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The corrosion behavior of the T1 (Al2CuLi) intermetallic compound in aqueous environments

The intermetallic compound T1 (Al2CuLi) is suspected to play an important role in the localized corrosion at subgrain boundaries in Al-Li-Cu alloys. The intermetallic was synthesized for characterization of its corrosion behavior. Experiments performed included open circuit potential measurements, potentiodynamic polarization, and corrosion rate vs. pH in solutions whose pH was varied over the range of 3 to 11. Subgrain boundary pitting and continuous subgrain boundary corrosion are discussed in terms of the data obtained. Evidence suggesting the dealloying of copper from this compound is also presented.

Buchheit, R. G.↗

Microstructural development of protective Al2O3 scales

Microstructural characteristics of Al2O3 scales grown as protective coatings on NiCrAl alloys used in jet engines are described. The alloys were pure or doped with 0.3 percent Zr or Y and oxidized in 1 atm air at 1100 C for 0.1, 1 or 20.0 hr. The scales were then examined under a microscope. Transient epitaxial scales, formed during the 0.1 hr treatment and containing Ni, Cr and Al, consisted of a mosaic of subgrains and precipitates of different phases. The Y and Zr dopants had no effect on the nucleation site locations. The appearance of intergranular porosity at 0.1 hr was exacerbated after the 1 hr treatment. A bimodal void distribution appeared after 20 hr, when no porosity was evident. The detection of local areas of preferred orientation is taken as a spur to further studies of scale growth to gain control of the grain size or even to produce single crystal scales.

Smialek, J. L.↗

The effects of zinc addition on the environmental stability of Al-Li alloys

It was found that relatively small addition of Zn can improve the stress corrosion cracking (SCC) resistance of Al-Li alloys. However, the mechanism by which this is accomplished is unclear. The role that Zn plays in altering the behavior of Alloy 8090 is investigated. Early results suggest that Zn additions increase the volume fraction of delta(Al3Li) precipitation and differential scanning calorimetry (DSC) on these alloys confirms this. The four alloys studied each had initial compositions lying in the 8090 window and had varying amounts of Zn added to them. Alloy 8090, like other Al-Li alloys, displays a delta' precipitate free zone (PFZ) upon artificial aging along the grain and subgrain boundaries. However Zn additions greatly decreased or eliminated a delta' PFZ after 100 hours at 160 C. This implies that the subgrain boundary precipitation kinetics are being altered and suppressed. Furthermore, there appears to be a window of Zn concentration above which a delta ' PFZ can reappear with the nucleation and growth of a currently unidentified precipitate on the boundaries. Polarization experiments were performed and the results presented. The experiments were performed in deaerated 3.5 w/o NaCl in both as received (T3) condition and at peak aging of 100 hours at 160 C. The aging profile was determined via Vickers Hardness tests.

Kilmer, Raymond J.↗

Time-Temperature-Precipitation Behavior in Al-Li Alloy 2195

Transmission electron microscopy was used to study time-temperature-precipitation (TTP) behavior in aluminum-lithium (Al-Li) 2195 alloy. Al-Li 2195 (nominally Al + 4 percent Cu + 1 percent Li + 0.3 percent Ag + 0.3 percent Mg + 0.1 percent Zr) was initially solutionized for 1 hr at 950 F and then stretched 3 percent. Heat treatments were conducted for up to 100 hr at temperatures ranging from 200 to 1,000 F. TTP diagrams were determined for both matrix and subgrain boundaries. Depending upon heat treatment conditions, precipitate phases (such as GP zone, theta'', theta', theta, delta', T1, TB, and T2) were found in the alloy. The TTP diagrams were applied as a guide to avoid T1 precipitation at subgrain boundaries, as part of an effort to improve the alloy's cryogenic fracture toughness (CFT). New understanding of TTP behavior was instrumental in the development of a two-step artificial aging treatment that significantly enhanced CFT in Al-Li 2195.

Chen, P. S.↗

Microstructure of Al2O3 scales formed on NiCrAl alloys

The structure of transient scales formed on pure and Y or Zr-doped Ni-15Cr-13Al alloys oxidized for 0.1 hr at 1100 C was studied by the use of transmission electron microscopy. Crystallographically oriented scales were found on all three alloys, but especially for the Zr-doped NiCrAl. The oriented scales consisted of alpha-(Al,Cr)2O3, Ni(Al,Cr)2O4 and gamma-Al2O3. They were often found in intimate contact with each other such that the close-packed planes and directions of one oxide phase were aligned with those of another. The prominent structural features of the oriented scales were approximately equal to micrometer subgrains; voids, antiphase domain boundaries and aligned precipitates were also prevalent. Randomly oriented alpha-Al2O3 was also found and was the only oxide ever observed at the immediate oxide metal interface. These approximately 0.15 micrometer grains were populated by intragranular voids which decreased in size and number towards the oxide metal interface. A sequence of oxidation was proposed in which the composition of the growing scale changed from oriented oxides rich in Ni and Cr to oriented oxides rich in Al. At the same time the structure changed from cubic spinels to hexagonal corundums with apparent precipitates of one phase in the matrix of the other. Eventually randomly oriented pure alpha-Al2O3 formed as the stable oxide with an abrupt transition: there was no gradual loss of orientation, no gradual compositional change or no gradual decrease in precipitate density.

Smialek, J. L.↗

Dispersion strengthening of precipitation hardened Al-Cu-Mg alloys prepared by rapid solidification and mechanical alloying

Several Al-4Cu-1Mg-1.5Fe-0.75Ce alloys have been processed from either rapidly solidified or mechanically alloyed powder using various vacuum degassing parameters and consolidation techniques. Strengthening by the fine subgrains, grains, and the dispersoids individually or in combination is more effective when the alloys contain shearable precipitates; consequently, the strength of the alloys is higher in the naturally aged rather than the artificially aged condition. The strengths of the mechanically alloyed variants are greater than those produced from prealloyed powder. Properties and microstructural features of these dispersion strengthened alloys are discussed in regards to their processing histories.

Gilman, P. S.↗

The effect of zinc additions on the environmental stability of Alloy 8090 (Al-Li-Cu-Mg-Zr)

Stress corrosion cracking (SCC) remains a problem in both Al-Li and conventional Al heat treatable alloys. It has recently been found that relatively small additions (less than or approximately 1 wt-percent) of Zn can dramatically improve the SCC performance of alloy 8090 (Al-Li-Cu-Mg-Zr). Constant load time to failure experiments using cylindrical tensile samples loaded between 30 and 85 percent of TYS indicate improvements of orders of magnitude over the baseline 8090 for the Zn-containing alloys under certain aging conditions. However, the toughnesses of the alloys were noticeably degraded due to the formation of second phase particles which primarily reside on grain and subgrain boundaries. EDS revealed that these intermetallic particles were Cu and Zn rich. The particles were present in the T3 condition and were not found to be the result of quench rate, though their size and distribution were. At 5 hours at 160 C, the alloys displayed the greatest susceptibility to SCC but by 20 hours at 160 C the alloys demonstrated markedly improved TTF lifetimes. Aging past this time did not provide separable TTF results, however, the alloy toughnesses continued to worsen. Initial examination of the alloys microstructures at 5 and 20 hours indicated some changes most notably the S' and delta' distributions. A possible model by which this may occur will be explored. Polarization experiments indicated a change in the trend of E(sub BR) and passive current density at peak aging as compared to the baseline 8090. Initial pitting experiments indicated that the primary pitting mechanism in chloride environments is one occurring at constituent (Al-Fe-Cu) particles and that the Cu and Zn rich boundary precipitates posses a breakaway potential similar to that of the matrix acting neither anodic or cathodic in the first set of aerated 3.5 w/o NaCl experiments. Future work will focus on the identification of the second phase particles, evaluation of K(sub 1SCC) and plateau da/dt via both DCB and slow strain rate techniques. A lower Zn content variant will be examined in the near future in hopes of optimizing toughness, density and SCC performance.

Kilmer, Raymond J.↗

Environmental fatigue of an Al-Li-Cu alloy. Part 2: Microscopic hydrogen cracking processes

Based on a fractographic analysis of fatigue crack propagation (FCP) in Al-Li-Cu alloy 2090 stressed in a variety of inert and embrittling environments, microscopic crack paths are identified and correlated with intrinsic da/dN-delta K kinetics. FCP rates in 2090 are accelerated by hydrogen producing environments (pure water vapor, moist air, and aqueous NaCl), as defined in Part 1. For these cases, subgrain boundary fatigue cracking (SGC) dominates for delta K values where the crack tip process zone, a significant fraction of the cyclic plastic zone, is sufficiently large to envelop 5 micron subgrains in the unrecrystallized microstructure. SGC may be due to strong hydrogen trapping at T1 precipitates concentrated at sub-boundaries. At low delta K, the plastic zone diameter is smaller than the subgrain size and FCP progresses along (100) planes due to either local lattice decohesion or aluminum-lithium hydride cracking. For inert environments (vacuum, helium, and oxygen), or at high delta K where the hydrogen effect on da/dN is small, FCP is along (111) slip planes; this mode does not transition with increasing delta K and plastic zone size. The SGC and (100) crystallographic cracking modes, and the governing influence of the crack tip process zone volume (delta K), support hydrogen embrittlement rather than a surface film rupture and anodic dissolution mechanism for environmental FCP. Multi-sloped log da/dN-log delta K behavior is produced by changes in process zone hydrogen-microstructure interactions, and not by purely micromechanical-microstructure interactions, in contradiction to microstructural distance-based fatigue models.

Robert S Piascik↗

Effect of composition and grain size on slow plastic flow properties of NiAl between 1200 and 1400 K

A series of about 15-micron diameter polycrystalline B2 crystal structure NiAl alloys ranging in composition from 43.9 to 52.7 Al (at. pct) have been compression tested at constant velocities in air between 1200 and 1400 K. All materials were fabricated via powder metallurgy techniques with hot extrusion as the densification process. Seven intermediate compositions were produced by blending various amounts of two master heats of prealloyed powder; in addition, a tenth alloy of identical composition, 48.25 Al, as one of the blended materials, was produced from a third master heat. Comparison of the flow stress-strain rate behavior for the two 48.25 Al alloys revealed that their properties were identical. The creep strength of materials for Al/Ni not above 1.03 was essentially equal, and deformation could be described by a single stress exponent and activation energy. Creep at low temperatures and faster strain rates is independent of grain sizes and appears to be controlled by a subgrain mechanism. However, at higher temperatures and slower strain rates, diffusional creep seems to contribute to the overall deformation rate.

Whittenberger, J. Daniel↗

The effect of trace additions of Zn on the precipitation behavior of alloy 8090 during artificial aging

The effect(s) of trace additions of Zn to the artificial aging behavior of alloy 8090 (Al-Li-Cu-Mg-Zr) was investigated in the approximate composition range 0-1 wt-pct Zn. Trace Zn additions were found to delay aging and under equivalent aging treatments (100 hrs at 160 C) the alloy without Zn and the 1.07 wt-pct Zn alloy developed delta-prime-free zones along subgrain boundaries, while the alloys of 0.21 and 0.58 wt-pct Zn did not. DSC analysis indicated that Zn was being incorporated into the delta-prime, shifting it's exotherm to higher temperatures, while having little if any effect on its associated endotherm making it unlikely that it is an artifact of a solvus shift. In the 8090 + 1.07 wt-pct Zn alloy, coarse precipitates were found to reside on subgrain boundaries and EDS indicated that they were rich in Cu and Zn. It was also noted that in the Zn containing 8090 varients, the S prime precipitates were more coarse in size than the baseline 8090.

Kilmer, R. J.↗

Time Temperature-Precipitation Behavior in An Al-Cu-Li Alloy 2195

Al-Cu-Li alloy 2195, with its combination of good cryogenic properties, low density, and high modulus, has been selected by NASA to be the main structural alloy of the Super Light Weight Tank (SLWT) for the Space Shuttle. Alloy 2195 is strengthened by an aging treatment that precipitates a particular precipitate, labeled as T1(Al2CuLi). Other phases, such as GP zone, (theta)', (theta)", theta, (delta)', S' are also present in this alloy when artificially aged. Cryogenic strength and fracture toughness are critical to the -SLWT application, since the SLWT will house liquid oxygen and hydrogen. Motivation for the Time-Temperature-Precipitation (TTP) study at lower temperature (lower than 350 F) comes in part from a recent study by Chen, The study found that the cryogenic fracture toughness of alloy 2195 is greatly influenced by the phases present in the matrix and subgrain boundaries. Therefore, the understanding of TTP behavior can help develop a guideline to select appropriate heat treatment conditions for the desirable applications. The study of TTP behavior at higher temperature (400 to 1000 F) was prompted by the fact that the SLWT requires a welded construction. Heat conduction from the weld pool affects the microstructure in the heat-affected zone (HAZ), which leads to changes in the mechanical properties. Furthermore, the SLWT may need repair welding for more than one time and any additional thermal cycles will increase precipitate instability and promote phase transformation. As a result considerable changes in HAZ microstructure and mechanical properties are expected during the construction of the SLWT. Therefore, the TTP diagrams can serve to understand the thermal history of the alloy by analyzing the welded microstructure. In the case welding, the effects of thermal cycles on the microstructure and mechanical properties can be predicted with the aid of the TTP diagrams. The 2195 alloy (nominally Al + 4 pct Cu + 1 pct Li + 0.3 pct Ag + 0.3 pct Mg + 0.1 pct Zr) used in this study was received in the form of 1.7 inch thick rolled plates. In brief goal of this study is to develop TTR diagram for the solutiontreated and stretched alloy 2195 from which the precipitation sequence at any service or aging conditions can be preducted.A subgrain boundary TTR diagram is also presented since precipitations at subgrain boundary can control and/or modify a wide veriety of material properties, such as cryogenic fracture toughness.

Chen, P. S.↗

Environmental fatigue of an Al-Li-Cu alloy. Part 3: Modeling of crack tip hydrogen damage

Environmental fatigue crack propagation rates and microscopic damage modes in Al-Li-Cu alloy 2090 (Parts 1 and 2) are described by a crack tip process zone model based on hydrogen embrittlement. Da/dN sub ENV equates to discontinuous crack advance over a distance, delta a, determined by dislocation transport of dissolved hydrogen at plastic strains above a critical value; and to the number of load cycles, delta N, required to hydrogenate process zone trap sites that fracture according to a local hydrogen concentration-tensile stress criterion. Transgranular (100) cracking occurs for process zones smaller than the subgrain size, and due to lattice decohesion or hydride formation. Intersubgranular cracking dominates when the process zone encompasses one or more subgrains so that dislocation transport provides hydrogen to strong boundary trapping sites. Multi-sloped log da/dN-log delta K behavior is produced by process zone plastic strain-hydrogen-microstructure interactions, and is determined by the DK dependent rates and proportions of each parallel cracking mode. Absolute values of the exponents and the preexponential coefficients are not predictable; however, fractographic measurements theta sub i coupled with fatigue crack propagation data for alloy 2090 established that the process zone model correctly describes fatigue crack propagation kinetics. Crack surface films hinder hydrogen uptake and reduce da/dN and alter the proportions of each fatigue crack propagation mode.

Piascik, Robert S.↗

Elevated Temperature Deformation of Fe-39.8Al and Fe-15.6Mn-39.4Al

The elevated temperature compressive properties of binary Fe-39.8 at % Al and Fe-15.6Mn-39.4Al have been measured between 1000 and 1300 K at strain rates between 10(exp 7) and 10(exp 3)/ s. Although the Mn addition to iron aluminide did not change the basic deformation characteristics, the Mn-modified alloy was slightly weaker. In the regime where deformation of FeAl occurs by a high stress exponent mechanism (n = 6), strength increases as the grain size decreases at least for diameters between approx. 200 and approx. 10 microns. Due to the limitation in the grain size-flow stress-temperature-strain rate database, the influence of further reductions of the grain size on strength is uncertain. Based on the appearance of subgrains in deformed iron aluminide, the comparison of grain diameters to expected subgrain sizes, and the grain size exponent and stress exponent calculated from deformation experiments, it is believed that grain size strengthening is the result of an artificial limitation on subgrain size as proposed by Sherby, Klundt and Miller.

Whittenberger, J. Daniel↗

Surface and Internal Structure of Pristine Presolar Silicon Carbide

Silicon carbide is the most well-studied type of presolar grain. Isotope measurements of thousands [1,2] and structural data from over 500 individual grains have been reported [3]. The isotope data indicate that approximately 98% originated in asymptotic giant branch stars and 2% in supernovae. Although tens of different polytypes of SiC are known to form synthetically, only two polytypes have been reported for presolar grains. Daulton et al. [3] found that for SiC grains isolated from Murchison by acid treatments, 79.4% are 3C cubic beta-SiC, 2.7% are 2H hexagonal alpha-SiC, 17.1% are intergrowths of and , and 0.9% are heavily disordered. They report that the occurrence of only the and polytypes is consistent with the observed range of condensation temperatures of circumstellar dust for carbon stars. Further constraint on the formation and subsequent alteration of the grains can be obtained from studies of the surfaces and interior structure of grains in pristine form, i.e., prepared without acid treatments [4,5]. The acid treatments remove surface coatings, produce etch pits around defect sites and could remove some subgrains. Surface oxides have been predicted by theoretical modeling as a survival mechanism for SiC grains exposed to the hot oxidizing solar nebula [6]. Scanning electron microscopy studies of pristine SiC shows some evidence for the existence of oxide and organic coatings [4]. We report herein on transmission electron microscopy studies of the surface and internal structure of two pristine SiC grains, including definitive evidence of an oxide rim on one grain, and the presence of internal TiC and AlN grains.

Stroud, Rhonda, M.↗

Temperature effects on the deformation and fracture of Al-Li-Cu-In alloys

The crack initiation and growth fracture resistance of Al-Cu-Li and Al-Cu-Li-In alloys were characterized and optimized for cryogenic tank applications. Presently, the effects of stress state and temperature is being determined on the fracture toughness and fracture mechanisms of commercially available Vintage 3 2090-T81 and experimental 2090+In-T6. Precracked J-integral specimens of both alloys were tested at ambient and cryogenic temperatures in the plane stress and plane strain conditions. Considering ambient temperature, results showed that 2090-T81 exhibited the highest toughness in both plane strain and plane stress conditions. For the plane strain condition, reasonable crack initiation and growth toughness of 1090-T81 are associated with a significant amount of delamination and transgranular fracture. Plane stress toughnesses were higher and fracture was characterized by shear cracking with minimal delaminations. In comparisons, the fracture behavior of 2090+In-T6 is significantly degraded by subgrain boundary precipitation. Toughness is low and characterized by intersubgranular fracture with no delamination in the plane stress or plane strain conditions. Intersubgranular cracking is a low energy event which presumably occurs prior to the onset of slip band cracking. Copious grain boundary precipitation is atypical of commercially available 2090. At cryogenic temperatures, both alloys exhibit increased yield strength, toughness, and amount of delamination and shear cracking. The change in fracture mode of 2090+In-T6 from intersubgranular cracking at ambient temperature to a combination of intersubgranular cracking, shear cracking, and delamination at cryogenic temperature is the subject of further investigation.

Wagner, John A.↗

Organic Nano-Grains in Comet 103P/Hartley 2: The Organic Glue of Porous Aggregate Grains?

The GNIRS instrument on the Gemini 8-­‐m telescope observed comet 103P/Hartley on 2010-­‐ Dec-­‐04UT, a month after the EPOXI Mission encounter, and detected the 3.3 and 3.4 um bands in emission. The 3.3/3.4 ratio and the broad band widths are consistent with experiments of heated (approximately 600 K) aliphatic carbon (-CH3, -CH2) thin films. For the 3.4 micron band to be in emission, the aliphatic bonds must be attached to a carrier possessing the strongly UV-­‐absorbing C=C aromatic rings, and these rings have to be less than 50-­‐100 carbon atoms (4-6 Angstrom) for attached -CH bonds to also generate a 3.3 micron-band in emission. Slightly larger (≥10Å) Very Small Grains (VSGs) can absorb single UV photons comparable to or exceeding their heat capacity, thermally fluctuate and release IR photon(s). The 3.3 micron and 3.4 micron bands observed by GNIRS suggest that organic macromolecules/ nano-­‐grains with both aliphatic and aromatic bonds are fluorescing/thermally fluctuating in the coma. Aliphatic and aromatic materials have been seen in Stardust samples and the primitive carbonaceous chondrite 'Tagish Lake'. The larger the ratio of the -CH2/-CH3 components of the aliphatic 3.4 micron band, the more 'primitive' the organic material. In a Stardust organic globule, some aliphatic bonds were transformed into aromatic bonds during the low dosage of Transmission Electron Microscope imaging. Conversely, lab experiments show irradiation of ices containing small PAHs generates aliphatic organics. Photo-­‐processing of ices also likely forms the ubiquitous aliphatic coatings that appear on the surfaces of all silicate subgrains constituting nine cometary interplanetary dust particles. The aliphatic coatings, dominated by -CH2, likely were important in sticking the aggregates together, and existed prior to incorporation of dust aggregates into comet nuclei. These comet aliphatics may be some of the sought-­‐after precursors to the more robust and complex organics studied as Insoluble Organic Matter in carbonaceous chondrites. Aliphatic coatings on submicron grains, however, will not be observable in absorption because they are fairly transparent, nor do the aliphatic carbonaceous coatings produce the 3.4 micron emission band because the particles they are attached to are too large (too many vibration modes). We must probe the nano-­‐sized organic carriers that undergo substantive thermal fluctuations in cometary comae and emit at 3.3 3.4 micron. Observations of the 3.3 and 3.4 micron emission features contribute to characterizing the evolution of organics prior to their incorporation into cometary nuclei as well as their rapid evolution in cometary comae, which in turn contributes to deepening our understanding of the evolution of organics on the surfaces of asteroids and outer icy bodies in our solar system. Studying organics in comets contributes to understanding the formation and evolution pathways of ISM organics through to the formation of the robust insoluble organic matter in meteorites. A'Hearn, M.F., et al. 2011, Science, 332, 1396; Bockelee-­‐Morvan, D. et al. 1995, Icarus, 116, 18; De Gregorio, B.T., et al. 2010, GCA, 74, 4454; Dello Russo, N., et al. 2011, ApJ, 734, L8; Dischler et al. 1983, Solid State Communications, 48, 105; Flynn, G., et al. 2010a, LPSC, 41, #1079; Flynn, G., et al. 2010b, COSPAR, 38, F31-­‐0012-­‐10; Flynn, G., Wirick, S. 2011, LPSC, 42, #1856; Fomenkova, et al. 1994, GCA 58, 4503; Matrajt, G., et al. 2013, ApJ, 765, 145; Schutte, et al. 1993, ApJ, 415, 397; Wooden, D.H. et al. 2011, EPSC-­‐DPS, 1557; Wooden, D.H. et al. 2013, submitted.

Stardust samples↗