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Microstructural evolution and intermetallic formation in Zn-3Mg (wt%) powder mixture processed by high-pressure torsion

Severe plastic deformation (SPD) techniques have been used extensively over the past 40 years for producing strong metals and alloys. High-pressure torsion (HPT) is one of the most promising SPD techniques for achieving high strength through nanoscale grain refinement and phase transformation. In this research, a mixture of pure zinc (Zn) and magnesium (Mg) powders, Zn-3Mg (wt%), was HPT-processed under a pressure of 6 GPa for 1, 5, 10, 20, and 30 turns at room temperature to achieve a high strength biodegradable material. In order to understand the effects of pre-consolidation on the resulting microstructure and hardness, HPT processing was performed on loose powders placed in the die and also on a pre-compacted powder mixture and the resulting HPT disks were characterized by X-ray diffraction, scanning electron microscopy, atom probe tomography, and Vickers microhardness. In both cases, the HPT disk microstructures contained nanoscale grains, and stable and metastable strain-induced intermetallics, but an unusual softening appeared at large shear strains. Grain size, grain morphology, and the formation of different intermetallics were analyzed to explain the unusual hardness distribution, and it was found that an inverse Hall-Petch relationship between hardness and grain size exists. It is suggested that thermally-activated phenomena such as grain boundary sliding contributed to the strain-induced softening of this nano-structured biomaterial due to its low melting point. Finally, the current results are compared with those for HPT-processed cast alloys and hybrids of the same composition.

36 MATERIALS SCIENCE↗

Mechanical Property Evaluation of CuNb Composites Manufactured with High-Pressure Torsion

Copper is under consideration as the optimum material for both high heat flux applications and high pulsed magnets. One challenge is that copper has low strength which is problematic to deployment in these applications. One solution is to alloy copper with BCC elements to improve its mechanical properties. However, the limited solubility of the BCC elements in copper requires high deformation processes to be used in order to manufacture these 3D composites. Here, high energy ball milling combined with high pressure torsion was used to manufacture 3D Cu-Nb composites. After the consolidation the mechanical properties of the composites were measured using micro- and nanohardness testing at room and elevated temperature. The results indicated that after 10 turns during the high-pressure torsion consolidation, the mechanical properties of the composites were completely saturated displaying uniform properties across the manufactured disk. Performing the high pressure torsion at temperature further improved consolidation of the disk. The high temperature nanoindentation also indicated a change in the deformation mechanism between 200 and 500 ºC.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Microstructural evolution in a precipitate-hardened (Fe 0.3 Ni 0.3 Mn 0.3 Cr 0.1 ) 94 Ti 2 Al 4 multi-principal element alloy during high-pressure torsion

Multi-principal element alloys demonstrate high strength, thermal stability, and irradiation resistance, making them excellent candidate materials for applications in nuclear reactors and other harsh environments. Some studies have examined the use of high-pressure torsion to strengthen MPEAs through grain size reduction and strain hardening. However, no studies have investigated the effect of HPT on secondary phases (precipitates) within an MPEA. Two alloys, (Fe 0.3 Ni 0.3 Mn 0.3 Cr 0.1 ) 94 Ti 2 Al 4 containing Ni(Ti, Al) B2 phase, and CrFe σ phase, and single-phase Fe 0.3 Ni 0.3 Mn 0.3 Cr 0.1 , were fabricated by casting and heat treatment. Both alloys were then processed with HPT to study microstructural evolution. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) were used to characterize the alloys before and after HPT processing. HPT processing produced a nanocrystalline structure in both alloys, but (Fe 0.3 Ni 0.3 Mn 0.3 Cr 0.1 ) 94 Ti 2 Al 4 exhibited a significantly smaller grain size and higher dislocation density than Fe 0.3 Ni 0.3 Mn 0.3 Cr 0.1 , with corresponding higher hardness. Before HPT, the (Fe 0.3 Ni 0.3 Mn 0.3 Cr 0.1 ) 94 Ti 2 Al 4 alloy consisted of large grain (~ 400 μm) and precipitates, including B2 of ~ 38 μm average size, B2 of ~ 0.7 μm average size, and small amounts of σ of ~ 1.5 μm average size. After HPT, the larger B2 precipitates were decreased in size and volume fraction, while the smaller B2 precipitates were completely dissolved; the σ precipitates appeared unaffected by HPT, likely due to their much higher hardness. Finally, observation of the B2 precipitate distribution along radial distance indicates that the strain caused the precipitates to fracture at intermediate strain (γ = 125) and dissolve at high strain (γ = 280).

36 MATERIALS SCIENCE↗

Quantification of grain rotation in bulk nanostructured copper via in situ heating white beam synchrotron X-ray diffraction

Grain rotation during microstructural relaxation under heating is conventionally studied extensively through transmission electron microscopy and simulations. However, there is a shortage in examining grain rotations at larger length and volume scales in bulk materials. It is critical to understand the thermal stability of bulk nanostructured metals, since those enhanced mechanical properties have been well recognized. Here, this study aimed to employ a white beam microdiffraction X-ray technique under in situ heating from 300 K to 1073 K at 12 K/min on a nanostructured copper processed by high-pressure torsion, yielding an initial grain size of ∼260 nm before the heating. Evaluation across a wide range of temperatures reveals transition temperatures associated with microstructural relaxation processes. By tracking separate Laue diffraction peaks stemming from individual grains, changes in their orientations can be estimated and quantified. This approach becomes particularly effective when the number of grains within the probed volume is reasonably small. At temperatures above 940 K, about 7.5 % of Cu grains are rotating at speeds of ∼2 × 10 –3 °/s. The radial direction of the disk specimen is found to be the preferred direction of grain rotation, with the rotation axis along the shear direction. Further analysis found no correlation between peak intensity and peak size, related to grain sizes and deviatoric strain, respectively, with rotation conditions or speed. These findings demonstrate that the diffraction technique utilizing white beam X-rays is a complementary and novel characterization tool for understanding microstructural evolution, especially in grain rotations, of bulk crystalline materials.

Grain orientation↗

Microstructural and material property changes in severely deformed Eurofer-97

Severe plastic deformation changes the microstructure and properties of steels, which may be favourable for their use in structural components of nuclear reactors. In this study, high-pressure torsion (HPT) was used to refine the grain structure of Eurofer-97, a ferritic/martensitic steel. Electron microscopy and X-ray diffraction were used to characterise the microstructural changes. Following HPT at room temperature to a maximum shear strain of 230, the average grain size reduced by a factor of ~30, with a marked increase in high-angle grain boundaries. Dislocation density also increased by more than one order of magnitude. The thermal stability of the deformed material was investigated via in-situ annealing during synchrotron X-ray diffraction. This revealed substantial recovery between 450 K – 800 K. Irradiation with 20 MeV Fe-ions to ~0.1 dpa caused a 20% reduction in dislocation density compared to the as-deformed material. However, HPT deformation prior to irradiation only had a minor effect in mitigating the irradiation-induced reductions in thermal diffusivity and surface acoustic wave velocity of the material. Microstructural and material property changes are dominated by deformation compared to irradiation. In light of this, the benefits of using HPT to improve the irradiation resistance of Eurofer-97 are limited. These results provide a multi-faceted view of the changes in ferritic/martensitic steels due to severe plastic deformation, and how these changes can be used to alter material properties.

ion-irradiation↗

Effect of a micro-scale dislocation pileup on the atomic-scale multi-variant phase transformation and twinning

In this paper, we perform concurrent atomistic–continuum (CAC) simulations to assess the contribution of the internal stress induced by the microscale dislocation pileup at an atomically structured interface to the atomic-scale phase transformations (PTs), reverse PTs, and twinning. The main novelty of this work is to unify the atomistic description of the interface and the coarse-grained (CG) description of the lagging dislocations away from the interface within one single framework. Our major findings are: (a) the interface dynamically responds to a pileup by forming steps/ledges, the height of which is proportional to the number of dislocations arriving at the interface; (b) the pileup-induced internal stress concentration profile follows neither the classical Eshelby model nor the super-dislocation model alone, but a combination of them; (c) when the pre-sheared sample is compressed, a direct square-to-hexagonal PT occurs ahead of the pileup tip and eventually grows into a wedge shape. The two variants of the hexagonal phases form a twin with respect to each other; (d) upon a further increase of the loading, part of the newly formed hexagonal phase transforms back to the square phase. The square product phase resulting from this reverse PT forms a twin with respect to the initial square phase. All phase boundaries (PBs) and twin boundaries (TBs) are stationary and correspond to zero thermodynamic Eshelby driving forces; and (e) the microscale dislocation pileup-induced internal shear stress and the structural change at the atomic-scale interface reduces the stress required for initiating a PT by a factor of 5.5, comparing with that in the sample containing no dislocations. This work is the first characterization of the behavior of PTs/twinning resulting from the reaction between a microscale dislocation slip and an atomically structured interface. In conclusion, the gained knowledge will advance our understanding of how the multi-phase material behaves in many complex physical processes, such as the synthesis of multi-phase high-entropy alloys or superhard ceramics under high-pressure torsion, deep mantle earthquakes in geophysics, and so on, which all involve dislocation slip, PTs, twinning, and their interactions across from the atomistic to the microscale and beyond.

36 MATERIALS SCIENCE↗

Use of a torsional pendulum as a high-pressure gage and determination of viscosity of helium gas at high pressures

Three torsional crystal parameters were examined for suitability in sensing pressure in gases up to 131 million newtons per square meter. The best parameters were found to be the change in crystal decrement at resonance and the change in crystal electrical resistance at resonance. The change in crystal resonant frequency did not appear to be a reliable pressure measuring parameter. Pure argon and pure helium gases were studied for use as working fluids. Helium functioned better over a wider pressure range. Calibration of the gage also provided a measure of the viscosity-density product of the gas as a function of pressure. These data, together with known extrapolated density data, permitted the determination of the viscosity of helium to 131 million N/square meter.

Maisel, J. E.↗

Unified constitutive material models for nonlinear finite-element structural analysis

Unified constitutive material models were developed for structural analyses of aircraft gas turbine engine components with particular application to isotropic materials used for high-pressure stage turbine blades and vanes. Forms or combinations of models independently proposed by Bodner and Walker were considered. These theories combine time-dependent and time-independent aspects of inelasticity into a continuous spectrum of behavior. This is in sharp contrast to previous classical approaches that partition inelastic strain into uncoupled plastic and creep components. Predicted stress-strain responses from these models were evaluated against monotonic and cyclic test results for uniaxial specimens of two cast nickel-base alloys, B1900+Hf and Rene' 80. Previously obtained tension-torsion test results for Hastelloy X alloy were used to evaluate multiaxial stress-strain cycle predictions. The unified models, as well as appropriate algorithms for integrating the constitutive equations, were implemented in finite-element computer codes.

Kaufman, A.↗

Unified constitutive material models for nonlinear finite-element structural analysis

Unified constitutive material models were developed for structural analyses of aircraft gas turbine engine components with particular application to isotropic materials used for high-pressure stage turbine blades and vanes. Forms or combinations of models independently proposed by Bodner and Walker were considered. These theories combine time-dependent and time-independent aspects of inelasticity into a continuous spectrum of behavior. This is in sharp contrast to previous classical approaches that partition inelastic strain into uncoupled plastic and creep components. Predicted stress-strain responses from these models were evaluated against monotonic and cyclic test results for uniaxial specimens of two cast nickel-base alloys, B1900+Hf and Rene 80. Previously obtained tension-torsion test results for Hastelloy X alloy were used to evaluate multiaxial stress-strain cycle predictions. The unified models, as well as appropriate algorithms for integrating the constitutive equations, were implemented in finite-element computer codes.

Kaufman, A.↗

From electronic structure to model application of key reactions for gasoline/alcohol combustion: Hydrogen-atom abstraction by $CH_3O\dot{O}$ radicals

Hydrogen atom abstraction by methyl peroxy ($CH_3O\dot{O}$) radicals can play an important role in gasoline/ethanol interacting chemistry for fuels that produce high concentrations of methyl radicals. Detailed kinetic reactions for hydrogen atom abstraction by $CH_3O\dot{O}$ radicals from the components of FGF-LLNL (a gasoline surrogate) including cyclopentane, toluene, 1-hexene, n -heptane, and isooctane have been systematically studied in this work. Here, the M06-2X/6-311 ++ G(d,p) level of theory was used to obtain the optimized structure and vibrational frequency for all stationary points and the low-frequency torsional modes. The 1-D hindered rotor treatment for low-frequency torsional modes was treated at M06-2X/6-31G level of theory. The UCCSD(T)-F12a/cc-pVDZ-F12 and QCISD(T)/CBS level of theory were used to calculate single point energies for all species. High pressure limiting rate constants for all hydrogen atom abstraction channels were performed using conventional transition state theory with unsymmetric tunneling corrections. Individual rate constants are reported in the temperature range from 298.15 to 2000 K. Our computed results show that the abstraction of allylic hydrogen atoms from 1-hexene is the fastest at low temperatures. When the temperature increases, the hydrogen atom abstraction reaction channel at the primary alkyl site gradually becomes dominant. Thermodynamics properties for all stable species and high-pressure limiting rate constants for each reaction pathway obtained in this work were incorporated into the latest gasoline surrogate/ethanol model to investigate the influence of the rate constants calculated here on model predicted ignition delay times.

33 ADVANCED PROPULSION SYSTEMS↗