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Unified constitutive model development for metal matrix composites at high temperature

Structural alloys used in high temperature applications exhibit complex thermomechanical behavior that is time dependent and hereditary. Recent attention is being focused on metal matrix composite materials for high temperature applications where they exhibit all the complexities of conventional alloys and their strong anisotropy adds further complexities. Here, a proven constitutive model for isotropic materials in which the inelastic strain rate and internal state are expressible as gradients of a dissipation potential is taken to depend on invariants that reflect local transverse isotropy. Applications illustrate the capability of the theory of representing the time dependent, hereditary, anisotropic behavior typical of these materials at high temperature.

Robinson, D. N.↗

Martensitic Phase Transition in Complex NiTi-Based Shape Memory Alloys from First-Principles Calculations

Recent rapid progresses in physics theory and computational power have made it possible to accurately predict the phase transitions and martensitic transition temperatures (MTTs) in shape memory alloys (SMAs) from first principles. However, previously theory and calculations [1-4] were applied only to study highly ordered stoichiometric binary alloys such as NiTi, PdTi and NiHf. Here we report on our recent first-principles investigations [5,6] on Ni 0.5 Ti 0.5-x Hf x and Pd x Ni 0.5-x Ti 0.5 ternaries and off-stoichiometric NiTi, and the predicted martensitic phase transitions in these complex SMAs are in good agreement with experimental findings. In particular, the calculated MTTs for all these compositions are within 100 K compared with the corresponding measured data, and our results also reveal the origin of the striking asymmetry in MTT of the off-stoichiometric NiTi near equiatomic compositions. We will address various techniques to overcome the difficulty encountered in studying ternaries and off-stoichiometic binaries associated with disorder and/or much lowered symmetry. Our theoretical approach is expected to be a broadly applicable and predictive theory for designing complex SMAs with desirable properties. References: [1] J. B. Haskins, A. E. Thompson, and J. W. Lawson, Phys. Rev B 94 , 214110 (2016). [2] J. B. Haskins and J. W. Lawson, J. App. Phys. 121 , 205103 (2017). [3] J. B. Haskins, H. Malmir, S. J. Honrao, L. A. Sandoval, and J. W. Lawson, Acta Materialia 212 , 116872 (2017). [4] Z. Wu, J. W. Lawson, and O. Benafan, Phys. Rev. B 106 , L140102 (2022). [5] Z. Wu, H. Malmir, O. Benafan, and J. W. Lawson, Acta Materialia 261 , 119362 (2023). [6] Z. Wu, J. W. Lawson, and O. Benafan, Phys. Rev. B 108 , L140103 (2023).

Zhigang Wu↗

Self-Reacting Friction Stir Welding for Aluminum Complex Curvature Applications

This viewgraph representation provides an overview of sucessful research conducted by Lockheed Martin and NASA to develop an advanced self-reacting friction stir technology for complex curvature aluminum alloys. The research included weld process development for 0.320 inch Al 2219, sucessful transfer from the 'lab' scale to the production scale tool and weld quality exceeding strenght goals. This process will enable development and implementation of large scale complex geometry hardware fabrication. Topics covered include: weld process development, weld process transfer, and intermediate hardware fabrication.

Brown, Randy J.↗

Design for Oxidation Resistance

Alloys intended for use in high-temperature environment rely on the formation of a continuous, compact, slow-growing oxide layer for oxidation and hot corrosion resistance. To be protective, this oxide layer must be chemically, thermodynamically stable. Successful alloy design for oxidative environment is best achieved by developing alloys that are capable of forming adherent scales of either alumina (Al2O3), chromia (Cr2O3), or silica (SiO2). In this article, emphasis has been placed on the issue related to high-temperature oxidation of superalloys used in gas turbine engine application. Despite the complexity of these alloys, optimal performance has been associated with protective alumina scale formation. As will be described below, both compositional makeup and protective coatings play key role in providing oxidation protection. Other high-temperature materials described include nickel and titanium aluminide intermetallics, refractory metal, and ceramics.

Smialek, James L.↗

The 1200 K compressive properties of N-containing NiAl

As part of a series of experiments to understand the role of N on the strength of NiAl, a heat of NiAl was enriched with N by melting and atomization to powder in a nitrogen atmosphere. Following consolidation of the powder by hot extrusion, 1200 K compressive properties were measured in air. Within the range of strain rates examined, 10(exp -3) to 10(exp -9) s(exp -1), the strength of the N-enriched NiAl was greater than that of a simple 15 micron grain size polycrystalline, binary NiAl alloy. For the most part the overall improvement in strength is ascribed to the fine grain size of the N-doped NiAl rather than the alloy chemistry; however, the alloy displayed a complex behavior exhibiting both weakening effects as well as strengthening ones.

Whittenberger, J. Daniel↗

1200 K Compressive Properties of N-Containing Nial

As part of a series of experiments to understand the role of N on the strength of NiAl, a heat of NiAl was enriched with N by melting and atomization to powder in a nitrogen atmosphere. Following consolidation of the powder by hot extrusion, 1200 K compressive properties were measured in air. Within the range of strain rates examined, 10 exp -3 to 10 exp -9/s, the strength of the N-enriched NiAl was greater than that of a simple 15 micron grain size polycrystalline, binary NiAl alloy. For the most part the overall improvement in strength is ascribed to the fine grain size of the N-doped NiAl rather than the alloy chemistry; however, the alloy displayed a complex behavior exhibiting both weakening effects as well as strengthening ones.

Whittenberger, J. D.↗

Fuel Manifold Resists Embrittlement by Hydrogen

Completely-cast hydrogen-compatible alloy preferable to protective plating. Complexity of plating, welding, and brazing unnecessary if hydrogen-compatible alloy used for entire casting instead of protective overlay. Parts exposed to high-pressure hydrogen made immune to hydrogen embrittlement if fabricated from new alloy, Incoly 903 (or equivalent). Material strong and compatible with hydrogen at all temperatures and adapted for outlet manifold of Space Shuttle main combustion chamber.

Adams, T.↗

Surface Segregation in Multicomponent Systems: Modeling of Surface Alloys and Alloy Surfaces

The study of surface segregation, although of great technological importance, has been largely restricted to experimental work due to limitations associated with theoretical methods. However, recent improvements in both first-particle and semi-empirical methods are opening, the doors to an array of new possibilities for surface scientists. We apply one of these techniques, the Bozzolo, Ferrante and Smith (BFS) method for alloys, which is particularly suitable for complex systems, to several aspects of the computational modeling of surfaces and segregation, including alloy surface segregation, structure and composition of alloy surfaces, and the formation of surface alloys. We conclude with the study of complex NiAl-based binary, ternary and quaternary thin films (with Ti, Cr and Cu additions to NiAl). Differences and similarities between bulk and surface compositions are discussed, illustrated by the results of Monte Carlo simulations. For some binary and ternary cases, the theoretical predictions are compared to experimental results, highlighting the accuracy and value of this developing theoretical tool.

Bozzolo, Guillermo↗

Zone leveling and solution growth of complex compound semiconductors in space

A research program on complex semiconducting compounds and alloys was completed that addressed the growth of single crystals of CdSe(y)Te(1-y), Zn(x)Cd(1-x)Te, Mn(x)Cd(1-x)Te, InP(y)As(1-y) and CuInSe2 and the measurement of fundamental physico-chemical properties characterizing the above materials. The purpose of this ground based research program was to lay the foundations for further research concerning the growth of complex ternary compound semiconductors in a microgravity environment.

Bachmann, K. J.↗

The Development of Titanium Alloys for Application in the Space Shuttle Main Engine

The high-strength-to-weight ratio of titanium alloys, particularly at cryogenic temperatures, make them attractive for application in rocket engines - offering the potential of superior performance while minimizing component weight. This was particularly attractive for rotating components, such as pump impellers, where titanium alloys presented the potential to achieve a major advance in rotational tip speed, with a reduction in stages and resultant saving in pump weight and complexity. The investigation into titanium alloys for application in cryogenic turbopumps began in the early 1960's. However, it was found that the reactivity of titanium limited applications and produced unique processing challenges. Specialized chemical compositions and processing techniques had to be developed. A substantial amount of material properties testing and trials in experimental turbopumps occurred, ultimately leading to application in the Space Shuttle Main Engine. One particular alloy stood out for use at liquid hydrogen temperatures, Ti-5Al-2.5Sn ELI. This alloy was employed for several critical components. This presentation deals with the development effort, the challenges that were encountered and operational experiences with Ti-5Al-2.5Sn ELI in the SSME.

Halchak, John A.↗

Periodic Cellular Structure Technology for Shape Memory Alloys

Shape memory alloys are being considered for a wide variety of adaptive components for engine and airframe applications because they can undergo large amounts of strain and then revert to their original shape upon heating or unloading. Transition45 Technologies, Inc., has developed an innovative periodic cellular structure (PCS) technology for shape memory alloys that enables fabrication of complex bulk configurations, such as lattice block structures. These innovative structures are manufactured using an advanced reactive metal casting technology that offers a relatively low cost and established approach for constructing near-net shape aerospace components. Transition45 is continuing to characterize these structures to determine how best to design a PCS to better exploit the use of shape memory alloys in aerospace applications.

Chen, Edward Y.↗

Preliminary study of oxide-dispersion-strengthened B-1900 prepared by mechanical alloys

An experimental oxide dispersion strengthened (ODS) alloy based on the B-1900 composition was produced by the mechanical alloying process. Without optimization of the processing for the alloy or the alloy for the processing, recrystallization of the extruded product to large elongated grains was achieved. Materials having grain length-width ratios of 3 and 5.5 were tested in tension and stress-rupture. The ODS B-1900 exhibited tensile strength similar to that of cast B-1900. Its stress-rupture life was lower than that of cast B-1900 at 760 C. At 1095 C the ODS B-1900 with the higher grain length-width ratio (5.5) had stress-rupture life superior to that of cast B-1900. It was concluded that, with optimization, oxide dispersion strengthening of B-1900 and other complex cast nickel-base alloys has potential for improving high temperature properties over those of the cast alloy counterparts.

Glasgow, T. K.↗

Preliminary Fatigue Studies on Aluminum Alloy Aircraft Girders

Preliminary information on the complex subject of the fatigue strength of fabricated structural members for aircraft is presented in the test results obtained on several different types of airship girders subjected to axial tension and compression in a resonance fatigue machine. A description of this machine as well as numerous photographs of the fatigue failures are given. There is also presented an extended bibliography on the subject of fatigue strength.

Source record↗

A Transmission Electron Microscopy Study of a Refractory Metal Grain from a Calcium-Aluminum-Rich Inclusion in the Leoville CV3 Chondrite

Introduction: Calcium-aluminum-rich inclusions (CAIs) are an important component of chondritic meteorites. They can contain materials that are thermodynamically predicted and isotopically age dated to be among the first-formed solids in our solar system [1-5]. Observed in some CAIs are micron to sub-micron sized inclusions rich in Fe, Ni, and high-Z elements such as Pt, Os, Ir and W, in the form of refractory metal nuggets (RMNs), fremdlinges, and ‘nugget like objects’ (NLOs) [1,6]. Refractory siderophile elements such as Os, Ir and Ru are thermodynamically predicted to condense at temperatures well in excess of the major CAI phases such as melilite, perovskite, spinel and hibonite [2,7-9]. These refractory metal inclusions in CAIs can therefore serve as probes into the thermodynamic landscape of the early solar protoplanetary disk. Here we report on a refractory grain identified in a CAI of the Leoville CV3 chondrite. This work is part of an ongoing effort to gain insight into the thermochemistry of the early solar system through systematic analyses of the structure and chemistry of various components in CAIs [10-13]. Sample and Analytical Techniques: A fluffy type A CAI (Fig. 1A) was identified in a section of the Leoville, CV3 chondrite (Center for Meteorite Studies, Arizona State University collection, #821_C_3) using a JOEL-JXA 8530F electron microprobe at Arizona State University. Backscattered electron (BSE) imaging and energy-dispersive X-ray spectroscopy (EDS) were used to identify refractory metal grains in the CAI using a Thermo Fisher (formerly FEI) Helios NanoLab 660 G3 focused-ion-beam scanning-electron microscope (FIBSEM) located at the Kuiper Materials Imaging and Characterization Facility (KMICF) at the Lunar and Planetary Laboratory, University of Arizona. The FIB is equipped with an EDAX EDS system. We selected one of the larger (micron-sized) refractory metal grains, designated as ‘Spud’ (Fig. 1B) for further analysis. ‘Spud’ was extracted and thinned to electron transparency (<100 nm) using the FIB-SEM located in KMICF, following methods described by [14- 15]. The FIB section was analyzed using a 200 keV Hitachi HF5000 scanning transmission electron microscope (S/TEM) located at KMICF. The HF5000 is equipped with cold-field emission gun, 3rd-order spherical aberration corrector for STEM imaging, and an Oxford Instruments X-Max N 100 TLE energydispersive spectroscopy (EDS) system with dual 100 mm2 windowless silicon-drift detectors (Ω = 2.0 sr). Selected-area electron-diffraction (SAED) patterns were acquired to aid in determination of crystallinity and phase. Results: The mineralogy, texture, and morphology of the CAI are consistent with that of a fluffy type A (FTA) CAI [16]. BSE imaging at high magnifications revealed grains with high contrast, indicative of compositions rich in elements of higher atomic number relative to surrounding material. These high-Z grains have sizes that range from ∼250 nm to 4 µm. EDS analyses confirm that the bright grains are metal-rich inclusions. A minor fraction of the grains are composed of only Fe and Ni, but the majority (∼60%) of the identified inclusions also contained various refractory siderophiles including Os, Ru, Zr, Ir and Mo. EDS analysis on the FIB-SEM of Spud shows that it contains Fe, Ni, Mo and Ru. High-angle annular dark-field (HAAFD) imaging and EDS mapping in the TEM (Fig. 2) show that Spud occurs in melilite (Ca1.9Al1.99Si1.06O7). Spud contains a subhedral to anhedral morphology and is compositionally heterogenous (polyphasic, Fig. 2). Local spatial correlation occurs among Fe, Ni, and Pt, and also among Os, Ru, and Mo. SAED patterns show that the Fe-Ni-Pt, Fe-Os-Mo-Ru and Fe-Pt regions are crystalline. Discussion: CAIs can contain various types of inclusions rich in Fe, Ni and refractory siderophiles such as Os, Ru, W and Pt [1]. RMNs are micron-sized, single phase alloy grains and can contain Os, Ir, Ru and Rh [1,7,17]. NLOs are also micron-sized inclusions, but contain two phases, a refractory metal, and an oxide [6]. Fremdlinge are the largest of such inclusions (tens of microns in size) and are complex aggregates of Fe-Ni alloy, silicates, oxides, and sulfides [1,17]. While the size of Spud matches previous descriptions of RMNs and NLOs, Spud is neither a single-phase alloy like RMNs, nor does it contain one metal phase and one oxide like NLOs. Spud does not match the above described categories of refractory metal inclusions. The presence of refractory siderophiles such as Mo, Os, Ru, and Pt suggests a high-temperature origin. Thermodynamic modelling by [7] indicates condensation temperatures of 1917 K, 1693 K, 1613 K and 1415 K for Os, Mo, Ru and Pt respectively. These models also show that following the initial condensation of a refractory metal, alloying of solutes such as Fe, Ni and W, occurs in levels proportional to their partial pressures in the surrounding gas. Such alloying occurs at temperatures above the condensation temperatures of common CAI phases such as melilite (1529 K), perovskite (1441 K), spinel (197 K) and forsterite (1354 K) [2]. The polyphasic nature of Spud could be the result of such high-temperature alloying, possibly shortly after the condensation of Mo and Ru at 1693 K and 1613 K respectively. That Spud occurs as an inclusion is consistent with it having formed prior to and at temperature above that of its host melilite in this FTA CAI, which is qualitatively consistent with such prior thermodynamic modeling. Further, the polyphasic nature of Spud is similar to refractory grains from a FTA CAI in the Northwest Africa (NWA) 8323, CV3 chondrite [11-13]. These data suggest that such refractory metal grains could have been widespread in the inner and early solar protoplanetary disk and represent some of the earliest formed solids to have condensed. Acknowledgments: Research and instrumentation supported by NASA grants #NNX12AL47G, #NNX15AJ22G and #80NSSC19K0509, and NSF grants #1531243 and #0619599. Fig 2. STEM data on ‘Spud’. HAADF Image (Top) False-color EDS Maps (Bottom) References: [1] MacPherson G. J. (2014) T. of Geochem. Vol I: Met. And Cosmochem. Processes, 139-179. [2] Lodders K. (2003) ApJ, 591, 1220-1247. [3] Ebel D. S. (2006) Met. & the Early S. Sys. II., 253- 277. [4] Amelin Y. (2002) Science, 297, 1678-1683. [5] Connelly J.N. et.al. (2012) Science, 338, 651-655. [6] Schwander D. et al. (2015) GCA, 18, 70-87. [7] Palme H. and Wlotzka F. (1976) EPSL, 33, 45-60. [8] Berg T. et al. (2009) ApJ, 702, 172-176. [9] Liffman K. et al. (2021) Icarus, 221, 89-105. [10] Zega T.J. et al. (2021) PSJ, 2, 115. [11] Ramprasad T. et al. (2020) LPSC LI, Abstract #2472. [12] Ramprasad T. et al. (2021) Microscopy & Microanalysis, S1, 2792-2794. [13] Ramprasad T. et al. (2021) 84th MetSoc, Abstract #6123. [14] Zega T.J. et al. (2007) MAPS, 42, 1373-1386. [15] Ramprasad T. et al. (2022) MAPS, in revision. [16] Grossman L. (1975), GCA, 39, 433-454. [17] El Goresy A. et al. (1978) LPSC IX, Abstract#1100

T. Ramprasad↗

The role of nickel content and the magnetic remanence in iron-nickel alloys of lunar composition

Lunar samples are magnetic primarily due to the body centered cubic (BCC) iron and iron-nickel alloys they contain. Presented for the first time are results which demonstrate that the magnitude of the martensitic thermal remanence (MTRM) induced on quenching iron-nickel alloy in the geomagnetic field depends on the nickel content of the alloy. High magnetic stability is due to the increasing dislocation density and increasingly complex microstructures associated with increasing nickel content in the alloys. The results agree with the mechanical and structural properties of the alloys. The characteristic quench martensite microstructure observed on metallographic examination provides a recognition criterion for the MTRM mechanism. These results are important for lunar and meteoritic research intending to ascertain the paleofield responsible for the observed remanent magnetization.-

Wasilewski, P.↗

Development of materials and process technology for dual alloy disks

Techniques for the preparation of dual alloy disks were developed and evaluated. Four material combinations were evaluated in the form of HIP consolidated and heat treated cylindrical and plate shapes in terms of elevated temperature tensile, stress rupture and low cycle fatigue properties. The process evaluation indicated that the pe-HIP AF-115 rim/loose powder Rene 95 hub combination offered the best overall range of mechanical properties for dual disk applications. The feasibility of this dual alloy concept for the production of more complex components was demonstrated by the scale up fabrication of a prototype CFM-56 disk made from this AF-115/Rene 95 combination. The hub alloy ultimate tensile strength was approximately 92 percent of the program goal of 1520 MPa (220 ksi) at 480 C (900 F) and the rim alloy stress rupture goal of 300 hours at 675 C (1250 F)/925 MPa (134 ksi) was exceeded by 200 hours. The low cycle fatigue properties were equivalent to those exhibited by HIP and heat treated alloys. There was an absence of rupture notch sensitivity in both alloys. The joint tensile properties were approximately 85 percent of the weaker of the two materials (Rene 95) and the stress rupture properties were equivalent to those of the weaker of the two materials (Rene 95).

Marder, J. M.↗

Hot corrosion of the B2 nickel aluminides

The hot corrosion behavior of the B2 nickel aluminides was studied to determine the inherent hot corrosion resistance of the beta nickel aluminides and to develop a mechanism for the hot corrosion of the beta nickel aluminides. The effects of the prior processing of the material, small additions of zirconium, stoichiometry of the materials, and preoxidation of the samples were also examined. Additions of 2, 5, and 15 w/o chromium were used to determine the effect of chromium on the hot corrosion of the beta nickel aluminides and the minimum amount of chromium necessary for good hot corrosion resistance. The results indicate that the beta nickel aluminides have inferior inherent hot corrosion resistance despite their excellent oxidation resistance. Prior processing and zirconium additions had no discernible effect on the hot corrosion resistance of the alloys. Preoxidation extended the incubation period of the alloys only a few hours and was not considered to be an effective means of stopping hot corrosion. Stoichiometry was a major factor in determining the hot corrosion resistance of the alloys with the higher aluminum alloys having a definitely superior hot corrosion resistance. The addition of chromium to the alloys stopped the hot corrosion attack in the alloys tested. From a variety of experimental results, a complex hot corrosion mechanism was proposed. During the early stages of the hot corrosion of these alloys the corrosion is dominated by a local sulphidation/oxidation form of attack. During the intermediate stages of the hot corrosion, the aluminum depletion at the surface leads to a change in the oxidation mechanism from a protective external alumina layer to a mixed nickel-aluminum spinel and nickel oxide that can occur both externally and internally. The material undergoes extensive cracking during the later portions of the hot corrosion.

Ellis, David L.↗