of silicon-based ceramics became more readily available, their desirable high temperature properties were confirmed. These materials retained strength to very high temperatures (i.e. 1300-1400 C). Further, they were lightweight and made from abundant materials. SiC and Si3N4 therefore emerged as leading ceramic candidates for components in heat engines, designed to operate at higher temperatures for better performance and fuel efficiency. The first US programs for ceramics in heat engines have been reviewed [6]. Selected programs on ceramic engine parts are summarized here in regard to their contributions to understanding the corrosion behavior of a heat engine environment.

Jacobson, Nathan S.↗

Petrography and classification of Apollo 17 non-mare rocks with emphasis on samples from the Station 6 boulder

The Apollo-17 nonmare rock collection consists largely of polymict breccias lithified by impact and characterized by a variety of types of lithic clasts, concentrations of siderophile elements that indicate substantial meteoritic contamination, and contents of metallic iron well above those of mare basalts. These materials may be subdivided into two compositional groups, one with 70-80% feldspar and the other with 50-60% feldspar. The high-feldspar group includes two characteristic textures: coarsely poikilitic and granulitic. The low-feldspar group includes (1) fragmental breccias with the most diverse lithic clast populations of all breccias and (2) crystalline breccias with poikilitic and subophitic to micropoikilitic textures containing tabular feldspar, granular textures with anhedral feldspar, and clast-rich ophitic textures containing less euhedral feldspar. In the poikilitic and subophitic to micropoikilitic textures, the clast population is dominated by the high-feldspar lithologies and An(94-47) plagioclase grains, indicating that these more refractory lithologies were abundant in the material from which the less feldspathic crystalline rocks formed.

Simonds, C. H.↗

Preparation of tantalum-based alloys by a unique CVD process

The paper describes a sequential pulsing technique for deposition of refractory alloys and evaluates the technique for the deposition of the tantalum-base alloys Ta-10W (Ta-10 st% W) and T-111 (Ta-8 wt% W-2 wt% Hf). The deposition cycle for Ta-10W was chosen as alternate injections of TaCl5 plus hydrogen and WCl6 plus hydrogen. The cycle for T-111 was chosen as injections of TaCl5 plus hydrogen interspersed with injections of WCl6 plus hydrogen. A temperature range of 900-1300 C was chosen for both alloys. The ability of the pulse process to blanket a uniformly heated section of substrate with a mixture of gases, whose composition varies not with position on the substrate but instead with time of residence in the reactor, allows metal of uniform thickness to be deposited. It is shown that Ta and W can be deposited at high temperature with the formation of a dense columnar grain structure, so that the feasibility of preparing uniformly thick deposits of these elements by a 'pulsing' modification of CVD is demonstrated. A similar attempt to deposit T-111 was unsuccessful due to the difficulty in reducing HfCl4.

Bryant, W. A.↗

Constraints on Mechanisms of Chondrule Formation from Chondrule Precursors and Chronology of Transient Heating Events in the Protoplanetary Disk

The mineralogy, petrography, and oxygen-isotope compositions of porphyritic chondrules—dominant chondrule type in most chondrite groups—suggest formation by incomplete melting of isotopically diverse precursors during localized transient heating events in dust-rich regions of the protoplanetary disk characterized by 16O-poor compositions (D17Odust+gas~ –7‰ to +4‰) relative to the inferred Sun’s value (D17O ~ –28 ± 2‰). The chondrule precursors included Ca,Al-rich inclusions (CAIs), amoeboid olivine aggregates (AOAs), chondrules of earlier generations, fine-grained matrix-like material, and possibly fragments of pre-existing planetesimals. Like porphyritic chondrules, igneous CAIs formed by melting of isotopically diverse precursors during transient heating events, but in an isotopically distinct, solar-like reservoir of the protoplanetary disk (D17O dust + gas ~ –24‰), probably near the proto Sun. Based on a narrow range of the initial 26Al/27Alratios inferred from the internal Al-Mg isochrons in igneous CAIs, their melting started at the very beginning of Solar System formation (t0), defined by the CV CAIs with U-corrected Pb-Pb age of 4567.3 ± 0.16 Ma and the canonical 26Al/27Al ratio of (5.25 ± 0.02) ¥ 10–5, and lasted at least 0.3 Ma. The U-corrected Pb-Pb absolute and 26Al-26Mg relative ages of porphyritic chondrules from type 3 ordinary, CO, CV, and CR carbonaceous chondrites (assuming uniform distribution of 26Al in the disk at the canonical level) suggest chondrule formation started at t0 and lasted for about 4 Ma. These observations may preclude formation of the majority of porphyritic chondrules by splashing of differentiated planetesimals and by collisions between planetesimals; instead, they are consistent with melting of dust balls by bow shocks or magnetized turbulence in the disk. Some porphyritic chondrules in equilibrated (petrologic type 4–6) ordinary chondrites contain relict fragments of coarse-grained chromite, ilmenite, phosphates, and albitic plagioclase. The similar mineral assemblage is commonly observed in type 4–6 ordinary chondrites, but is absent in type 3 chondrites, suggesting these chondrules formed by incomplete melting of thermally metamorphosed ordinary chondrite material, possibly by impacts. The CB metal-rich carbonaceous chondrites contain exclusively magnesian non-porphyritic chondrules crystallized from complete melts. These chondrules formed in a gas-melt plume generated by a hypervelocity (≥20 km/s) collision between planetesimals ~4.8 Ma after t0 in a transition or a debris disk. One of the colliding bodies was probably differentiated. The CH metal-rich carbonaceous chondrites contain chondrules formed by different mechanisms. The magnesian non-porphyritic chondrules formed in the CB impact plume ~4.8 Ma after t0. The chemically diverse (magnesian, ferroan, and Al-rich) porphyritic chondrules formed by incomplete melting of isotopically diverse precursors in the protoplanetary disk, most likely prior the CB impact plume event. We conclude that there are multiple mechanisms of chondrule formation that operated over the entire life-time of the disk.

Chondrules↗

Neural network kinetics for exploring diffusion multiplicity and chemical ordering in compositionally complex materials

Diffusion involving atom transport from one location to another governs many important processes and behaviors such as precipitation and phase nucleation. The inherent chemical complexity in compositionally complex materials poses challenges for modeling atomic diffusion and the resulting formation of chemically ordered structures. Here, we introduce a neural network kinetics (NNK) scheme that predicts and simulates diffusion-induced chemical and structural evolution in complex concentrated chemical environments. The framework is grounded on efficient on-lattice structure and chemistry representation combined with artificial neural networks, enabling precise prediction of all path-dependent migration barriers and individual atom jumps. To demonstrate the method, we study the temperature-dependent local chemical ordering in a refractory NbMoTa alloy and reveal a critical temperature at which the B2 order reaches a maximum. The atomic jump randomness map exhibits the highest diffusion heterogeneity (multiplicity) in the vicinity of this characteristic temperature, which is closely related to chemical ordering and B2 structure formation. The scalable NNK framework provides a promising new avenue to exploring diffusion-related properties in the vast compositional space within which extraordinary properties are hidden.

36 MATERIALS SCIENCE↗

Fast Electromechanical Switches Based on Carbon Nanotubes

Electrostatically actuated nanoelectromechanical switches based on carbon nanotubes have been fabricated and tested in a continuing effort to develop high-speed switches for a variety of stationary and portable electronic equipment. As explained below, these devices offer advantages over electrostatically actuated microelectromechanical switches, which, heretofore, have represented the state of the art of rapid, highly miniaturized electromechanical switches. Potential applications for these devices include computer memories, cellular telephones, communication networks, scientific instrumentation, and general radiation-hard electronic equipment. A representative device of the present type includes a single-wall carbon nanotube suspended over a trench about 130 nm wide and 20 nm deep in an electrically insulating material. The ends of the carbon nanotube are connected to metal electrodes, denoted the source and drain electrodes. At bottom of the trench is another metal electrode, denoted the pull electrode (see figure). In the off or open switch state, no voltage is applied, and the nanotube remains out of contact with the pull electrode. When a sufficiently large electric potential (switching potential) is applied between the pull electrode and either or both of the source and drain electrodes, the resulting electrostatic attraction bends and stretches the nanotube into contact with the pull electrode, thereby putting the switch into the "on" or "closed" state, in which substantial current (typically as much as hundreds of nanoamperes) is conducted. Devices of this type for use in initial experiments were fabricated on a thermally oxidized Si wafer, onto which Nb was sputter-deposited for use as the pull-electrode layer. Nb was chosen because its refractory nature would enable it to withstand the chemical and thermal conditions to be subsequently imposed for growing carbon nanotubes. A 200- nm-thick layer of SiO2 was formed on top of the Nb layer by plasma-enhanced chemical vapor deposition. In the device regions, the SiO2 layer was patterned to thin it to the 20-nm trench depth. The trenches were then patterned by electron- beam lithography and formed by reactive- ion etching of the pattern through the 20-nm-thick SiO2 to the Nb layer.

Kaul, Anupama↗

Control of Two Solid Electrolyte Interphases at the Negative Electrode of an Anode‐Free All Solid‐State Battery based on Argyrodite Electrolyte

Abstract Anode‐free all solid‐state batteries (AF‐ASSBs) employ “empty” current collector with three active interfaces that determine electrochemical stability; lithium metal – Solid electrolyte (SE) interphase (SEI‐1), lithium – current collector interface, and collector – SE interphase (SEI‐2). Argyrodite Li 6 PS 5 Cl (LPSCl) solid electrolyte (SE) displays SEI‐2 containing copper sulfides, formed even at open circuit. Bilayer of 140 nm magnesium/30 nm tungsten (Mg/W‐Cu) controls the three interfaces and allows for state‐of‐the‐art electrochemical performance in half‐cells and fullcells. AF‐ASSB with NMC811 cathode achieves 150 cycles with Coulombic efficiency (CE) above 99.8%. With high mass‐loading cathode (8.6 mAh cm −2 ), AF‐ASSB retains 86.5% capacity after 45 cycles at 0.2C. During electrodeposition of Li, gradient Li‐Mg solid solution is formed, which reverses upon electrodissolution. This promotes conformal wetting/dewetting by Li and stabilizes SEI‐1 by lowering thermodynamic driving force for SE reduction. Inert refractory W underlayer is required to prevent ongoing formation of SEI‐2 that also drives electrochemical degradation. Inert Mo and Nb layers likewise protect Cu from corroding, while Li‐alloying layers (Mg, Sn) are less effective due to ongoing volume changes and associated pulverization. Mechanistic explanation for observed Li segregation within alloying Li x Mg layer is provided through mesoscale modelling, considering opposing roles of diffusivity differences and interfacial stresses.

Wang, Yixian [Materials Science and Engineering Pr↗

Carbon-rich Chondritic Clast PV1 from the Plainview H-chondrite Regolith Formation from H3 Chondrite Material by Possible Cometary Impact

Chondritic clast PV1 from the Plainview H-chondrite regolith breccia is a subrounded, 5-mm diameter unequilibrated chondritic fragment that contains 13 wt% C occurring mainly within irregularly shaped 30-400-micron-size opaque patches. The clast formed from H3 chondrite material as indicated by the mean apparent chondrule diameter (310 micron vs. approximately 300 micron in H3 chondrites), the mean Mg-normalized refractory lithophile abundance ratio (1.00 +/- 0.09 XH), the previously determined 0-isotopic composition (Delta O-17 = 0.66% vs. 0.68 +/- 0.04%0 in H3 chondrites and 0.73 +/- 0.09% in H4-6 chondrites), the heterogeneous olivine compositions in grain cores (with a minimum range of Fal-19), and the presence of glass in some chondrules. Although the clast lacks the fine-grained, ferroan silicate matrix material present in type 3 ordinary chondrites, PV1 contains objects that appear to be recrystallized clumps of matrix material. Similarly, the apparent dearth of radial pyroxene and cryptocrystalline chondrules in PV1 is accounted for by the presence of some recrystallized fragments of these chondrule textural types. All of the chondrules in PV1 are interfused indicating that temperatures must have briefly reached approximately 1100C (the approximate solidus temperature of H-chondrite silicate). The most likely source of this heating was by an impact. Some metal was lost during impact heating as indicated by the moderately low abundance of metallic Fe-Ni in PV1 (approximately 14 wt%) compared to that in mean H chondrites (approximately 18 wt%). The carbon enrichment of the clast may have resulted from a second impact event, one involving a cometary projectile, possibly a Jupiter-family comet. As the clast cooled, it experienced hydrothermal alteration at low water/rock ratios as evidenced by the thick rims of ferroan olivine around low-FeO olivine cores. The C-rich chondritic clast was later incorporated into the H-chondrite parent-body regolith and extensively fractured and faulted.

Rubin, Alan E.↗

Mg vacancy and impurity-limited MgO single crystal thermal conductivity

Magnesium oxide (MgO) exhibits one of the highest thermal conductivities among oxides and is widely used as a dielectric material and substrate in semiconductor devices, in refractory applications, and as a promising filler in thermal interface materials for electronics. Its high thermal conductivity may be sensitive to impurity and defects, yet this influence is still uncertain. Here, in this study, the impact of the common impurities, i.e., Al, Ca, Ti, V, Fe, Si, B, Nb, Zr, Na, and K, as well as Mg and O vacancies on phonon scattering and thermal conductivity of MgO is studied using a fully first-principles T-matrix framework. It is found that B, Nb, and Zr impurities, along with Mg vacancies, lead to exceptionally strong reductions in thermal conductivity. By contrast, O vacancies and other impurities have modest to minimal impacts. Leveraging the T-matrix results, we reassess the perturbative, mass-only formalism whose use is pervasive in the literature and show that neglecting bond disorder does not necessarily lead to underestimation: for all transition-metal impurities studied, bond perturbations partially cancel mass disorder, causing the traditional perturbative model to overestimate scattering. We propose a simple modified perturbative expression that incorporates both mass and bond disorder and closely reproduces the T-matrix trends. Our predicted low-temperature trends by including phonon-impurity and phonon-boundary scattering match reasonably well with experiments. This work provides an in-depth study of impurity- and vacancy-limited thermal conductivity of MgO and suggests that reported “high-purity” MgO values have likely not yet reached the intrinsic upper limit, which may be substantially higher.

36 - MATERIALS SCIENCE↗

Early Petrologic Processes on the Ureilite Parent Body

We present a petrographic and petrologic analysis of 21 olivine-pigeonite ureilites, along with new experimental results on melt compositions predicted to be in equilibrium with ureilite compositions. We conclude that these ureilites are the residues of a partial melting/smelting event. Textural evidence preserved in olivine and pigeonite record the extent of primary smelting. In pigeonite cores, we observe fine trains of iron metal inclusions that formed by the reduction of olivine to pigeonite and metal during primary smelting. Olivine cores lack metal inclusions but the outer grain boundaries are variably reduced by a late-stage reduction event. The modal proportion of pigeonite and percentage of olivine affected by late stage reduction are inversely related and provide an estimation of the degree of primary smelting during ureilite petrogenesis. In our sample suite, this correlation holds for 16 of the 21 samples examined. Olivine-pigeonite-liquid phase equilibrium constraints are used to obtain temperature estimates for the ureilite samples examined. Inferred smelting temperatures range from approximately 1150 C to just over 1300 C and span the range of estimates published for ureilites containing two or more pyroxenes. Temperature is also positively correlated with modal percent pigeonite. Smelting temperature is inversely correlated with smelting depth--the hottest olivine-pigeonite ureilites coming from the shallowest depth in the ureilite parent body. The highest temperature samples also have oxygen isotopic signatures that fall toward the refractory inclusion-rich end of the carbonaceous chondrite-anhydrous mineral (CCAM) slope 1 mixing line. These temperature-depth variations in the ureilite parent body could have been created by a heterogeneous distribution of heat producing elements, which would indicate that isotopic heterogeneities existed in the material from which the ureilite parent body was assembled.

Singletary, S. J.↗

In situ synchrotron X-ray imaging and mechanical properties characterization of additively manufactured high-entropy alloy composites

Laser beam directed energy deposition has become an increasingly popular advanced manufacturing technique for materials discovery as a result of the in situ alloying capability. In this study, we leverage an additive manufacturing enabled high throughput materials discovery approach to explore the composition space of a graded W x (CoCrFeMnNi) 100–x sample spanning 0 ≤ x ≤ 21 at%. In addition to microstructural and mechanical characterization, synchrotron high speed x-ray computer aided tomography was conducted on a W 20 (CoCrFeMnNi) 80 composition to visualize melting dynamics, powder-laser interactions, and remelting effects of previously consolidated material. Results reveal the formation of the Fe 7 W 6 intermetallic phase at W concentrations> 6 at%, despite the high configurational entropy. Unincorporated W particles also occurred at W concentrations> 10 at% accompanied by a dissolution band of Fe 7 W 6 at the W/matrix interface and hardness values greater than 400 HV. In this work, the primary strengthening mechanism is attributed to the reinforcement of the Fe 7 W 6 and W phases as a metal matrix composite. The in situ high speed x-ray imaging during remelting showed that an additional laser pass did not promote further mixing of the Fe 7 W 6 or W phases suggesting that, despite the dissolution of the W into the Fe 7 W 6 phase being thermodynamically favored, it is kinetically limited by the thickness/diffusivity of the intermetallic phase, and the rapid solidification of the laser-based process.

36 MATERIALS SCIENCE↗

Irradiation of ultrasonic sensors and adhesive couplants for application in light water reactor primary loop piping and components

The Electric Power Research Institute (EPRI) Nuclear Sector and US Department of Energy Light Water Reactor Sustainability Program are committed to engaging in research and development endeavors to address materials aging issues specific to long term operation of light water power reactors. To this effect, EPRI launched an industry initiative to develop nondestructive evaluation systems for online monitoring of existing cracks in light water reactor primary coolant loop piping and components. One of the goals of this initiative is to develop a sensor system (or systems) that can determine nondestructively if cracks are growing or arrested and, in the case of the former, to characterize their growth rates. A missing component of this initiative is an experimental assessment of how sensors and adhesive couplants will perform in service when exposed to chronic energetic neutron radiation, particularly at the primary coolant loop hot and cold leg dissimilar metal welds, which join the primary loop piping to the reactor pressure vessel and reside in the vicinity of the reactor core. The objective of this experimental study was to determine how ultrasonic transducers and adhesive couplants perform when exposed to irradiation in a test reactor to simulate and accelerate in-service exposure. Further, to achieve this objective, the signal stability of piezoelectric transducers and performance of adhesive couplants as a function of accumulated fast neutron fluence were characterized by collecting ultrasonic data in-situ during irradiation. Of particular interest were the ultrasonic signal quality and time decay of the amplitude of acoustic reflections as a function of fast neutron fluence. The results of the study showed that, of the 8 transducer/substrate sample assemblies tested, only 3 generated usable ultrasonic signals through the conclusion of the irradiation campaign. It was found that high temperature epoxy tends to ultrasonically couple the sensors to the substrates better than three types of refractory ceramic cements studied, as is supported by post irradiation examination. The results obtained through this experimental study will be utilized in the achievement of the overall goal of development of a sensor system to perform online monitoring of primary loop components.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗

Thin-Film Ceramic Thermocouples Fabricated and Tested

The Sensors and Electronics Technology Branch of the NASA Glenn Research Center is developing thin-film-based sensors for surface measurement in propulsion system research. Thin-film sensors do not require special machining of the components on which they are mounted, and they are considerably thinner than wire- or foil-based sensors. One type of sensor being advanced is the thin-film thermocouple, specifically for applications in high-temperature combustion environments. Ceramics are being demonstrated as having the potential to meet the demands of thin-film thermocouples in advanced aerospace environments. The maximum-use temperature of noble metal thin-film thermocouples, 1500 C (2700 F), may not be adequate for components used in the increasingly harsh conditions of advanced aircraft and next-generation launch vehicles. Ceramic-based thermocouples are known for their high stability and robustness at temperatures exceeding 1500 C, but are typically in the form of bulky rods or probes. As part of ASTP, Glenn's Sensors and Electronics Technology Branch is leading an in-house effort to apply ceramics as thin-film thermocouples for extremely high-temperature applications as part of ASTP. Since the purity of the ceramics is crucial for the stability of the thermocouples, Glenn's Ceramics Branch and Case Western Reserve University are developing high-purity ceramic sputtering targets for fabricating high-temperature sensors. Glenn's Microsystems Fabrication Laboratory, supported by the Akima Corporation, is using these targets to fabricate thermocouple samples for testing. The first of the materials used were chromium silicide (CrSi) and tantalum carbide (TaC). These refractory materials are expected to survive temperatures in excess of 1500 C. Preliminary results indicate that the thermoelectric voltage output of a thin-film CrSi versus TaC thermocouple is 15 times that of the standard type R (platinum-rhodium versus platinum) thermocouple, producing 20 mV with a 200 C temperature gradient. The photograph on the left shows the CrSi-TaC thermocouple in a test fixture at Glenn, and the resulting output signal is shown on the right. The temperature differential across the sample, from the center of the sample inside the oven to the sample mount outside the oven, is measured using a type R thermocouple on the sample.

Wrbanek, John D.↗

Deformation Behaviors in Single BCC‐Phase Refractory Multi‐Principal Element Alloys under Dynamic Conditions

The mechanical behavior and microstructural evolution of a BCC-phase NbTaTiV refractory multi-principal element alloy (RMPEA) is studied over a wide range of strain rates (10 −3 to 10 3 s −1 ) and temperatures (room temperature to 850 °C). The mechanical property of present RMPEA shows less strain-rate dependence and strong resistance to softening at high temperatures. Under high strain-rate loading, the formation of thin type-I twins is observed, which could lead to an increase in strain-hardening rates. However, this hardening mechanism competes with adiabatic heating effects, resulting in the deterrence of strain-hardening behaviors. In contrast, substantial strain-hardening occurs at cryogenic temperatures due to the formation of twins, which act as stronger barriers to dislocation motion and interact with each other. To further understand the different strain-hardening behaviors, density functional theory (DFT) calculations predict relatively low stacking fault energies and high twinning stress for the NbTaTiV RMPEA.

36 MATERIALS SCIENCE↗

Compositional inhomogeneity and its effect on the hardness of nanostructured refractory high-entropy alloys

The pronounced compositional inhomogeneity observed in refractory high-entropy alloys (HEAs), as opposed to non-refractory HEAs, has an important influence on their mechanical properties, thereby posing a significant challenge for the development of high-performance refractory HEAs. In this work, by combining transmission electron microscopy imaging, chemical analysis, and nano-hardness tests, we investigate the compositional inhomogeneities in a series of sintered nanostructured HEAs and elucidate their influence on the material's hardness. Further, we reveal that the compositional inhomogeneity of the sintered nanostructured HEAs is temperature- and component- dependent. By correlating the hardness of nanostructured HEAs to the evolving compositional inhomogeneity, our work demonstrates that the compositional inhomogeneity in nanostructured HEAs can be tuned by sintering temperature or alloying towards optimized microstructure and hardness.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Perspectives on novel refractory amorphous high-entropy alloys in extreme environments

Two new refractory amorphous high-entropy alloys (RAHEAs) within the W–Ta–Cr–V and W–Ta–Cr–V–Hf systems were herein synthesized using magnetron-sputtering and tested under high-temperature annealing and displacing irradiation using in situ Transmission Electron Microscopy. While the 14W-41Ta-26Cr-19V in at.% RAHEA (defined as WTaCrV RAHEA) was found to be unstable under such tests, additions of Hf in this system composing a new quinary 24W-40Ta-18Cr-5V-13Hf in at.% RAHEA (defined as WTaCrVHf RAHEA) was found to be a route to achieve stability both under annealing and irradiation. A new effect of nanoprecipitate reassembling observed to take place within the WTaCrVHf RAHEA under irradiation indicates that a duplex microstructure composed of an amorphous matrix with crystalline nanometer-sized precipitates enhances the radiation response of the system. Further, it is demonstrated that tunable chemical complexity arises as a new alloy design strategy to foster the use of novel RAHEAs within extreme environments. New perspectives for the alloy design and application of chemically-complex amorphous metallic alloys in extreme environments are presented with focus on their thermodynamic phase stability when subjected to high-temperature annealing and displacing irradiation.

36 MATERIALS SCIENCE↗

Performance of Ceramics in Severe Environments

Ceramics are generally stable to higher temperatures than most metals and alloys. Thus the development of high temperature structural ceramics has been an area of active research for many years. While the dream of a ceramic heat engine still faces many challenges, niche markets are developing for these materials at high temperatures. In these applications, ceramics are exposed not only to high temperatures but also aggressive gases and deposits. In this chapter we review the response of ceramic materials to these environments. We discuss corrosion mechanisms, the relative importance of a particular corrodent, and, where available, corrosion rates. Most of the available corrosion information is on silicon carbide (SIC) and silicon nitride (Si3N4) monolithic ceramics. These materials form a stable film of silica (SO2) in an oxidizing environment. We begin with a discussion of oxidation of these materials and proceed to the effects of other corrodents such as water vapor and salt deposits. We also discuss oxidation and corrosion of other ceramics: precurser derived ceramics, ceramic matrix composites (CMCs), ceramics which form oxide scales other than silica, and oxide ceramics. Many of the corrosion issues discussed can be mitigated with refractory oxide coatings and we discuss the current status of this active area of research. Ultimately, the concern of corrosion is loss of load bearing capability. We discuss the effects of corrosive environments on the strength of ceramics, both monolithic and composite. We conclude with a discussion of high temperature wear of ceramics, another important form of degradation at high temperatures.

Jacobson, Nathan S.↗

A quinary WTaCrVHf nanocrystalline refractory high-entropy alloy withholding extreme irradiation environments

In the quest of new materials that can withstand severe irradiation and mechanical extremes for advanced applications (e.g. fission & fusion reactors, space applications, etc.), design, prediction and control of advanced materials beyond current material designs become paramount. Here, through a combined experimental and simulation methodology, we design a nanocrystalline refractory high entropy alloy (RHEA) system. Compositions assessed under extreme environments and in situ electron-microscopy reveal both high thermal stability and radiation resistance. We observe grain refinement under heavy ion irradiation and resistance to dual-beam irradiation and helium implantation in the form of low defect generation and evolution, as well as no detectable grain growth. The experimental and modeling results—showing a good agreement—can be applied to design and rapidly assess other alloys subjected to extreme environmental conditions.

36 MATERIALS SCIENCE↗