Development of protective coatings for tantalum T-22 alloy Final summary report
Oxidation resistance tests of protective coatings for tantalum alloy
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Oxidation resistance tests of protective coatings for tantalum alloy
A high-efficiency after-treatment technology has been required to meet the increasingly stringent regulations on the emissions of nitrogen oxides (NO x ), hydrocarbons (HCs), and carbon monoxide (CO) exhausts from diesel engine vehicles throughout the world. The diesel oxidation catalyst (DOC) is an indispensable part of a diesel-fueled exhaust system, which mainly functions in the oxidation of unburned HCs and CO to CO 2 and H 2 O (in the case of HCs) and a proportion of NO to NO 2 . However, the DOC will unavoidably be poisoned by trace gaseous SO 2 or accumulated sulfur on the catalyst under real operational conditions and hence impair the overall purification efficiency of the aftertreatment system. There have been significant research efforts from both academia and industry involving sulfur-relevant diesel oxidation chemistry and development of robust sulfur-resistant oxidation catalysts. In this review, we focus on recent advances in the study of SO 2 effects on the catalytic oxidation of NO, HCs, and CO over DOCs, with particular attention to the fundamentals beneath apparent observations of sulfur influence on PGM-based and non-noble metal-based catalysts in the different oxidation reactions. Regeneration methods and design rationale for sulfur-resistant catalysts are also covered. Several challenges in the future research regarding microscopic insights into the SO 2 -influencing mechanism and next-generation sulfur-resistant DOC design are highlighted toward real-world practice.
Cermet compositions having high temperature oxidation resistance, high hardness and high abrasion and wear resistance, and particularly adapted for production of high temperature resistant cermet insulator bodies are presented. The compositions are comprised of a sintered body of particles of a high temperature resistant metal or metal alloy, preferably molybdenum or tungsten particles, dispersed in and bonded to a solid solution formed of aluminum oxide and silicon nitride, and particularly a ternary solid solution formed of a mixture of aluminum oxide, silicon nitride and aluminum nitride. Also disclosed are novel ceramic compositions comprising a sintered solid solution of aluminum oxide, silicon nitride and aluminum nitride.
Alloys based on the intermetallic compound NiAl are of technological interest as high temperature structural alloys. These alloys possess a relatively low density, high melting temperature, good thermal conductivity, and (usually) good oxidation resistance. However, NiAl and NiAl-base alloys suffer from poor fracture resistance at low temperatures as well as inadequate creep strength at elevated temperatures. This research program explored macroalloying additions to NiAl-base alloys in order to identify possible alloying and processing routes which promote both low temperature fracture toughness and high temperature strength. Initial results from the study examined the additions of Fe, Co, and Hf on the microstructure, deformation, and fracture resistance of NiAl-based alloys. Of significance were the observations that the presence of the gamma-prime phase, based on Ni3Al, could enhance the fracture resistance if the gamma-prime were present as a continuous grain boundary film or 'necklace'; and the Ni-35Al-20Fe alloy was ductile in ribbon form despite a microstructure consisting solely of the B2 beta phase based on NiAl. The ductility inherent in the Ni-35Al-20Fe alloy was explored further in subsequent studies. Those results confirm the presence of ductility in the Ni-35Al-20Fe alloy after rapid cooling from 750 - 1000 C. However exposure at 550 C caused embrittlement; this was associated with an age-hardening reaction caused by the formation of Fe-rich precipitates. In contrast, to the Ni-35Al-20Fe alloy, exploratory research indicated that compositions in the range of Ni-35Al-12Fe retain the ordered B2 structure of NiAl, are ductile, and do not age-harden or embrittle after thermal exposure. Thus, our recent efforts have focused on the behavior of the Ni-35Al-12Fe alloy. A second parallel effort initiated in this program was to use an alternate processing technique, mechanical alloying, to improve the properties of NiAl-alloys. Mechanical alloying in the conventional sense requires ductile powder particles which, through a cold welding and fracture process, can be dispersion strengthened by submicron-sized oxide particles. Using both the Ni-35Al-Fe alloys to contain approx. 1 v/o Y2O3. Preliminary results indicate that mechanically alloyed and extruded NiAl-Fe + Y2O3 alloys when heat treated to a grain-coarsened condition, exhibit improved creep resistance at 1000 C when compared to NiAl; oxidation resistance comparable to NiAl; and fracture toughness values a factor of three better than NiAl. As a result of the research initiated on this NASA program, a subsequent project with support from Inco Alloys International is underway.
The electric resistance of woven SiC fiber reinforced SiC matrix composites were measured under tensile loading conditions. The results show that the electrical resistance is closely related to damage and that real-time information about the damage state can be obtained through monitoring of the resistance. Such self-sensing capability provides the possibility of on-board/in-situ damage detection and accurate life prediction for high-temperature ceramic matrix composites. Woven silicon carbide fiber-reinforced silicon carbide (SiC/SiC) ceramic matrix composites (CMC) possess unique properties such as high thermal conductivity, excellent creep resistance, improved toughness, and good environmental stability (oxidation resistance), making them particularly suitable for hot structure applications. In specific, CMCs could be applied to hot section components of gas turbines [1], aerojet engines [2], thermal protection systems [3], and hot control surfaces [4]. The benefits of implementing these materials include reduced cooling air requirements, lower weight, simpler component design, longer service life, and higher thrust [5]. It has been identified in NASA High Speed Research (HSR) program that the SiC/SiC CMC has the most promise for high temperature, high oxidation applications [6]. One of the critical issues in the successful application of CMCs is on-board or insitu assessment of the damage state and an accurate prediction of the remaining service life of a particular component. This is of great concern, since most CMC components envisioned for aerospace applications will be exposed to harsh environments and play a key role in the vehicle s safety. On-line health monitoring can enable prediction of remaining life; thus resulting in improved safety and reliability of structural components. Monitoring can also allow for appropriate corrections to be made in real time, therefore leading to the prevention of catastrophic failures. Most conventional nondestructive evaluation (NDE) techniques such as ultrasonic C-scan, x-ray, thermography, and eddy current are limited since they require structural components of complex geometry to be taken out of service for a substantial length of time for post-damage inspection and assessment. Furthermore, the typical NDE techniques are useful for identifying large interlaminar flaws, but insensitive to CMC materials flaws developed perpendicular to the surface under tensile creep conditions. There are techniques such as piezoelectric sensor [7,8], and optical fiber [9,10] that could be used for on-line health monitoring of CMC structures. However, these systems involve attaching an external sensor or putting special fibers in CMC composites, which would be problematic at high temperature applications.
A method was developed for predicting oxidation performance, in an earth atmospheric entry environment, of reinforced carbon-carbon material, coated for oxidation resistance. A model was developed which describes oxidation control mechanisms, and the equations defining these mechanisms were derived. These relations were used to correlate oxidation test data, and to infer pertinent rate constants. Predictions were made of material oxidation performance in a representative entry environment, and the predictions were compared with ground test data. Results indicate that the method can be successfully used for predicting material oxidation performance.
Some nickel based superalloys show reduced oxidation resistance from the lack of an adherent oxide layer during high temperature cyclic oxidation. The segregation of sulfur to the oxide-metal interface is believed to effect oxide adhesion, since low sulfur alloys exhibit enhanced adhesion. X ray Photoelectron Spectroscopy (XPS) was combined with an in situ sample heater to measure sulfur segregation in NiCrAl, PWA 1480, and NiAl alloys. The polished samples with a 1.5 to 2.5 nm (native) oxide were heated from 650 to 1100 C with hold times up to 6 hr. The sulfur concentration was plotted as a function of temperature versus time at temperature. One NiCrAl sulfur study was performed on the same casting used by Browning to establish a base line between previous Auger Electron Spectroscopy (AES) results and the XPS results of this study. Sulfur surface segregation was similar for PWA 1480 and NiCrAl and reached a maximum of 30 at% at 800 to 850 C. Above 900 C the sulfur surface concentration decreased to about 3 at% at 1100 C. These results are contrasted to the minimal segregation observed for low sulfur hydrogen annealed materials which exhibit improved scale adhesion.
Here, U 3 Si 2 is a potential candidate for accident tolerant fuels because of its high uranium density and excellent thermal conductivity in comparison to UO 2 . However, U 3 Si 2 suffers from oxidation, steam corrosion, and subsequent disintegration/pulverization. The detailed investigation of kinetics that incorporates fundamental treatment of oxidation of U 3 Si 2 is scarcely reported, and the oxidation mechanisms have not been fully elucidated. In this paper, the oxidation behavior of microcrystalline (mc - ) and nanocrystalline (nc - ) U 3 Si 2 have been systematically investigated using a thermogravimetric analysis (TGA) apparatus through a series of isothermal and non-isothermal kinetic studies. The isothermal kinetic study with a model-fitting approach indicates oxidation activation energy of 85 kJ/mol for dense mc - U 3 Si 2 and 96.4 kJ/mol for nc - U 3 Si 2 pellets, while the isoconversional approach leads to an activation energy in the range of 70–85 kJ/mol for mc - U 3 Si 2 and 75–86 kJ/mol for nc - U 3 Si 2 with three most common model-free methods, including Kissinger–Akahira–Sunose, Flynn–Wall–Ozawa, and Friedman methods. The derivation of oxidation activation energies using both isothermal and isoconversional methods highlights the approach to evaluate the oxidation resistance of nuclear materials using TGA quantitatively and makes it possible to compare among various nuclear fuels.
High temperature ferritic-martensitic steels are candidate materials for heavy-duty diesel engine pistons. The envisioned transition to hydrogen blended fuels is expected to alter the post-combustion atmosphere in the engines, primarily resulting in a higher water vapor content (> 20 vol%) and potentially higher exhaust gas temperatures. The oxidation resistance of existing and newly developed alloys will be a critical life-limiting mechanism under these conditions. In the present work, the oxidation behavior of candidate piston alloys was evaluated in air+10 vol.% H2O and air+30 vol.% H2O at 700°C. Thermal cyclic (1h cycle) exposures were conducted for two variants of commercial UNSS42200 ferritic-martensitic steel and two developmental alloy steels for up to 300h. The developmental alloys each have similar compositions but with one containing elevated Cu levels of 3 wt.%, A significant reduction in resistance to breakaway oxidation was observed for the commercial alloys in the higher water vapor atmosphere. Microstructural characterization (optical metallography, scanning electron microscopy and electron microprobe analysis) revealed the formation of thick Fe-rich oxides even for the high Cr (~12 wt.%) steels after an initial stage of protective oxidation with MnCr-rich spinels. The impact of the evaporation-induced loss of Cr on the time and temperature dependent compositional changes in the alloys was correlated with experimental findings. For the developmental alloys, Cu additions appear to play a role in significantly reducing oxidation kinetics in air+30 vol.% H2O at 700°C.
We quantified the oxygen tracer diffusion in amorphous hafnium oxide thin films. These tracer diffusion values are consistent with the experimentally measured retention times of hafnium oxide resistive memory devices.
Composites synthesized from bismaleimide have superior strength and oxidation resistance at elevated temperatures when compared with similar composites prepared with epoxy or silicon polymers of similar cost. Polyimide synthesis technique and processing method yield essentially void-free fiber-glass reinforced composites.
The thermal fatigue resistance of several oxide dispersion strengthened (ODS) alloys has been evaluated through cyclic exposure in fluidized beds. The ODS nickel-base alloy MA 754 and ODS iron-base alloy MA 956 as well as four experimental ODS Ni-16Cr-4.5Al base alloys with and without Ta additions were examined. Both bare and coated alloys were subjected to up to 6000 cycles where each cycle consisted of a 3 minute immersion in a fluidized bed at 1130 C followed by a 3 minute immersion in a bed at 357 C. Testing revealed that the thermal fatigue resistance of the ODS nickel-base alloys was excellent and about equal to that of directionally solidified superalloys. However, the thermal fatigue resistance of MA 956 was found to be poor. Metallographic examination of tested specimens revealed that, in general, the post-test microstructures can be rationalized on the basis of previous diffusion, mechanical property, and oxidation studies.
Properties of FeCrAl alloys under neutron irradiation are of interest because of these materials’ potential application as accident-tolerant fuel cladding in nuclear systems. In parallel, alumina-forming austenitic (AFA) alloys are of interest for use as structural materials in advanced nuclear systems for their potential higher resistance to embrittlement and high-temperature steam oxidation resistance. An irradiation campaign for fiscal year 2024 has been developed under the Advanced Fuels Campaign to perform irradiation testing of various FeCrAl and AFA alloys in Oak Ridge National Laboratory’s High Flux Isotope Reactor (HFIR). The goals of this irradiation campaign are to (1) study the impact of minor alloying elements on the neutron-irradiated mechanical properties of FeCrAl alloys and (2) collect neutron-irradiated mechanical properties on AFA alloys for comparison with those of FeCrAl alloys. This campaign will include both tensile and fracture toughness specimens tested following HFIR irradiation at temperatures representative of normal operating conditions in light-water reactors. The pre-irradiation characterization to date, the irradiation plan for the FeCrAl and AFA specimens, and the subsequent post-irradiation experimental test plan are presented in this report, along with the status of HFIR builds and scheduled insertion dates.
The oxidation behavior of GRCop-84 (Cu-8 at %Cr-4 at %Nb) has been investigated in air and in oxygen, for durations of 0.5 to 50 hours and temperatures ranging from 500 to 900 C. For comparison, data was also obtained for the oxidation of Cu and NARloy-Z (Cu-3 wt% Ag-0.5 wt% Zr) under the same conditions. Arrhenius plots of those data showed that all three materials had similar oxidation rates at high temperatures (> 750 C). However, at intermediate temperatures (500 to 750 C) GRCop exhibited significantly higher oxidation resistance than Cu and NARloy-Z. The oxidation kinetics of GRCop-84 exhibited a sharp and discontinuous jump between the two regimes. Also, in the high temperature regime GRCop-84 oxidation rate was found to change from a high initial value to a significantly smaller terminal value at each temperature, with progress of oxidation; the two different oxidation rates were found to correlate with a porous intial oxide and a dense final oxide, respectively.
Alumina-forming MAX phases are well-known for their excellent oxidation resistance, rivaling many metallic NiAl, NiCrAl, and FeCrAl counterparts and with upper temperature capability possible to approximately1400C. However a number of limitations have been emerging that need to be acknowledged to permit robust performance in demanding applications. Ti2AlC and Ti3AlC2 possess excellent scale adhesion, cyclic oxidation/moisture/volatility resistance, and TBC compatibility. However they are very sensitive to Al content and flux in order to maintain an exclusive Al2O3 scale without runaway oxidation of ubiquitous TiO2 transient scales. Accelerated oxidation has been shown to occur for Al-depleted, damaged, or roughened surfaces at temperatures less than 1200C. Conversely, Cr2AlC is less sensitive to transients, but exhibits volatile losses at 1200C or above if common Cr7C3 impurity phases are present. Poor scale adhesion is exhibited after oxidation at 1150C or above, where spallation occurs at the Cr7C3 (depletion zone) interface. Delayed spallation is significant and suggests a moisture-induced phenomenon similar to non-adherent metallic systems. Re-oxidation of this surface does not reproduce the initial pure Al2O3 behavior, but initiates a less-protective scale. Cr2AlC has also been shown to have good long term bonding with superalloys at 800C, but exhibits significant Beta-NiAl + Cr7C3 diffusion zones at 1100C and above. This may set limits on Cr2AlC as a high temperature TBC bond coat on Ni-based superalloys, while improving corrosion resistance in lower temperature applications.
Alumina-forming austenitic (AFA) alloys are relatively inexpensive high performance materials which combine the creep resistance of low-cost austenitic alloys and the oxidation resistance of expensive alumina forming alloys. However, a fundamental understanding of the role of key alloying elements such as Ni, Cr, Al, Nb, Ti, V, B and C in the experimentally observed oxidation behavior of these alloys is still lacking. The present work is a first in a series of studies aiming to quantitatively describe the role of Ni in promoting or disrupting protective Al 2 O 3 scale formation on AFA alloys. Here, ternary Fe-Al-xNi model alloys with three different Ni contents were isothermally exposed in an atmosphere with a low partial pressure of oxygen between 800–1000 °C for 24 h to evaluate the role of Ni in the observed internal oxidation behavior. Increasing Ni contents had no impact on the internal oxidation behavior of the alloys. The experimental and theoretical analyses in the present work suggested a negligible effect of the internal oxide precipitates on the inward diffusion of oxygen, typically expected in these systems, while simultaneously highlighting the barriers in the development of reliable models for computation-assisted design of these alloys.
Two grades of hot pressed boron nitride and a boron nitride composite were subjected to oxidation tests in a 2.5 megawatt atmospheric arc jet. The results showed that fabrication and/or composition influenced thermal shock and oxidation resistance. Changes in surface structure and recession due to oxidation suggest correlation with specimen composition. The boron nitride composite reacted with the oxygen in the hot subsonic airstream to produce a glassy coating on the hot face surface.
The role of trace additions of reactive elements like Y, Ce, Th, or Hf to Cr bearing alloys was studied by applying a new developed technique of transverse section analytical electron microscopy. This reactive-element effect improves the high temperature oxidation resistance of alloys by strongly reducing the high temperature oxidation rate and enhancing the adhesion of the oxide scale, however, the mechanisms for this important effect remain largely unknown. It is indicated that the presence of yttrium affects the oxidation of Fe-Cr-Y alloys in at least two ways. The reactive element alters the growth mechanism of the oxide scale as evidenced by the marked influence of the reactive element on the oxide scale microstructure. The present results also suggest that reactive-element intermetallic compounds, which internally oxidize in the metal during oxidation, act as sinks for excess vacancies thus inhibiting vacancy condensation at the scale-metal interface and possibly enhancing scale adhesion.