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Influence of processing on secondary phase formation and microstructural evolution at U-10Mo alloy and Zr interlayer interfaces

Thermo-mechanical processing of uranium-10 wt. % molybdenum (U-10Mo) fuel plates leads to microstructure changes at the U-10Mo/Zr interfaces. Secondary phases formed at this interface are particularly important to interfacial bond strength, process optimization, and maintaining structural integrity of the U-10Mo fuel plates during irradiation. In this work, we determined the phases and phase transformation products occurring at the interface of the U-10Mo fuel and Zr interlayer when the fuel plate is subjected to short and long hot isostatic pressure times. Interfacial morphology, structure and composition of phases formed, and relative hardness across the U-10Mo/Zr interfaces were studied using a multi-length scale, multi-modal characterization approach involving electron microscopy, atom probe tomography, and atomic force microscopy. Here, results highlight that the extent of phase transformations, secondary phase formation, and hardness variability across interfaces can be controlled by modifying processing parameters. Phase diagram construction and thermodynamic calculations were performed using the Thermocalc software to identify expected phases formed at interfaces during the maximum hold temperature of 560 °C experienced during HIP.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Microstructure evolution and mechanical performance of copper processed by equal channel angular rolling

Highlights: • Copper was processed by equal channel angular rolling (ECAR) up to 33 passes. • A very fine grained microstructure with high dislocation density was developed. • A decrease of dislocation density was observed for high numbers of passes. • The proof stress saturated at a value of about 400 MPa. • ECAR is a possible way of commercialization of ultrafine-grained materials. - Abstract: Ultrafine-grained (UFG) oxygen free high conductivity (OFHC) Cu samples were processed by severe plastic deformation (SPD) using the method of equal channel angular rolling (ECAR) up to 33 passes at room temperature. It was found that the grain size gradually decreased from ~ 40 μm to ~ 250 nm with increasing the number of passes. A maximum dislocation density of ~ 21 × 10{sup 14} m{sup − 2} was achieved after 13 passes of ECAR. For large numbers of passes (between 23 and 33), the dislocation density decreased to ~ 14 × 10{sup 14} m{sup − 2}. The proof stress was saturated at the value of about 400 MPa. The stored energy was measured by calorimetry and compared with the values calculated from the parameters of the microstructure. The reduction of the released heat after 13 and 33 passes suggested structural relaxation of the UFG microstructure. For these numbers of passes, the reduction of area in tensile testing was improved without decreasing the proof stress. The correlation between the microstructure and the mechanical behavior was discussed in detail. It was found that ECAR is capable for the mass-production of UFG metallic materials with high strength, therefore this method is a possible way of commercialization of SPD-processed materials.

36 MATERIALS SCIENCE↗

Fundamental Studies of Irradiation-Induced Modifications in Microstructural Evolution and Mechanical Properties of Advanced Alloys

This final technical report summarizes the research performed during October 2014 and December 2017, with a focus on investigating the radiation-induced microstructural and mechanical property modifications in optimized advanced alloys for sodium-cooled fast reactor (SFR) structural applications. To accomplish these objectives, the radiation responses of several different advanced alloys, including austenitic steel Alloy 709 (A709) and 316H, and ferritic/ martensitic Fe–9Cr steels T91 and G92, were investigated using a combination of microstructure characterizations and nanoindentation measurements. Different types of irradiation, including ex situ bulk ion irradiation and in situ transmission electron microscopy (TEM) ion irradiation, were employed in this study. Radiation-induced dislocations, precipitates, and voids were characterized by TEM. Scanning transmission electron microscopy with energy dispersive X-ray spectroscopy (STEM-EDS) and/or atom probe tomography (APT) were used to study radiation-induced segregation and precipitation. Nanoindentation was used for hardness measurements to study irradiation hardening. Austenitic A709 and 316H was bulk-irradiated by 3.5 MeV Fe ++ ions to up to 150 peak dpa at 400, 500, and 600°. Compared to neutron-irradiated stainless steel (SS) 316, the Frank loop density of ion-irradiated A709 shows similar dose dependence at 400°, but very different temperature dependence. Due to the noticeable difference in the initial microstructure of A709 and 316H, no systematic comparison on the Frank loops in A709 vs 316H was made. It would be helpful that future ion irradiation study on 316 stainless steel could be conducted to directly compare the temperature dependence of Frank loop density in ion-irradiated 316 SS with that in neutron-irradiated 316 SS. In addition, future neutron irradiation on A709 at 400–600° at relative high dose (≥10 dpa) can be carried out to compare with ion-irradiated A709. The radiation-induced segregation (RIS) of Ni and Si was observed in both A709 and 316H in all irradiated conditions and was found at various sinks: line dislocations, dislocation loops, void surfaces, carbide-matrix interfaces, etc. Radiation also induced the formation of Ni,Si-rich precipitates. As suggested in a previous study on neutron-irradiated 316 stainless steel, one possible consequence of the significant RIS of Si is that the enrichment at defect sinks depletes the silicon in the matrix, which can lead to enhanced void nucleation rate. The enrichment of Ni and Si is accompanied by the depletion of Cr at defect sinks, which could also affect the corrosion resistance. Radiation-induced change in the orientation relationship of pre-existing MX precipitates was observed at 600°. It is believed that this change is associated with the network dislocations formed under irradiation. The underlying mechanism is still not well understood. This change could be a positive indication that the MX precipitates can survive high density network dislocations. It would be helpful if neutron irradiation at similar dose conditions could be carried out to verify that this effect is not unique for ion irradiation. Intragranular Cr-rich carbides with a core-shell structure, i.e. Cr-rich carbide core and Ni,Si-rich shell was found at 500° and 600° in the highest dose (150 peak dpa) specimens. Coarse voids (30 nm in diameter) were only commonly found at 500° in the 50 and 150 peak dpa specimens in regions less than 750 nm in depth. The highest swelling for A709 irradiated to 50 and 150 peak dpa at 500° is about 0.44% and 0.37%, respectively. Due to the choice of 100 degree temperature intervals, this study did not attempt to precisely identify peak void swelling conditions, merely the range of irradiation temperatures where this could be a concern. It is known high-dose ion irradiation can significantly suppress void nucleation. Future neutron irradiation in the 500–600° range (without considering the temperature shift) is needed to determine the onset of accelerated void swelling (possibly at lower dose).

36 MATERIALS SCIENCE↗

Microstructure Evolution and Stress Corrosion Cracking Susceptibility of 12Cr Martensitic Steel Upon Long-Term Service in Power Plants

After 230,000-h long-term service at 550 °C/13.7 MPa, the microstructure of a kind of 12Cr martensitic steel was investigated using scanning electron microscopy, backscattering electron microscope and x-ray diffraction analysis. The results show that the precipitation and coarsening of carbides at grain/lath boundaries are the main cause of microstructure degradation. The static immersion tests and the slow strain rate test coupled with electrochemical impedance spectroscopy were conducted on the served steel in 1.0% NaCl solution, and it turns out that the pitting corrosion resistance and repassivation ability of the steel are significantly reduced as a result of microstructure degradation. The stress corrosion cracking susceptibility of the steel was also studied. Fracture morphology analysis shows that the secondary crack in conjunction with slip lines is a result of the coalescence of micro-cracks nucleated from the pits.

36 MATERIALS SCIENCE↗

An Investigation on Microstructure Evolution, Mechanical Properties, and Strain Aging of Mg-1.8Zn-0.7Si-0.4Ca Biomedical Alloy Processed by Equal Channel Angular Pressing

The influence of equal channel angular pressing (ECAP) on microstructure and mechanical behavior, as well as, strain aging during ECAP and post-ECAP of Mg-1.8Zn-0.7Si-0.4Ca biomedical alloy was examined. The alloy in solid solution heat-treated condition was processed by ECAP with route B{sub C} at 350 and 400 °C. The specimens ECAPed at 350 °C were aged at 125 and 150 °C for different times. The hardness and shear punch test results indicated that performing ECAP at 350 °C for 4 passes increases the hardness and shear strength of the alloy from 48 HV and 110 MPa to 71 HV and 188 MPa, respectively. It was revealed that the average grain size of the alloy decreases from 78 µm to about 3 µm after 4 passes of ECAP. Three precipitates of CaMgSi, Ca{sub 2}Mg{sub 6}Zn{sub 3}, and Mg{sub 2}Si were detected in the solid solution specimen. After 4 passes of ECAP at 350 °C, Ca{sub 2}Mg{sub 6}Zn{sub 3} was completely dissolved and the morphology of Mg{sub 2}Si changed from Chinese script to fiber-shaped particles. Dynamic strain aging occurred at high-temperature ECAP, and the specimens were overaged during post-ECAP aging. Small MgZn particles were detected in the overaged sample.

36 MATERIALS SCIENCE↗

Microstructural evolution and deformation behavior of Al-Cu alloys: A Transmission X-ray Microscopy (TXM) and micropillar compression study

In this paper, a unique approach to correlating an evolving 3D microstructure in an Al-Cu alloy and its micro-scale mechanical properties has been introduced. Using these nanoscale three-dimensional microstructures derived from Transmission X-ray Microscopy (TXM), individual contributions from different strengthening mechanisms were quantified. The spatial distribution and morphology of the individual θ' and θ phases were seen to play an important role in influencing dislocation storage. Uniaxial micro-compression experiments were used to quantify the stress-strain response of the alloy at different aging times. Transmission electron microscopy (TEM) aided in discerning dislocation activity at these precipitates. A model is proposed to accurately predict the variation in yield stress by using appropriate morphological parameters from the 3D microstructure and its validity has been corroborated using experimental measurements. Distributions of 2D and 3D inter-precipitate spacing were seen to provide crucial insights on influencing deformation in such precipitation-strengthened alloys. In conclusion, the transition in deformation behavior and origin of numerous strain bursts were investigated using in situ micropillar compression testing.

36 MATERIALS SCIENCE↗

Microstructural evolutions, phase transformations and hard magnetic properties in polycrystalline Ce–Co–Fe–Cu alloys

This work focuses on systematic studies of Ce–Co based 1:5 permanent magnet alloys of CeCo 4.4-x Fe x Cu 0.6 and CeCo 3.9-x Fe x Cu 1.2 (x = 0, 0.3, 0.6, 0.9, 1.2, 1.8) by varying Co:Fe. The overarching aim of this manuscript is to elucidate the hard-magnetic properties through a better understanding of phase formation by the structural, microstructural, and magnetic properties in these materials. Improved mutual solubility of Fe in the 1:5 phase has been observed with an extended homogeneity range by Cu substitution. For both composition series, Fe contents of x ≤ 0.6 show a homogeneous microstructure with a single 1:5 phase and good magnetic properties. The composition region 0.6 < x ≤ 0.9 appears to be near the boundary of solubility and evolution of other phases. At x = 1.8, it is found that the homogeneous 1:5 phase and magnetic hardness deteriorated due to the evolution of secondary phases such as 2:17, 2:7, and Fe–Co. Furthermore, the addition of Fe improved both the magnetization and Curie temperature via increased effective exchange interactions, while an increase in Cu content enhanced coercivity.

33 ADVANCED PROPULSION SYSTEMS↗

Deformational Features and Microstructure Evolution of Copper Fabricated by a Single Pass of the Elliptical Cross-Section Spiral Equal-Channel Extrusion (ECSEE) Process

The objectives of this work are to study the deformational feature, textures, microstructures, and dislocation configurations of ultrafine-grained copper processed by the process of elliptical cross-section spiral equal-channel extrusion (ECSEE). The deformation patterns of simple shear and pure shear in the ECSEE process were evaluated with the analytical method of geometric strain. The influence of the main technical parameters of ECSEE die on the effective strain distribution on the surface of ECSEE-fabricated samples was examined by the finite element simulation. The high friction factor could improve the effective strain accumulation of material deformation. Moreover, the pure copper sample fabricated by ECSEE ion shows a strong rotated cube shear texture. The refining mechanism of the dislocation deformation is dominant in copper processed by a single pass of ECSEE. The inhomogeneity of the micro-hardness distribution on the longitudinal section of the ECSEE-fabricated sample is consistent with the strain and microstructure distribution features.

36 MATERIALS SCIENCE↗

Effect of heat treatment on microstructural evolution and hardness homogeneity in laser powder bed fusion of alloy 718

The thermal history developed in laser powder bed fusion (LPBF) processes has been shown to be complex resulting in equally complex microstructures and mechanical properties. Microscopic observations and Vickers micro-hardness mapping measurements were carried out on diff ;erent section planes of LPBF alloy 718 cuboids. Three-dimensional finite element analysis was used to simulate thermal history and to predict the residual stress distribution in the as-built material. Computational thermodynamics was used to predict the micro-segregation and nucleation driving force of various phases in the bulk and in segregated regions. Varied heat-treatments such as simulated hot isostatic pressing, and double aging were applied. Their influence on the microstructure, microsegregation, precipitate formation, and micro-hardness variations of LPBF alloy 718 were investigated. Hardness map results showed heterogeneous micro-hardness on the xy- and xz-planes of the as-built parts where the bottom plane and center regions had larger hardness of ~315 HV 0.5 while the top plane and contours showed hardness of ~300 HV 0.5 . It was found that the aging treatment increased the overall hardness of the as-built condition from ~310 HV 0.5 to 470 HV 0.5 but also increased the hardness gradient throughout the coupon. After simulated hot isostatic pressing process (i.e., without applied pressure) at 1020 °C for 4 h followed by water quench (HIPWQ), the hardness gradient and hardness was minimized (~210 HV 0.5 ) as the microstructure transitioned from heterogeneous columnar grains in the as-built condition to more uniform recrystallized grains. A double aging treatment was applied to enhance hardness from ~210 HV 0.5 to ~440 HV 0.5 . Finally, HIPWQ followed by double aging produced a homogeneous microstructure and more uniform hardness map with enhanced mechanical properties in LPBF alloy 718 coupons.

36 MATERIALS SCIENCE↗

Microstructure Evolution During Continuous Cooling in AISI 5140 Steel Processed by Induction Heating Chromizing

In this study, induction heating chromizing (IHC) and box-type furnace heating chromizing (BFHC) were conducted on commercial AISI 5140 steels, respectively. Microstructure, microhardness and wear resistance of the chromized samples were characterized. The results show that the IHC samples have thicker Cr coating layer and stronger interface bond due to pre-compressive stress among the packed powders. Three kinds of microstructures including alloyed cementite (AC-layer), fine pearlite zone (FP-zone) and carbon-poor zone (CP-zone) are formed near the interface in the IHC samples. The main reason given for this is that different contents of Cr and C have different effects on pearlite phase and morphology. The IHC sample shows better wear properties due to its stronger interface bonding strength than that of the BFHC sample. The formation mechanism of CP-zone and its influences on microhardness and wear resistance are also discussed.

36 MATERIALS SCIENCE↗

Microstructural evolution during quenching and partitioning of 0.2C-1.5Mn-1.3Si steels with Cr or Ni additions

Here, the influence of Cr and Ni additions and quench and partition (Q&P) processing parameters on the microstructural development, including carbide formation and austenite retention during Q&P, was studied in two steels with a base composition of 0.2C-1.5Mn-1.3Si wt.% and additions of 1.5 wt.% Cr (1.5Cr) or Ni (1.5Ni). Additions of 1.5 wt.% Cr significantly slowed the kinetics of austenite decomposition relative to the 1.5Ni alloy at all partitioning temperatures, promoting greater austenite retention, lower retained austenite carbon (C) contents, and reduced sensitivity of the retained austenite amounts to processing variables. In the 1.5Cr alloy after partitioning at 400 °C for 300 s, η-carbides were identified by transmission electron microscopy (TEM) and atom probe tomography (APT) revealed no significant enrichment of substitutional elements in the carbides. In the 1.5Ni alloy after partitioning at 450 °C for 300 s, both plate-like and globular carbides were observed by TEM. APT analysis of the globular carbides clearly revealed significant Si rejection and Mn enrichment. Mössbauer effect spectroscopy was used to quantify the amount of carbides after Q&P. In general, carbide amounts below ~0.3% of Fe were measured in both alloys after partitioning for short times (10 s), irrespective of quench or partitioning temperature, which corresponds to a relatively small portion of the bulk C. With increasing partitioning time, carbide amounts remained approximately constant or increased, depending on the alloy, quench temperature, and/or partitioning temperature.

36 MATERIALS SCIENCE↗

From Cryogenic to High Temperatures: A Microstructural Evolution of δ-phase Pu-Ga Alloys Investigated by Time-of-Flight High-resolution Neutron Diffraction

Phase stability and phase transformations in binary Pu alloys are critical for multiple applications. Long-term phase stability affects mechanical properties, microstructure, corrosion behavior, and structural integrity. A clear and detailed understanding of phase transformations and phase stability mechanisms is necessary to assess the behavior and response to unexpected stimuli. Gaining advanced knowledge on the behavior of Pu and Pu alloys at a variety of temperatures, pressures, and time will ensure better predictions and control on evolution outside laboratory measurements.

36 MATERIALS SCIENCE↗

Microstructure Evolution and Mechanical Properties of the AZ91 Magnesium Alloy with Sr and Ti Additions in the As-Cast and As-Aged Conditions

Effect of different amounts of Sr and Ti additions with T6 heat treatment on microstructure and mechanical properties of the AZ91 alloy was investigated. The microstructure of the AZ91 alloy is consisted of the α-Mg phase surrounded by the semicontinuous network of β-Mg{sub 17}Al{sub 12} intermetallics. The average grain size and volume fraction of β phase decreased up to 1 wt.% Sr and 0.1 wt.% Ti additions. Exceeding Ti additions led to increase in both grain size and volume fraction. It was found that the grain refinement mechanism of AZ91 alloys with Sr additions was grain restriction factor. Also, 0.1 wt.% Ti addition could refine the grain structure of the AZ91 alloy by the formation of Al{sub 3}Ti particles that act as nucleation sites for the α-Mg phase. Furthermore, adding 1 wt.% Sr and 0.1 wt.% Ti enhanced the hardness values for both cast and aged AZ91 alloy. Moreover, ultimate tensile strength and tensile elongation values reached their maximum amounts with the 0.5 wt.% Sr and 0.1 wt.% Ti additions and more Sr and Ti additions deteriorated the mechanical properties of cast and aged AZ91 alloys. The fracture surface characterizations had good relations with the tensile properties. The fracture modes were cleavage and quasi-cleavage in the cast and aged AZ91 alloys. Furthermore, the optimum levels of Sr and Ti additions altered the fracture modes to more quasi-cleavage fractures.

36 MATERIALS SCIENCE↗

Effect of stored strain energy heterogeneity on microstructure evolution of 90% cold rolled AISI 304L stainless steel during interrupted annealing treatment

Highlights: • Study of usefulness of stored strain energy distribution map of the material for variable temperature range. • Advantage of using stored strain energy distribution map • Variation observed in stored energy between isothermal annealing treatment and interrupted annealing treatment. - Abstract: This research work is an attempt to understand the effect of stored strain energy heterogeneity over macro-scale, induced during interrupted annealing treatment, on the micro structural evolution in a heavily cold rolled AISI 304L austenitic stainless steel. The cold rolled AISI 304L stainless steel (SS) samples were subjected to different annealing treatments. The microstructures obtained after each annealing treatment were characterized using optical and electron microscopy techniques. Further, an attempt was made to estimate the stored strain energy by a novel approach of micro hardness measurement both over small scale (area 3600 μm{sup 2}) and large scale (area ~0.25 mm{sup 2}). The stored strain energy was determined using hardness values. Using these data, spatial stored strain energy distribution contour maps were created. They were, in turn, used to characterize the local softening behavior both at micro and macro-scale levels after each interrupted annealing treatment. The results showed that, interrupted annealing treatment induces increased stored strain energy heterogeneity after each annealing interruptions. Also, it was possible to determine recrystallization kinetics of the material using stored strain energy map, which helps in designing annealing cycles for achieving ultrafine grained microstructure.

36 MATERIALS SCIENCE↗

Probing the Influence of Thermally Induced Structural Changes on the Microstructural Evolution in Shale using Multiscale X-ray Scattering Measurements

Various pathways to accelerate the recovery of hydrocarbons from unconventional subsurface environments have been proposed, including the use of high-temperature fluids. However, the influence of temperature on the structural and microstructural changes in complex subsurface materials characterized by compositional and morphological heterogeneity are not very well understood. In this study, in operando ultrasmall angle, small angle, and wide-angle X-ray scattering (USAXS/ SAXS/WAXS) measurements were performed to link the structural and morphological changes in shale when heated from 30 to 1150 °C. The structural changes observed from the wide-angle X-ray scattering measurements were complemented by the changes in the porosity, particle size, and surface morphology. Overall, we report the combined USAXS/SAXS measurements showed enhanced smoothness in the pore–solid interface on heating. The dehydroxylation of illite and calcination of calcium carbonate were noted prior to the formation of denser and sintered silicate and alumino-silicate phases such as Mg 2 SiO 4 (forsterite), Fe 0.3 Mg 0.7 (SiO 3 ) (enstatite), and Al 2.35 Si 0.64 O 4.82 (mullite).

54 ENVIRONMENTAL SCIENCES↗

Chemical, Molecular, and Microstructural Evolution of Kerogen during Thermal Maturation: Case Study from the Woodford Shale of Oklahoma

Integrated elemental, spectroscopic (infrared spectroscopy and X-ray absorption near-edge structure), and gas intrusion (helium pycnometry and nitrogen adsorption) analyses are used to characterize the bulk chemical, molecular, and physical microstructures of kerogen spanning a thermal maturity transect (vitrinite reflectance, Ro, from 0.5% to 2.6%) across the Woodford Shale of the Anadarko Basin, Oklahoma. The integration takes advantage of novel procedures to prepare kerogen isolates that preserve both the chemical and physical properties of the organic matter in the bulk shale. The Woodford kerogens follow the expected trends in H/C and O/C coordinates during thermal maturation for type II kerogen. Infrared spectra show that loss of hydrogen from kerogen is related to cracking of hydrogen-rich aliphatic (alkyl) carbon structures from aromatic carbons. Within the range of Ro values < 1.5%, peripheral aromatic carbons remain highly substituted with alkyl (methyl and methylene) and probably heteroatom functional groups. At Ro values > 1.5%, these substitutions are substantially removed and replaced by hydrogen. The evolution of carbon structures inferred from the IR spectra is supported by known carbon bond dissociation energies for carbonaceous materials. Total organic sulfur and sulfur-XANES data show that sulfur in Woodford kerogens is dominated by aromatic sulfur (thiophene) and that reactive, aliphatic sulfur (sulfide) is eliminated at low degrees of thermal stress (Ro ≤ 0.9%). At higher thermal stress, sulfur speciation is stable and dominated by thermally stable thiophene. The physical properties of Woodford kerogens evolve during thermal maturation in a manner consistent with their molecular characteristics. Skeletal density of kerogen increases during maturation in a manner that is linearly correlated to its atomic H/C ratio and inferred aromatic carbon content. The specific surface area of kerogen also increases during maturation, reflecting the development of internal pores within the kerogen skeletal framework as aliphatic carbon structures are preferentially cracked and expelled from solid kerogen. The quantitative chemical and structural changes expressed by the Woodford kerogens during thermal maturation, including their hydrogen and carbon content, carbon speciation, and skeletal density, are shown by comparison to not be measurably different for other type II kerogens from numerous oil- and gas-producing shale plays, indicating that thermal stress acts to drive maturation of type II kerogen in a similar way globally.

58 GEOSCIENCES↗

Microstructure Evolution and Improved Creep Behavior of Mg-Al-Si Alloy Matrix Composite Reinforced with SiC Nanoparticles

The Mg-9Al-1Si matrix composite reinforced with SiC nanoparticles is fabricated by semisolid stirring-assisted ultrasonic vibration, which contains finer grains and a more uniform microstructure compared to that of the Mg-9Al-1Si alloys. The sizes of the Mg{sub 17}Al{sub 12} and Mg{sub 2}Si phases decreased continuously as the volume fraction of n-SiCp increased from 0 to 1% and then increased apparently when the volume fraction of n-SiCp increased to 1.5%. The steady-creep rates of the 1 vol.% n-SiCp/Mg-9Al-1Si are approximately two times lower than those of the Mg-9Al-1Si matrix alloy at 200 °C under applied stress of 70 MPa due to the strengthening effect of the nanosized SiCp. The reason for the improved creep properties is mainly attributed to the obvious grain boundary strengthening, the Orowan strengthening mechanism, the load transfer effect, and the pinning effect of the n-SiCp and the refined Mg{sub 17}Al{sub 12} and Mg{sub 2}Si phases.

36 MATERIALS SCIENCE↗