The Constituent Phases and Micromechanical Properties of Steel Corrosion Layers Generated by Hyperbaric-Oxygen Accelerated Corrosion Test.

Hyperbaric oxygen-accelerated corrosion testing (HOACT) is a newly developed method to study in the labor the corrosion behavior of steel bars in concrete. This work aimed to intensively investigate the mechanical properties and microstructures of HOACT-generated corrosion products by means of nano-indentation tests, Raman micro-spectrometry, and scanning electron microscopy. The local elastic modulus and nanohardness varied over wide ranges of 6.8-75.2 GPa and 0.38-4.44 GPa, respectively. Goethite, lepidocrocite, maghemite, magnetite, and akageneite phases were identified in the corrosion products. Most regions of the rust layer were composed of a complex and heterogeneous mix of different phases, while some regions were composed of maghemite or akageneite only. The relationship between the micromechanical properties and typical microstructural features is finally discussed at the micro-scale level. It was found that the porosity of corrosion products can significantly influence their micromechanical properties.

A strategy of designing high-entropy alloys with high-temperature shape memory effect.

Shape memory effect, the ability to recover a pre-deformed shape on heating, results from a reversible martensitic transformation between austenite and martensite phases. Here, we demonstrate a strategy of designing high-entropy alloys (HEAs) with high-temperature shape memory effect in the CrMnFeCoNi alloy system. First, we calculate the difference in Gibbs free energy between face-centered-cubic (FCC) and hexagonal-close-packed (HCP) phases, and find a substantial increase in thermodynamic equilibrium temperature between the FCC and HCP phases through composition tuning, leading to thermally- and stress-induced martensitic transformations. As a consequence, the shape recovery temperature in non-equiatomic CrMnFeCoNi alloys can be increased to 698 K, which is much higher than that of conventional shape memory alloys (SMAs) and comparable to that of B2-based multi-component SMAs containing noble metals (Pd, Pt, etc.) or refractory metals (Zr, Hf, etc.). This result opens a vast field of applications of HEAs as a novel class of cost-effective high-temperature SMAs.

Twinning behavior of orthorhombic-α" martensite in a Ti-7.5Mo alloy.

Deformation microstructure of orthorhombic-α" martensite in a Ti-7.5Mo (wt.%) alloy was investigated by tracking a local area of microstructure using scanning electron microscopy, electron back-scattered diffraction, and transmission electron microscopy. The as-quenched α" plates contain {111}α"-type I transformation twins generated to accommodate transformation strain from bcc-ß to orthorhombic-α" martensite. Tensile deformation up to strain level of 5% induces {112}α"-type I deformation twins. The activation of {112}α"-type I deformation twinning mode is reported for the first time in α" martensite in ß-Ti alloys. {112}α"-type I twinning mode was analyzed by the crystallographic twinning theory by Bilby and Crocker and the most possible mechanism of atomic displacements (shears and shuffles) controlling the newly reported {112}α"-type I twinning were proposed.

Quantitative analysis of {332}〈113〉 twinning in a Ti-15Mo alloy by in situ scanning electron microscopy.

We have performed quantitative analysis of {332}〈113〉 twinning in a ß-Ti-15Mo (wt.%) alloy by in situ scanning electron microscopy and electron backscattering diffraction (EBSD). Microstructure-twinning relations were evaluated by statistical analysis of the evolving twin structure upon deformation at room temperature. Our analysis reveals that at the early stages of deformation (ε < 1.5 to 2.0%), primary twinning is mainly determined by the applied macroscopic stress resolved on the twin system. Most of the primary twins (~70-80% of the analyzed twins) follow Schmid's law with respect to the macroscopic stress, and most of the growth twins (~ 85% of the analyzed twins) correspond to the higher stressed variant. In the grain size range studied here (40-120 µm), we find that several twin parameters such as number of twins per grain and number of twins per grain boundary area exhibit grain size dependence. We ascribe these effects to the grain size dependence of twin nucleation stress and apparent critical resolved shear stress for twinning, respectively.

Microstructure study of a severely plastically deformed Mg-Zn-Y alloy by application of low angle annular dark field diffraction contrast imaging.

Microstructural investigation of extremely strained samples, such as severely plastically deformed (SPD) materials, by using conventional transmission electron microscopy techniques is very challenging due to strong image contrast resulting from the high defect density. In this study, low angle annular dark field (LAADF) imaging mode of scanning transmission electron microscope (STEM) has been applied to study the microstructure of a Mg-3Zn-0.5Y (at%) alloy processed by high pressure torsion (HPT). LAADF imaging advantages for observation of twinning, grain fragmentation, nucleation of recrystallized grains and precipitation on second phase particles in the alloy processed by HPT are highlighted. By using STEM-LAADF imaging with a range of incident angles, various microstructural features have been imaged, such as nanoscale subgrain structure and recrystallization nucleation even from the thicker region of the highly strained matrix. It is shown that nucleation of recrystallized grains starts at a strain level of revolution [Formula: see text] (earlier than detected by conventional bright field imaging). Occurrence of recrystallization of grains by nucleating heterogeneously on quasicrystalline particles is also confirmed. Minimizing all strain effects by LAADF imaging facilitated grain size measurement of [Formula: see text] nm in fully recrystallized HPT specimen after [Formula: see text].

Study of {332}<113> twinning in a multilayered Ti-10Mo-xFe (x = 1-3) alloy by ECCI and EBSD.

We have investigated the propagation of {332}<113> twins in a multilayered Ti-10Mo-xFe (x = 1-3) alloy fabricated by multi-pass hot rolling. The material contains a macroscopic Fe-graded structure (about 130 µm width) between 1 and 3 wt% Fe in the direction perpendicular to rolling. We observe strong influence of the Fe-graded structure in the twin propagation behavior. The propagation of {332}<113> twins that are nucleated in Fe-lean regions (~1 wt% Fe) is interrupted in the grain interiors at a specific Fe content, namely, about 2 wt% Fe. We ascribe this effect to the role of Fe content in solid solution on the stress for twin propagation. The interruption of twins in the grain interiors results in the development of characteristic dislocation configurations such as highly dense dislocation walls (HDDWs) associated to strain localization phenomena. The nucleation and propagation of these dislocation configurations is ascribed to the underlying plastic accommodation mechanisms of the stress field at the twin tips. We find that the crystallographic alignment of HDDWs is determined by the stress field at the twin tips and the deformation texture. The excellent plastic accommodation at the interrupted twin tips allows attaining the good ductility of the present material (total elongation of 28%).

Longitudinal Hierarchy Co3O4 Mesocrystals with High-dense Exposure Facets and Anisotropic Interfaces for Direct-Ethanol Fuel Cells.

Novel electrodes are needed for direct ethanol fuel cells with improved quality. Hierarchical engineering can produce catalysts composed of mesocrystals with many exposed active planes and multi-diffused voids. Here we report a simple, one-pot, hydrothermal method for fabricating Co3O4/carbon/substrate electrodes that provides control over the catalyst mesocrystal morphology (i.e., corn tubercle pellets or banana clusters oriented along nanotube domains, or layered lamina or multiple cantilevered sheets). These morphologies afforded catalysts with a high density of exposed active facets, a diverse range of mesopores in the cage interior, a window architecture, and vertical alignment to the substrate, which improved efficiency in an ethanol electrooxidation reaction compared with a conventional platinum/carbon electrode. On the atomic scale, the longitudinally aligned architecture of the Co3O4 mesocrystals resulted in exposed low- and high-index single and interface surfaces that had improved electron transport and diffusion compared with currently used electrodes.

Cytocompatibility evaluation and surface characterization of TiNi deformed by high-pressure torsion.

Effect of high-pressure torsion (HPT) deformation on biocompatibility and surface chemistry of TiNi was systematically investigated. Ti-50 mol% Ni was subjected to HPT straining for different numbers of turns, N=0.25, 0.5, 1, 5 and 10 at a rotation speed of 1 rpm. X-ray photoelectron spectroscopy observations after 7 days of cell culture revealed the changes in the surface oxide composition, enrichment of Ti and detection of nitrogen derived from organic molecules in the culture medium. Plating efficiency of L929 cells was slightly increased by HPT deformation though no significant difference was observed. Albumin adsorption was higher in HPT-deformed samples, while vitronectin adsorption was peaked at N=1. HPT deformation was also found to effectively suppress the Ni ion release from the TiNi samples into the cell culture medium even after the low degree of deformation at N=0.25.

Effect of high-pressure torsion deformation on surface properties and biocompatibility of Ti-50.9 mol. %Ni alloys.

Ti-50.9 mol. %Ni was subjected to high-pressure torsion (HPT) deformation for different number of rotations (N) of 0.25, 0.5, 1, 5, and 10. The structural changes induced by HPT were analyzed using x-ray diffractometer (XRD). The surfaces of the samples before and after cell culture were characterized using x-ray photoelectron spectroscopy (XPS). The biocompatibility of the samples was evaluated based on a colony formation assay, nickel ion release, and protein adsorption behavior. XRD analysis revealed the occurrence of grain refinement, phase transformation, and amorphization in the TiNi samples by HPT deformation due to high dislocation density. The changes in chemical composition and thickness of the passive film formed on the surface observed in XPS analysis reveals improvement in the stability of the passive film by HPT deformation. The microstructural change due to the deformation was found to influence the biocompatibility behaviors of TiNi. Plating efficiency and protein adsorption were found to be higher when the samples are in stress-induced martensitic or amorphous state. HPT deformation was found to alter the surface behavior of the TiNi, which effectively reduced the Ni ion release and improved its biocompatibility.

Low temperature heat capacity of a severely deformed metallic glass.

The low temperature heat capacity of amorphous materials reveals a low-frequency enhancement (boson peak) of the vibrational density of states, as compared with the Debye law. By measuring the low-temperature heat capacity of a Zr-based bulk metallic glass relative to a crystalline reference state, we show that the heat capacity of the glass is strongly enhanced after severe plastic deformation by high-pressure torsion, while subsequent thermal annealing at elevated temperatures leads to a significant reduction. The detailed analysis of corresponding molecular dynamics simulations of an amorphous Zr-Cu glass shows that the change in heat capacity is primarily due to enhanced low-frequency modes within the shear band region.

First-principles study of electronic structures and stability of body-centered cubic Ti-Mo alloys by special quasirandom structures.

The electronic structures and structural properties of body-centered cubic Ti-Mo alloys were studied by first-principles calculations. The special quasirandom structures (SQS) model was adopted to emulate the solid solution state of the alloys. The valence band electronic structures of Ti-Mo and Ti-Mo-Fe alloys were measured by hard x-ray photoelectron spectroscopy. The structural parameters and valence band photoelectron spectra were calculated using first-principles calculations. The results obtained with the SQS models showed better agreement with the experimental results than those obtained using the conventional ordered structure models. This indicates that the SQS model is effective for predicting the various properties of solid solution alloys by means of first-principles calculations.