Engineering topics

Lozano-Perez, Sergio

Publications and source records attributed to Lozano-Perez, Sergio.

9 records

DOE OSTI2019

Mechanism of the α-Zr to hexagonal-ZrO transformation and its impact on the corrosion performance of nuclear Zr alloys

Displacive transformations have been widely reported in metals, alloys and ceramics, but rarely reported to be important in the aqueous corrosion of alloys. We report here our analysis of the formation of the hexagonal-ZrO suboxide during the aqueous corrosion of α-Zr alloys and propose this to be a paraequilibrium displacive transformation with the rate controlled by oxygen diffusion. Two orientation relationships were identified between α-Zr and hexagonal-ZrO, ( 0002 ) α − Z r ∥ ( 1 ¯ 011 ) h − Z r O and [ 2 ¯ 110 ] α - Z r ∥ [ 10 1 ¯ 2 ] h - Z r O or ( 0002 ) α − Z r ∥ ( 22 4 ¯ 1 ¯ ) h − Z r O and [ 2 ¯ 110 ] α − Z r ∥ [ 1 1 ¯ 01 ] h − Z r O , with the first one more commonly observed. No specific orientation relationships between either hexagonal-ZrO and monoclinic-ZrO 2 or α-Zr and monoclinic-ZrO 2 were identified, which suggests that the formation of often-reported bulk oxide texture during aqueous corrosion is not related directly to the texture of the metallic substrate. In conclusion, these results provide a guideline for understanding the mechanisms of crystallographic evolution during oxide growth on commercial zirconium alloys, and also demonstrate the capability of transmission Kikuchi diffraction to investigate orientation relationships in nano-scale materials.

36 MATERIALS SCIENCE↗

DOE OSTI2019

Investigating the stability of second phase particles in Zr-Nb alloys under irradiation

The stability of the β-Nb Second Phase Particles (SPPs) in two types of Zr–Nb alloys (recrystallised Zr-1.0Nb and Zr-2.5Nb) was studied by in-situ heavy ion irradiation in a transmission electron microscope (TEM), combined with ex-situ analysis by energy dispersive x-ray spectroscopy (EDX). TEM thin foils were irradiated by 1 MeV Kr + ions at four different temperatures from 50 K to 873 K, and by 350 keV Kr + ions at different doses up to 39dpa. The change in size of individual β-Nb SPPs has been measured quantitatively, and the degradation mechanisms under irradiation at different temperatures discussed. It has been shown that the Nb redistribution between the SPPs and the Zr matrix is governed both by radiation induced mixing and local diffusion in the surrounding Zr matrix. Finally, under the radiation conditions reported in this study, the β-Nb SPPs have shown remarkably stability against irradiation, and the extent of Nb redistribution between the SPPs and Zr matrix is very limited under all experimental conditions.

36 MATERIALS SCIENCE↗

DOE OSTI2019

Effect of neutron and ion irradiation on the metal matrix and oxide corrosion layer on Zr-1.0Nb cladding alloys

A detailed study has been carried out on recrystallised Zr-1.0Nb alloys corroded and irradiated under different conditions, including ex-autoclave and ex-reactor samples. After 540 days in reactor and damage around 5 dpa, the neutron irradiated sample shows no serious evidence for radiation enhanced corrosion and is still in pre-transition stage. The good corrosion resistance of the neutron irradiated Zr-1.0Nb can be related to the higher volume fraction of tetragonal phase and fewer interconnected nano porosity/cracks in the oxide. This indicates less tetragonal to monoclinic transition, leads to more protective oxide in the neutron irradiated sample, containing little evidence for short circuit paths for the penetration of oxygen or water towards the metal-oxide interface. These observations on a sample with a slow overall oxidation rate are consistent with the hypothesis that interconnected porosity can lead to early transitions and rapid oxidation. Tetragonal oxide can be either stabilised by irradiation, or stabilised by local release of impurity species from SPPs such as dissolution of Fe from Zr-Nb-Fe precipitates or radiation introduced precipitates (RIPs) which is likely to be small β-Nb clusters. The oxide consists of well-aligned columnar-equiaxed microstructure in the autoclave sample while a more complex oxide grain structure was observed in the neutron-irradiated sample. As oxide continues to grow, there are more < a > and < c > loops, dissolved Fe and RIPs in the metal matrix, however, the corrosion rate is low enough for the tetragonal oxide to stabilise and suboxide + Zr(Osat) phases exist for protectiveness, so there is no enhanced corrosion after radiation. In situ ion irradiation in the TEM revealed no visible defect clusters or voids in the oxide, suggesting that radiation damage to the metal matrix rather than oxide may have a stronger effect on corrosion mechanisms after neutron irradiation, however, cascade damages are not visible in this case. Neutron irradiation also seems to have little effect on promoting fast oxidation or dissolution of β-Nb precipitates into the surrounding oxide or metal during irradiation. Furthermore, these results are discussed in the light of the current mechanisms for corrosion of nuclear fuel cladding alloys.

(S)TEM↗

DOE OSTI2019

Atom Probe Tomography Interlaboratory Study on Clustering Analysis in Experimental Data Using the Maximum Separation Distance Approach

We summarize the findings from an interlaboratory study conducted between ten international research groups and investigate the use of the commonly used maximum separation distance and local concentration thresholding methods for solute clustering quantification. The study objectives are: to bring clarity to the range of applicability of the methods; identify existing and/or needed modifications; and interpretation of past published data. Participants collected experimental data from a proton-irradiated 304 stainless steel and analyzed Cu-rich and Ni–Si rich clusters. The datasets were also analyzed by one researcher to clarify variability originating from different operators. The Cu distribution fulfills the ideal requirements of the maximum separation method (MSM), namely a dilute matrix Cu concentration and concentrated Cu clusters. This enabled a relatively tight distribution of the cluster number density among the participants. By contrast, the group analysis of the Ni–Si rich clusters by the MSM was complicated by a high Ni matrix concentration and by the presence of Si-decorated dislocations, leading to larger variability among researchers. While local concentration filtering could, in principle, tighten the results, the cluster identification step inevitably maintained a high scatter. Recommendations regarding reporting, selection of analysis method, and expected variability when interpreting published data are discussed.

APT, Round Robin Studies, atom probe tomography, c↗

DOE OSTI2018

Irradiation-induced amorphization in the zirconium suboxide on Zr-0.5Nb alloys

For the first time, the observation of irradiation-induced amorphization of the zirconium suboxide formed during aqueous corrosion of Zr-0.5Nb alloys is discussed. High-resolution transmission electron microscopy results reveal amorphization of the hexagonal-ZrO suboxide under heavy ion irradiation at cryogenic temperatures. This irradiation-induced amorphization behaviour is discussed in relation to the arrangement of oxygen interstitials and the formation of stable superlattices. The sensitivity of the suboxide to irradiation damage can lead to phase changes and the accumulation of defects near the oxide/metal interface, which needs to be considered in the development of mechanistic models addressing radiation-assisted acceleration of corrosion rates in zirconium alloys.

36 MATERIALS SCIENCE↗

DOE OSTI2017

Dislocation loop evolution during in-situ ion irradiation of model FeCrAl alloys

Model FeCrAl alloys of Fe-10%Cr-5%Al, Fe-12%Cr-4.5%Al, Fe-15%Cr-4%Al, and Fe-18%Cr-3%Al (in wt %) were irradiated with 1 MeV Kr++ ions in-situ with transmission electron microscopy to a dose of 2.5 displacements per atom (dpa) at 320 °C. In all cases, the microstructural damage consisted of dislocation loops with ½< 111 > and <100 > Burgers vectors. The proportion of ½< 111 > dislocation loops varied from ~50% in the Fe-10%Cr-5%Al model alloy and the Fe-18Cr%-3%Al model alloy to a peak of ~80% in the model Fe-15%Cr-4.5%Al alloy. The dislocation loop volume density increased with dose for all alloys and showed signs of approaching an upper limit. The total loop populations at 2.5 dpa had a slight (and possibly insignificant) decline as the chromium content was increased from 10 to 15 wt %, but the Fe-18%Cr-3%Al alloy had a dislocation loop population ~50% smaller than the other model alloys. As a result, the largest dislocation loops in each alloy had image sizes of close to 20 nm in the micrographs, and the median diameters for all alloys ranged from 6 to 8 nm. Nature analysis by the inside-outside method indicated most dislocation loops were interstitial type.

36 MATERIALS SCIENCE↗

DOE OSTI2016

Understanding corrosion and hydrogen pickup of zirconium fuel cladding alloys: The role of oxide microstructure, porosity, sub-oxides, and second-phase particles - 2016-0071

We used a range of advanced microscopy techniques to study the microstructure, nanoscale chemistry, and porosity in zirconium alloys at different stages of oxidation. Samples from both autoclave and in-reactor conditions were available, including ZIRLO{sup TM}, Zr-1.0Nb, and Zr-2.5Nb samples with different heat treatments. Scanning transmission electron microscopy (STEM), transmission Kikuchi diffraction (TKD), and automated crystal orientation mapping with TEM were used to study the grain structure and phase distribution. Significant differences in grain morphology were observed between samples oxidized in the autoclave and in-reactor, with shorter, less well-aligned monoclinic grains and more tetragonal grains in the neutron-irradiated samples. A combination of energy-dispersive X-ray mapping in STEM and atom probe tomography analysis of second-phase particles (SPPs) can reveal the main and minor element distributions respectively. Neutron irradiation seems to have little effect on promoting fast oxidation or dissolution of β-niobium precipitates but encourages the dissolution of iron from Laves-phase precipitates. An electron energy-loss spectroscopy (EELS) analysis of the oxidation state of niobium in β-niobium SPPs in the oxide revealed the fully oxidized Nb{sup 5+} state in SPPs deep into the oxide but Nb{sup 2+} in crystalline SPPs near the metal-oxide interface. EELS analysis and automated crystal orientation mapping with TEM revealed Widmanstatten-type suboxide layers in some samples with the hexagonal ZrO structure predicted by ab initio modeling. The combined thickness of the ZrO suboxide and oxygen-saturated layers at the metal-oxide interface correlated well to the instantaneous oxidation rate, suggesting that this oxygen-rich zone is part of the protective oxide that is rate limiting in the transport processes involved in oxidation. Porosity in the oxide had a major influence on the overall rate of oxidation, and there was more porosity in the rapidly oxidizing annealed Zr-1.0Nb alloy than in either the recrystallized alloy or the similar alloy exposed to neutron irradiation. (authors)

36 MATERIALS SCIENCE↗

DOE OSTI2013

Examinations of Oxidation and Sulfidation of Grain Boundaries in Alloy 600 Exposed to Simulated Pressurized Water Reactor Primary Water

High-resolution characterizations of intergranular attack in alloy 600 (Ni-17Cr-9Fe) exposed to 325 °C simulated pressurized water reactor (PWR) primary water have been conducted using a combination of scanning electron microscopy, NanoSIMS, analytical transmission electron microscopy and atom probe tomography. The intergranular attack exhibited a two-stage microstructure that consisted of continuous corrosion/oxidation to a depth of ~200 nm from the surface followed by discrete Cr-rich sulfides to a further depth of ~500 nm. The continuous oxidation region contained primarily nanocrystalline MO-structure oxide particles and ended at Ni-rich, Cr-depleted grain boundaries with spaced CrS precipitates. Three-dimensional characterization of the sulfidized region using site-specific atom probe tomography revealed extraordinary grain boundary composition changes, including total depletion of Cr across a several nm wide dealloyed zone as a result of grain boundary migration.

36 MATERIALS SCIENCE↗

DOE OSTI2011

Towards an integrated materials characterization toolbox

The material characterization toolbox has recently experienced a number of parallel revolutionary advances, foreshadowing a time in the near future when material scientists can quantify material structure evolution across spatial and temporal space simultaneously. This will provide insight to reaction dynamics in four-dimensions, spanning multiple orders of magnitude in both temporal and spatial space. This study presents the authors’ viewpoint on the material characterization field, reviewing its recent past, evaluating its present capabilities, and proposing directions for its future development. Electron microscopy; atom probe tomography; x-ray, neutron and electron tomography; serial sectioning tomography; and diffraction-based analysis methods are reviewed, and opportunities for their future development are highlighted. Advances in surface probemicroscopy have been reviewed recently and, therefore, are not included [D.A.Bonnell et al.: Rev.Modern Phys. in Review]. In this study particular attention is paid to studies that have pioneered the synergetic use of multiple techniques to provide complementary views of a single structure or process; several of these studies represent the stateof- the-art in characterization and suggest a trajectory for the continued development of the field. Based on this review, a set of grand challenges for characterization science is identified, including suggestions for instrumentation advances, scientific problems in microstructure analysis, and complex structure evolution problems involving material damage. The future of microstructural characterization is proposed to be one not only where individual techniques are pushed to their limits, but where the community devises strategies of technique synergy to address complex multiscale problems in materials science and engineering.

characterization↗