The Effect of Hf Addition on the Boronizing and Siliciding Behavior of CoCrFeNi High Entropy Alloys

The effect of a boronizing and siliciding process on CoCrFeNiHf0.1–0.42 high entropy alloys was examined in this study. When increasing the amount of added Hf in CoCrFeNiHfx, the structure of the alloys gradually transformed from single-phase FCC to firstly Ni7Hf2 + FCC, and finally to C15 Laves and FCC phases. The boronizing/siliciding process resulted in the formation of a silicon-rich layer and a boride layer (BL). Increasing the amount of Hf in the alloys resulted in a decrease in the combined layer thickness, which was measured for CoCrFeNi, CoCrFeNiHf0.1, CoCrFeNiHf0.2, and CoCrFeNiHf0.42 to be 70 \ub5m, 63 \ub5m, 20 \ub5m, and 15 \ub5m, respectively. In contrast, the thickness of the transition zone/diffusion zone increased with more Hf in the alloys. While silicon atoms were gathered close to the BL, they were not transferred into the CoCrFeNi substrate. In contrast to the observation for CoCrFeNi, Si atoms penetrated through the Ni-rich phase (Ni7Hf2) in the CoCrFeNiHfx alloys. Furthermore, the Cr-B rich area (Cr5B3) in the coating limited the transport of Si into the CoCrFeNiHfx substrates. XRD analysis showed that the BL contained Ni2Si, FeB, Fe2B, Co2B, and Cr5B3 phases

Elemental distribution in a decommissioned high Ni and Mn reactor pressure vessel weld metal from a boiling water reactor

In this paper, weld metal from unique material of a decommissioned boiling water reactor pressure vessel is investigated. The reactor was in operation for 23 effective full power years. The elemental distribution of Ni, Mn, Si and Cu in the material is analysed using atom probe tomography. There are no well-defined clusters of these elements in the weld metal. However, some clustering tendencies of Ni was found, and these are interpreted as a high number density of small features. Cu atoms were found to statistically be closer to Ni atoms than in a fully random solid solution. The impact of the non-random elemental distribution on mechanical properties is judged to be limited

Carbide precipitation in a low alloyed steel during aging studied by atom probe tomography and thermodynamic modeling

Carbide precipitation in martensitic low alloyed steels contributes to the mechanical properties through precipitation hardening. A high number density of carbides is desired to maximize the hardening effect, which is achieved through the precipitation of carbides on the dislocations in the martensitic structure. In this study, the nucleation, growth, and coarsening of vanadium and molybdenum carbides during aging at 600◦C for periods up to four weeks were investigated. The work covers characterization with atom probe tomography, which showed that the nucleation of V and Mo rich MC/M2C carbides takes place on dislocations. The growth of these carbides proceeds by the diffusion of elements to the dislocations, which has been modeled using Dictra software, confirming the rate of the reaction as well as the depletion of carbide formers in the matrix. For longer aging times, particle coarsening will decrease the number density of particles with a transition from dislocation-based carbides to separate rounded carbides

Tin clustering and precipitation in the oxide during autoclave corrosion of Zircaloy-2

Atom probe tomography has been used to study the evolution of tin distribution during the corrosion process in Zircaloy-2. From being completely soluble in the Zr metal matrix, some clustering is evident already in the newly formed oxide close to the metal-oxide interface. Analysis of thicker oxides a few hundred nanometers away from the interface reveals fully developed precipitates of metallic Sn particles of up to 20 nm in size. Although the precipitates contain significant amounts of Zr, it is concluded that they are in the process of being depleted in Zr, which is limited only by the slow diffusion in the oxide scale. The findings are interpreted as being a result of the nobility of the Sn yielding a strong driving force to remain in a metallic state after incorporation in the barrier oxide layer. As Sn occupies substitutional sites in the ZrO2 lattice it is oxidized to a 4+ state when incorporated into the oxide, and in order to remain metallic it must nucleate into precipitates within the inner part of the oxide scale before being re-oxidized to 2+ and eventually to 4+ when the oxygen activity is sufficiently high in the outer parts of the oxide

Multiple Influences of Molybdenum on the Precipitation Process in a Martensitic PH Stainless Steel

Molybdenum has been found to influence the complex precipitation process in a martensitic precipitation hardening stainless steel during aging at 475 degrees C in several different ways. Three steels with different Mo content (0, 1.2 and 2.3 at.%) were investigated. Studies of the microstructure were performed with atom probe tomography and energy filtered transmission electron microscopy. It is shown that, at the initial stage of aging, a faster nucleation of Cu-rich clusters takes place with increasing Mo content. The Cu-clusters act as precipitation sites for other solute elements and promote the nucleation of Ni-rich phases. During further aging, a higher Mo content in the material instead slows down the growth and coarsening of the Ni-rich phases, because Mo segregates to the interface between precipitate and matrix. Additionally, Mo promotes decomposition of the matrix into alpha and alpha\u27 regions. After longer aging times (>40 h) quasicrystalline Mo-rich R\u27 phase forms (to a greater extent in the material having the highest Mo content). The observations serve to understand the hardness evolution during aging

Quantitative Evaluation of Spinodal Decomposition in Fe-Cr by Atom Probe Tomography and Radial Distribution Function Analysis

Nanostructure evolution during low temperature aging of three binary Fe-Cr alloys has been investigated by atom probe tomography. A new method based on radial distribution function (RDF) analysis to quantify the composition wavelength and amplitude of spinodal decomposition is proposed. Wavelengths estimated from RDF have a power-law type evolution and are in reasonable agreement with wavelengths estimated using other more conventional methods. The main advantages of the proposed method are the following: (1) Selecting a box size to generate the frequency diagram, which is known to generate bias in the evaluation of amplitude, is avoided. (2) The determination of amplitude is systematic and utilizes the wavelength evaluated first to subsequently evaluate the amplitude. (3) The RDF is capable of representing very subtle decomposition, which is not possible using frequency diagrams, and thus a proposed theoretical treatment of the experimental RDF creates the possibility to determine amplitude at very early stages of spinodal decomposition

Complete precipitate dissolution during adiabatic shear localisation in a Ni-based superalloy

Whereas microstructure evolution in adiabatic shear bands have been thoroughly studied, reports on the stability of hardening precipitates during shear localisation are scarce. We report an atomic scale investigation of solute distribution in adiabatic shear bands in a precipitation strengthened Ni-Fe-based superalloy, showing that the hardening particles are completely dissolved. Temperature estimations indicate that peak temperatures in the shear band above the solvus limits of the precipitates are not unrealistic, and thus diffusion-assisted transformations during the severe plastic deformation cannot be ruled out

Integrated effect of thermal ageing and low flux irradiation on microstructural evolution of the ferrite of welded austenitic stainless steels

With the purpose to quantify microstructural changes with respect to ageing degradation, the microstructure of aged type 308 stainless steel welds with a ferrite content of 5-7% has been analysed using atom probe tomography. The weld metal of the core barrel of a decommissioned light water reactor, irradiated during operation of the reactor to 0.1 dpa, 1 dpa and 2 dpa at 280-285\ub0C (231,000 h), are compared to two similar thermally aged welds. In the ferrite of the irradiated welds, there is spinodal decomposition into Cr-rich α’ and Fe-rich α, with a similar degree of decomposition for all investigated doses, amplitudes of 21-26% and wavelengths between 6 and 9 nm. The ferrite of the thermally aged material showed evidence of decomposition when aged at 325\ub0C (an amplitude of 13-14% and wavelength of 5 nm), but not when aged at 291\ub0C, thus the irradiation significantly increases the rate of spinodal decomposition. There is G-phase (Ni Si Mn ) precipitation in the ferrite of all the weld metals except the one that was thermally aged at the lowest temperature. After irradiation to 1 and 2 dpa, the G-phase is considerably more well developed than after 0.1 dpa or thermal ageing

Atomically Resolved Interfacial Analysis of Bone-Like Hydroxyapatite Nanoparticles on Titanium

Titanium is commonly used for medical devices, including osseointegrating implants, owing to its biocompatibility and mechanical properties. Nanostructuring titanium implants is known to enhance the healing process by promoting bone growth on the implant surface. Hydroxyapatite nanoparticles, resembling natural bone mineral, have been used to further improve osseointegration. While previous studies have investigated the osseointegration of titanium implants using atom probe tomography, limited research has focused on the attachment of synthetic hydroxyapatite to titanium. Herein, electron microscopy and atom probe tomography are used to reveal the assembly of synthetic hydroxyapatite nanoparticles in the titanium oxide surface. By sputter coating with chromium, a suitable matrix is formed for detailed interfacial analysis. The results demonstrate the diffusion of calcium, phosphorus, and carbon from hydroxyapatite nanoparticles into the titanium oxide surface. Titanium is commonly used for medical devices, owing to its biocompatibility and mechanical properties. Nanostructuring titanium implants with hydroxyapatite nanoparticles, resembling natural bone mineral, enhances the healing process by promoting bone growth on the implant surface. Herein, atom probe tomography reveals the assembly of synthetic hydroxyapatite nanoparticles in the titanium oxide surface.image & COPY; 2023 WILEY-VCH Gmb

The Nanostructure of the Oxide Formed on Fe-10Cr-4Al Exposed in Liquid Pb

An Fe-10Cr-4Al alloy containing reactive elements developed for application in high-temperature liquid lead environments was analyzed after exposure in 600 and 750\ub0C lead with dissolved oxygen for 1,000-2,000 h. Atom probe tomography, transmission electron microscopy, and X-ray scattering were all used to study the protective oxide formed on the surface. Exposure at 750\ub0C resulted in a 2-μm thick oxide, whereas the 600\ub0C exposure resulted in a 100-nm thick oxide. Both oxides were layered, with an Fe-Al spinel on top, and an alumina layer toward the metal. In the 600\ub0C exposed material, there was a Cr-rich oxide layer between the spinel and the alumina. Metallic lead particles were found in the inner and middle parts of the oxide, related to pores. The combination of the experimental techniques, focusing on atom probe tomography, and the interpretations that can be done, are discussed in detail