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At least 91 records · Page 5

Decoding anomalous grain growth at room temperature during pressure-induced phase transformations

Significant grain growth is observed during the high-pressure phase transformations (PTs) at room temperature in various materials. The main focus here is grain growth from a few hundred nanometers to 10 μm within an hour during α → ω PT in Zr. No existing theory explains this phenomenon since without PT, Zr nanocrystals do not grow at room temperature even for up to 10 years. Here, in this study, a multistep mechanism for the grain growth during α → ω PT in Zr is suggested. Phase interfaces (PI) and grain boundaries (GBs) coincide and move together as a combined PI-GBs under the action of the combined thermodynamic driving force. Such a combined motion changes the diffusional grain growth mechanism to the transformational one and the martensitic mechanism of PT to a reconstructive one via an intermediate disordered phase. The primary condition is that the GB energy of the ω phase is smaller than that of the α phase, which promotes the nucleation of ω-Zr and is consistent with the absence of the reverse PT and reduction in the PT pressure with reducing grain size. Several intermediate steps for such motion are suggested and justified kinetically. Nonhydrostatic stresses due to volume reduction in the growing ω grain promote continuous growth of the existing ω grain instead of a new nucleation at other GBs. In situ synchrotron Laue diffraction experiments confirm the main predictions of the theory. The suggested mechanism provides a new insight into synergistic interaction between PTs and microstructure evolution.

anomalous grain growth during phase transformation↗

High-surface-area corundum nanoparticles by resistive hotspot-induced phase transformation

Abstract High-surface-area α-Al 2 O 3 nanoparticles are used in high-strength ceramics and stable catalyst supports. The production of α-Al 2 O 3 by phase transformation from γ-Al 2 O 3 is hampered by a high activation energy barrier, which usually requires extended high-temperature annealing (~1500 K, > 10 h) and suffers from aggregation. Here, we report the synthesis of dehydrated α-Al 2 O 3 nanoparticles (phase purity ~100%, particle size ~23 nm, surface area ~65 m 2 g −1 ) by a pulsed direct current Joule heating of γ-Al 2 O 3 . The phase transformation is completed at a reduced bulk temperature and duration (~573 K, < 1 s) via an intermediate δʹ-Al 2 O 3 phase. Numerical simulations reveal the resistive hotspot-induced local heating in the pulsed current process enables the rapid transformation. Theoretical calculations show the topotactic transition (from γ- to δʹ- to α-Al 2 O 3 ) is driven by their surface energy differences. The α-Al 2 O 3 nanoparticles are sintered to nanograined ceramics with hardness superior to commercial alumina and approaching that of sapphire.

Deng, Bing (ORCID:0000000305308410)↗

Heterogeneous phase transformation pathways in additively manufactured Al-Ce-Mn alloys

Heat treatment of additively manufactured Al-Ce based multicomponent alloys leads to complex microstructure evolution. In this research, the ability to extend the phase transformation theories involving nucleation of a product phase from a heterogeneous multi-phase microstructure typical to that of additively manufactured samples is explored. The Al-10Ce-8Mn (wt%) was used as a model alloy system. Under additive manufacturing conditions different solidification microstructures were obtained due to spatial and temporal variations of thermal gradients (G) and liquid-solid interface velocities (R) within a given melt pool. Near the melt pool boundary (high G and low R, referred as MPB region), initially, Al 20 Mn 2 Ce forms from the liquid followed by a eutectic of FCC Al and Al 11 Ce 3 . In the melt pool interiors (low G and high R referred as ES region) a eutectic structure between FCC Al and Al 20 Mn 2 Ce is observed. During subsequent heat treatments, the MPB and ES regions transform into different sets of microstructures. In the MPB region, a fine globular microstructure containing FCC Al, Al 11 Ce 3 , Al 6 Mn, and Al 12 Mn results from the decomposition of Al 20 Mn 2 Ce. In the ES region a faceted Al 51 Mn 7 Ce 4 plate phase results from the decomposition of Al 20 Mn 2 Ce. The formation of the Al 51 Mn 7 Ce 4 phase within the eutectic microstructure at the boundaries of FCC Al and Al 20 Mn 2 Ce has not been reported in the literature. Further, these two distinct phase transformation pathways are rationalized based on the role of driving force on the nucleation of (Al 6 Mn) and/or metastable intermetallic (Al 51 Mn 7 Ce 4 ) phases at the interface of aluminum (FCC) and the non-equilibrium intermetallic (Al 20 Mn 2 Ce) phases.

36 MATERIALS SCIENCE↗

Mechanism of the gamma-beta phase transformation of Mg2SiO4 at high temperature and pressure

The results of experiments on the phase transformation of Mg2SiO4 olivine at 15 GPa pressure in a multianvil cell are reported. At this pressure and a temperature of 900 C, early formed metastable gamma-spinel transforms partially to the beta-phase. The observed microstructures, which are similar to those in shocked meteorites, show that the gamma-to-beta transformation can occur either by diffusion-controlled growth or by a martensitic mechanism, depending on how far the pressure-temperature conditions deviate from their values at phase equilibrium. The results suggest that the diffusion-controlled mechanism is most likely to operate at the beta/gamma phase boundary in the mantle, but martensitic beta-to-gamma transformation might occur in subduction zones and could reduce the shear strength of the subducting slab.

Rubie, D. C.↗

In Situ X-ray Diffraction Investigation of Hydrogen Effects on Deformation-Induced Phase Transformation in Forged and Additively Manufactured 304L Stainless Steels

Here, this study utilized high energy synchrotron x-ray diffraction to probe microstructural evolution during uniaxial deformation of conventionally manufactured and additively manufactured (AM) 304L stainless steel with and without internal hydrogen. The objective of this effort is to highlight the effect of hydrogen on deformation-induced martensite phase transformations in austenitic stainless steels. Solute hydrogen depresses the required applied strain to initiate austenite transformation to ε-martensite and α'-martensite in both forged and AM stainless steel. Similarly, the total fraction of transformation product is larger when the microstructure is saturated with hydrogen. Deformation induced phase transformations also lead to a variation in strain partitioning behavior, which is linked to the chemical composition and stacking fault energy of the starting and hydrogen-charged materials.

36 MATERIALS SCIENCE↗

Energy Conversion from Heat to Electricity by Highly Reversible Phase-Transforming Ferroelectrics

The search for performant multiferroic materials has attracted general research interest in energy science as they have been increasingly exploited as the conversion media among thermal, electric, magnetic, and mechanical energies by using their temperature-dependent ferroic properties. Here we report a material development strategy that guides us to discover a reversible phase-transforming ferroelectric material exhibiting enduring energy harvesting from small temperature differences. The material satisfies the crystallographic compatibility condition between polar and nonpolar phases, which shows only 2.5°C thermal hysteresis and a high figure of merit. It stably generates 15μA of electricity in consecutive thermodynamic cycles in the absence of any bias fields. We demonstrate our device to consistently generate 6μA/cm 2 current density near 100°C over 540 complete phase transformation cycles without any electric and functional degradation. The energy-conversion device can light up an LED directly without attaching an external power source. Furthermore, this promising material candidate brings the low-grade waste-heat harvesting closer to a practical realization, e.g., small temperature fluctuations around the water boiling point can be considered as a clean energy source.

30 DIRECT ENERGY CONVERSION↗

X-ray diffraction study of phase transformation dynamics of Fe and Fe-Si alloys along the shock Hugoniot using an x-ray free electron laser

The x-ray free electron laser (XFEL) enables probing a highly compressed material response at the subnanosecond timescale. Here we exploit the ultrafast XFEL pulse to combine reflection x-ray diffraction and laser-driven shock compression to perform a study of the phase transformation and stability in Fe and Fe-Si alloys. Our approach enables us to observe that solid-solid phase transformations occur in Fe and Fe- Si 8.5 wt % in ≤ 130 ps at ~ 130 GPa; no transformation is observed in Fe- Si 16 wt % up to 110 GPa. Density functional theory calculations predict similar phase relations.

36 MATERIALS SCIENCE↗

Reversible Phase Transformation of Colloidal 2D Lead Halide Perovskite Platelets under Photoirradiation

The photostability of lead halide perovskites is an important criterion for their utilization in light harvesting applications. Colloidal two-dimensional mixed halide perovskites offer a convenient approach to probe photoinduced transformations using spectroscopy tools. We employed suspensions of colloidal 2D methylammonium lead halide perovskite platelets with butylammonium and octylammonium as organic spacer cations. Upon irradiation of the mixed halide perovskite (BAOAMAPb 2 (Br 3.5 I 3.5 )) colloidal platelet suspension, we observe a phase transformation, as seen from the formation of bromide rich domains (BAOAMAPb 2 Br 7 ) and an iodide complex (PbI 3 – ). Unlike in the case of 3D mixed halide films, we did not observe the formation of iodide rich domains as part of the photoinduced phase segregation process. Instead, we observed the dissociation of the BAOAMAPb 2 I 7 to form an iodide complex, PbI 3 – . Interestingly, this photoinduced phase transformation was reversible, as the products which were confined in the colloidal core restored the original mixed halide phase upon storage in dark. The spectroscopic measurements that characterize excited states of different colloidal methylammonium lead halide perovskites and kinetics of photoinduced transformation and their dark recovery are presented. Furthermore, these new phototransformations of colloidal perovskite platelets provide new insights into the processes that dictate their overall photostability.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Quantitative kinetic rules for plastic strain-induced α - ω phase transformation in Zr under high pressure

Plastic strain-induced phase transformations (PTs) and chemical reactions under high pressure are broadly spread in modern technologies, friction and wear, geophysics, and astrogeology. However, because of very heterogeneous fields of plastic strain $E$ p and stress σ tensors and volume fraction c of phases in a sample compressed in a diamond anvil cell (DAC) and impossibility of measurements of σ and $E$ p , there are no strict kinetic equations for them. Here, we develop a kinetic model, finite element method (FEM) approach, and combined FEM-experimental approaches to determine all fields in strongly plastically predeformed Zr compressed in DAC, and specific kinetic equation for α-ω PT consistent with experimental data for the entire sample. Since all fields in the sample are very heterogeneous, data are obtained for numerous complex 7D paths in the space of 3 components of the plastic strain tensor and 4 components of the stress tensor. Kinetic equation depends on accumulated plastic strain (instead of time) and pressure and is independent of plastic strain and deviatoric stress tensors, i.e., it can be applied for various above processes. Our results initiate kinetic studies of strain-induced PTs and provide efforts toward more comprehensive understanding of material behavior in extreme conditions.

36 MATERIALS SCIENCE↗

Crack mitigation in additively manufactured AlCrFe 2 Ni 2 high-entropy alloys through engineering phase transformation pathway

The far-from-equilibrium solidification during additive manufacturing often creates large residual stresses that induce solid-state cracking. Here we present a strategy to suppress solid-state cracking in an additively manufactured AlCrFe 2 Ni 2 high-entropy alloy via engineering phase transformation pathway. We investigate the solidification microstructures formed during laser powder-bed fusion and directed energy deposition, encompassing a broad range of cooling rates. At high cooling rates (10 4 –10 6 K/s), we observe a single-phase BCC/B2 microstructure that is susceptible to solid-state cracking. At low cooling rates (10 2 –10 4 K/s), FCC phase precipitates out from the BCC/B2 matrix, resulting in enhanced ductility (~10 %) and resistance to solid-state cracking. Site-specific residual stress/strain analysis reveals that the ductile FCC phase can largely accommodate residual stresses, a feature which helps relieve residual strains within the BCC/B2 phase to prevent cracking. Our work underscores the value of exploiting the toolbox of phase transformation pathway engineering for material design during additive manufacturing.

36 MATERIALS SCIENCE↗

He bubble-induced phase transformation of W grain boundaries revealed by accelerated molecular dynamics

The growth of He bubbles and the resulting impact on the microstructural evolution of W are of paramount importance to the plasma-facing materials community due to the application of W in Tokamak fusion reactors. Using accelerated molecular dynamics (AMD) techniques, we outline the structural evolution of grain boundaries (GBs) caused by growing He bubbles. It is discovered that when an alternative, low energy, high density GB structure or phase is available, He bubbles can induce a progressive phase transformation of the GB to the higher density phase by the continual nucleation of W Frenkel pairs. Here, we find that the resulting W self-interstitials migrate to sites at the GB which are structurally related to the higher density phase, leading to the transformation. We discuss the implications of this progressive microstructural evolution on the growing He bubble and consider in general how He bubbles will impact the structural evolution of an arbitrary W GB. These findings of GB phase transformation are predicted to impact other damage events in W such as recrystallization, GB migration and defect segregation which must take these findings into account in order to accurately simulate a realistic W microstructure and hence extract experimentally meaningful data.

36 MATERIALS SCIENCE↗

Stress-dependent χ phase transformation in a Ni-based superalloy

The ongoing push to elevate operating temperatures in aerospace gas turbine engines – driven by goals of enhanced fuel efficiency and reduced CO 2 emissions – mandates advancements in the creep resistance of Ni- and Co-based superalloys, which are integral for critical engine components. This study elucidates the role of stress assisted localized phase transformations in the creep properties of these alloys. By leveraging chemo-mechanical coupling, self-healing γ′ precipitates are designed to immobilize planar defects, thereby increasing creep resistance. Employing advanced characterization techniques such as high-resolution Scanning Transmission Electron Microscopy (HR-STEM), in conjunction with atomistic simulations and thermodynamic calculations, novel deformation pathways facilitated by χ local phase transformation (LPT) strengthening have been uncovered; notably, the formation of χ nano-laths through microtwinning and superlattice intrinsic stacking fault (SISF) shearing. This study highlights critical insights into the compositional boundaries necessary for optimizing LPT strengthening while avoiding deleterious bulk formation of η/χ phases. These advancements will guide the design of new alloys maximizing high-temperature creep strength for advanced aerospace applications.

Egan, Ashton J. [Friedrich-Alexander University Er↗

Utilizing local phase transformation strengthening for nickel-based superalloys

Almost 75 years of research has been devoted to producing superalloys capable of higher operating temperatures in jet turbine engines, and there is an ongoing need to increase operating temperature further. Here, a new disk Nickel-base superalloy is designed to take advantage of strengthening atomic-scale dynamic complexions. This local phase transformation strengthening provides the alloy with a three times improvement in creep strength over similar disk superalloys and comparable strength to a single crystal blade alloy at 760 °C. Ultra-high-resolution chemical mapping reveals that the improvement in creep strength is a result of atomic-scale η (D024) and χ (D019) formation along superlattice stacking faults. To understand these results, the energy differences between the L12 and competing D024 and D019 stacking fault structures and their dependence on composition are computed by density functional theory. This study can help guide researchers to further optimize local phase transformation strengthening mechanisms for alloy development.

Timothy M. Smith↗

Radio-Frequency Rapid Thermal Processing Enabling Spatial Phase Transformation and Nanocrystallization of Soft Magnetic Amorphous Alloys

Thermal processing of soft magnetic amorphous and nanocrystalline alloys is explored under the influence of radio-frequency induction-heating techniques. Direct induction-heating concepts based on longitudinal and transverse flux heating are examined and the details of electromagnetic fields interaction with metallic strips are discussed by analytical calculations as well as finite element analysis. Initial experimental results confirming spatial control of phase transformations and nanocrystallization within a single strip of Finemet Fe-based amorphous ribbons are reported. Here, the degree to which primary and secondary crystallization temperature are achieved depends on the spacing between the ribbon relative to the induction coil as well as the coil design and configuration. For transverse coil configurations, the local temperature and therefore microstructural evolution is different across the lateral dimension of processed ribbons, with reduced gap sizes producing enhanced peak temperatures and larger temperature distributions with greater spatial variation in microstructure. In addition, indirect susceptor-based induction heating under tension is performed and the impact of microstructure is demonstrated. Herein, potential for exploiting spatially optimized phase transformations is illustrated through electromagnetic field–assisted processing in a scalable manufacturing process with amorphous and nanocrystalline soft magnetic alloys.

36 MATERIALS SCIENCE↗

Raman spectroscopic characterization of SiO 2 phase transformation and Si substrate stress relevant to EBC performance

To accurately model the long-term durability of environmental barrier coatings (EBCs), a more complete understanding of the phase composition and transformations of the thermally grown oxide SiO 2 (TGO) is desired. For the TGO formed during thermal cycling in steam, cristobalite formation and the subsequent β- to α-cristobalite transformation has been identified as a potentially life-limiting mechanism. In this study, Raman micro-spectroscopy was used to quantify the cristobalite transformation on a polycrystalline Si coupon that was exposed to steam at 1350°C for 100 h. The phase transformation was mapped at 200–260°C on the TGO surface at different ramp rates using a heating stage and a micro-positioning stage. The stress in the Si substrate was also determined using Raman spectroscopy by measuring the stress induced peak shift. The α→β phase transformation produced a 300–500 MPa tensile stress in the Si substrate, which compared well to the stress predicted from the volumetric expansion of the cristobalite. In conclusion, quantifying the phase transformation and residual stress are critical tools in developing the next generation of high performance EBCs.

36 MATERIALS SCIENCE↗

Phase Transformations In Mullite-Precursor Xerogels

Report describes experimental study of phase transformations occurring in monophasic and diphasic xerogels of overall stoichiometric mullite composition during thermal treatment. Mullite valued as refractory material because of relatively high mechanical strength, excellent resistance to thermal shock, high resistance to creep, low density, low thermal conductivity, and stability at high temperature. Part of continuing effort to develop precursor materials transformed into mullite and sintered at temperatures low enough to avoid degradation of non-mullite reinforcing fibers in manufacture of mullite/fiber composites.

Hyatt, Mark J.↗

Kinetics of moisture-induced phase transformation in inorganic halide perovskite

The high-temperature (high-T) phase of cesium lead iodide (CsPbI 3 ) presents great promise for photovoltaic applications; however, exposure to ambient moisture at room temperature transforms it into its less-desirable low-temperature (low-T) phase with a larger band gap. While there have been theoretical predictions on the influence of moisture level on the phase transformation kinetics, the corresponding quantitative experimental evidence has remained limited. Tracking CsPbI 3 phase transformation under controlled relative humidity (RH), we find that rising RH increases the nucleation rate of low-T CsPbI 3 exponentially, but has a weak effect on its growth. The overall transformation is nucleation limited, with higher RH leading to a lower nucleation barrier. Finally, we find that heating between 40°C and 80°C facilitates water desorption and suppresses phase transformation. Our findings elucidate the relationship between moisture and the phase energetics of CsPbI 3 , which can serve as references for thin film applications of CsPbI 3 and future designs of stable photovoltaics systems.

36 MATERIALS SCIENCE↗