Plastic deformation induced microstructure transition in nano-fibrous Al-Si eutectics
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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.
This study investigates the effect of mechanical cold work (0, 50, and 90% cross-sectional area reduction via swaging) on the creep properties of cast aluminum alloys with high electrical conductivity including high-purity Al (HP-Al), Al-0.15Zr (Al-Zr), and Al-0.27Zr-0.08Sn (Al-Zr-Sn, wt%). The Al-Zr alloy is strengthened by Zr in solid solution while the Al-Zr-Sn alloy is additionally strengthened by Al3Zr nanoprecipitates (8 nm diameter). After 90% cold swaging, the alloys exhibit grains elongated along the swaging direction with their widths ranging between 8 and 152 μm perpendicular to the swaging direction. Creep testing at 200 °C shows that the minimum creep rate of all 90% swaged alloys shows high sensitivity to stress, which can be modeled via a threshold stress σth. Increasing swaging magnitude from 0 to 50 to 90% in Al-Zr-Sn improves the creep resistance without reducing electrical conductivity. The formation of subgrains, increased dislocation density, and columnar grain structure in swaged alloys all enhance creep resistance. HP-Al swaged to 90% exhibits much lower creep resistance (σth = 18 MPa) due to subgrain coarsening and the absence of precipitates compared to Al-Zr (σth = 40 MPa) and Al-Zr-Sn (σth = 40 MPa), which maintain stable subgrain structures and benefit from solid solution strengthening and Al3Zr nanoprecipitates, respectively. Although Al3Zr precipitates are known to stabilize the deformed microstructure by pinning grain-boundaries, this work demonstrates that Zr in solid solution alone can effectively stabilize the deformed microstructure resulting in enhanced creep resistance. This effect of Zr solute on stabilizing grain boundaries for creep performance was not previously well-defined in the literature. Despite similar creep performances of Al-Zr and Al-Zr-Sn, the latter shows 70% higher room-temperature microhardness and slightly improved electrical conductivity (56%IACS (International Annealed Copper Standard) vs. 57%IACS, respectively). This work provides new insights into creep mechanisms of cold-worked Al–Zr alloys that will guide the design of heat-resistant Al conductors for high-demand applications.
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.
Surface abrasion has been shown to introduce heavy shear stress and produce a few hundred nanometers thick altered surface layer (ASL) on Al alloys. Such ASLs exhibit microstructural changes at room temperature and different corrosion resistance than the underlying substrate. Here, we report how sample dimensions and temperature affect the deformed subsurface microstructure evolution on an abraded Al–Zn–Mg–Cu alloy using transmission electron microscopy (TEM) and atom probe tomography. The ASL microstructure evolves differently in the bulk sample than in the thin TEM specimen. In the freshly abraded ASL, the original η'/η precipitates and grain boundaries were deformed toward the abrasion direction. After 7-day natural aging of the freshly abraded bulk sample, well-defined subgrains formed locally in the ASL, and unusual Al 2 Cu (θ) and Mg x Zn y phases precipitated at the subgrain boundaries. However, during natural aging of this TEM specimen taken from the abraded and aged bulk samples, much faster changes occurred, including the continued formation of subgrains and θ particles in the entire ASL, and the diffusion of Zn atoms out of Mg x Zn y particles to form a Zn particle. On the other hand, no obvious microstructural changes occurred in the ASL during 3-month natural aging of the TEM specimen immediately taken from the freshly abraded sample. Finally, this work advances the understanding of how Al alloy microstructures respond during and following any shear deformation, and complex and unexpected effects of sample dimensions on the behavior.
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.
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.
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.
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.
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.
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.
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.
Here, a CrCoNi based medium entropy alloy with small additions of Ti, Al and Nb (denoted as (CrCoNi) 93 Al 4 Ti 2 Nb) in the as-quenched condition, exhibits tensile properties comparable to those of the equiatomic CrCoNi alloy at room temperature. Dark field transmission electron microscopy (TEM), atomic resolution high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) together with atom probe tomography (APT) show that spatially-localized long range ordering (LRO) L1 2 domains exist in this alloy. The evolution of deformation substructure with plastic deformation in this alloy was characterized using electron backscatter diffraction (EBSD), electron channeling contrast imaging (ECCI) and STEM based techniques including the recently developed weak beam dark field STEM imaging. Plastic deformation occurs by the slip of a/2<110>dislocations, which are narrowly dissociated into Shockley partial dislocations on {111} slip planes. Their dissociation distances in the (CrCoNi) 93 Al 4 Ti 2 Nb alloy are much smaller than the widths of the corresponding partials in the equiatomic CrCoNi alloy due to one or more of the minor alloying elements (Al, Ti, Nb). Dislocation slip in this alloy has a pronounced planar character. The leading dislocations in slip bands glide as pairs due to the existence of LRO domains. Multipoles were formed through the slip of dislocations with opposite signs on adjacent {111} slip planes. Those multipoles serve as building blocks for the formation of subgrain structures consisting of fine slip bands. The distances between slip bands were continuously refined during plastic deformation and dynamic refinement of slip bands plays a crucial role in strain hardening. The effects of LRO domains on planar dislocation slip, the deactivation of deformation twinning and strain hardening of this alloy are discussed.
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.
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.
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.
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.
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.