High-resolution Synchrotron Radiation X-ray Research Articles

In situ X-ray tomography of fracture behaviour in low-porosity L-PBF AlSi10Mg alloy with laser shock peening

ABSTRACT In this study, we employed a novel hybrid AM process, in which periodic laser shock peening (LSP) treatments were added to the standard laser powder bed fusion (L-PBF) process, for fabricating the AlSi10Mg alloy. As a result, the porosity of the alloy was reduced by approximately 90%. To monitor damage evolution, we conducted in situ tensile tests using high-resolution synchrotron radiation X-ray micro-computed tomography. The results indicate that in the LSP-treated L-PBF AlSi10Mg alloy, with a porosity of around 0.05%, the plasticity of vertical tensile samples significantly increases, and the fracture strain closely resembles that of the horizontal sample. The reduction in porosity results in increased spacing between adjacent defects, which decreases the interaction between defects. Consequently, the rapid fracture caused by the merge of large defects is prevented. Notably, micro-cracks observed in the vertical samples before tensile fracture primarily originates at the molten pool boundaries rather than from defects.

Anharmonicity effects and thermal expansion of thermoelectric (M,M’,M”)NiSn (M,M’,M”=Ti, Zr, Hf) half-Heusler alloys

High-resolution synchrotron radiation X-ray powder diffraction was used for the structural characterization of half-Heusler alloys with compositions MNiSn, M0.5M′0.5NiSn, and M0.5M′0.25M”0.25NiSn ((M, M′, M”) = Ti, Zr, Hf). These alloys were synthesized by arc melting and subsequent thermal annealing. Rietveld refinements of the room temperature patterns revealed that the unit cell parameter is larger for ZrNiSn and smaller for TiNiSn, in accordance with the respective atomic radii. The site occupation of each atomic species exhibited similar trends to those reported in the literature. The values of the linear coefficient of thermal expansion (α) for all the investigated phases within the alloys are < 10−5 K−1. In addition, the value of the Debye temperature (θD) is estimated by analyzing the temperature dependence of the isotropic atomic displacement parameters. In the case of these half-Heusler alloys, it is observed that a lower θD corresponds to a lower α. The good agreement between the temperature dependence of the Debye temperature and the calculated values using the Thirring-Stern expansion enables us to demonstrate the significant role of anharmonicity: the lighter the compound, the lower the anharmonicity. Furthermore, we also discuss the implications of anharmonicity on the thermal conductivity of this family of half-Heusler compounds at room temperature.

(Invited) Thin Epitaxial Single-Crystal Si on Sige Followed By in-Situ Deposition of High-k Dielectrics – Novel Gate Stacks for Achieving Extremely Low Dit and Highly Reliable SiGe MOS

Silicon-germanium (SiGe) is replacing silicon (Si) as the channel layer for the p-type metal-oxide-semiconductor (pMOS) in the aggressively scaled complementary MOS (CMOS) technology. Many research efforts involving SiGe gate stacks have resulted in the attainment of low interfacial trap densities (Dits). Si-passivated SiGe gate stacks are the most promising method to achieve both low Dit and high device reliability. However, regardless of the growth methods, most publications reported the pileup of Ge atoms on top of the grown Si even after extensive treatments. The subsequent process in forming gate stacks, including oxidation, inevitably caused the segregated Ge to form GeOx, leading to degradation of the interfacial quality of the gate stacks.We have used molecular beam epitaxy (MBE) to grow thin single-crystal Si of 0.79nm thickness (six MLs) epitaxially on epi-Si1-xGex(001) under ultra-high vacuum (UHV). Different from its counterpart of chemical vapor deposition (CVD), MBE enables epi-Si growth on Ge at growth temperatures below 300 °C. The measurements using reflection high-energy electron diffraction (RHEED), high-resolution synchrotron radiation X-ray diffraction (HR-XRD), and the scanning transmission electron microscopy with high-angle annular-dark-field (STEM-HAADF) have revealed high crystallinity of the epi-Si, the Si1-xGex layers and abrupt interfaces of the high-k/epi-Si/Si1-xGex layers. Moreover, our unique capability of epi growth/analysis enabled the study of the electronic surface structures of epi-Si/epi-Ge using in-situ high-resolution synchrotron radiation photoemission spectroscopy (SRPES) via a portable sample transfer station under UHV. We have used SRPES to demonstrate that the as-grown Si1−xGex(001)-2×1 surfaces with Ge content ranging from 0.1 to 0.9 are all terminated with buckled Ge–Ge dimers, and the surface electronic structure is similar to that of epi-Ge(001)-2×1. The direct deposition of epi-Si on as-grown SiGe removed the top buckled Ge-Ge dimers, which diffused into the epi-Si and some segregated to the top of the Si. As a result, the topmost layer beneath the epi-Si was 1 ML of Ge, and the interfaces of high-k/epi-Si/Si1−xGex are similar to those of the high-k/epi-Si/Ge. Again, the hetero-interfaces of our gate dielectrics are different from those grown using CVD.The well-controlled interfaces have enabled the achievement of low interfacial trap densities (Dit) of (3 - 6) × 1011 eV-1cm-2 in these high-k/epi-Si/Si1-xGex samples. The minimum Dit values remained at 3 × 1011 eV-1cm-2 regardless of the Ge content, demonstrating the effective passivation of the low-temperature deposited epi-Si. The limited Ge segregation during the low-temperature growth of epi-Si may attribute to the attainment of the low Dit values. We have benchmarked the minimum Dit (Dit, min) of our work with other state-of-the-art SiGe gate stacks. The Dit,min values from the other efforts increased with increasing Ge content, which may be caused by the GeOx formation that was difficult to control in the high-Ge-content (HGC) Si1-xGex.The effective charge sheet densities for the Si1-xGex gate stacks were extracted via examination of capacitance-voltage (C-V) hysteresis with decreasing stress voltage in the accumulation region of the MOS capacitors. We have attained very high acceleration factors of 8-12, indicating high reliability of the HfO2/epi-Si/Si1-xGex pMOS gate stacks.Furthermore, we have used a scavenging method, consisting of a cyclic process of an O2 exposure followed by a UHV annealing, to eliminate the segregated and diffused Ge in epi-Si before high-k deposition. Upon O2 exposure at room temperature, both the Si and Ge surface atoms are simultaneously oxidized to give rise to four Si charge states and Ge suboxides, respectively. The subsequent in-situ annealing at 500 °C under UHV moved the oxygen atom in the Ge suboxides to bond with the nearby Si atom. The annealing also caused the diffused Ge inside the epi-Si to segregate to the surface. The processes of O2 exposure followed by annealing were repeated three times resulting in an oxidized Si/Ge surface having only the four Si oxidized states without GeOx, but with a minimal amount of segregated Ge.

Oxidation Mechanisms of Hafnium Overlayers Deposited on an Si(111) Substrate.

The oxidation mechanism of hafnium overlayers on an Si(111) substrate [Hf-Si(111), including the outermost metallic Hf overlayers and interfacial Hf silicides (HfSi and HfSi4)] was investigated via high-resolution synchrotron radiation X-ray photoelectron spectroscopy (SR-XPS) of Hf 4f5/2,7/2, Si 2p1/2,3/2, and O 1s core levels. The atomic-scale interaction of O2 molecules with Hf-Si(111) is discussed by comparing the results obtained following thermal O2 exposures [translational energy (Et) ≈ 0.03 eV] with those obtained following supersonic O2 molecular beam (SOMB) irradiation (Et ≈ 2.2 eV). Metallic Hf and interfacial HfSi were immediately oxidized to HfO2 and Hf (sub)silicates (Hf-O-Si configurations) via trapping-mediated dissociative adsorption. Upon excessive SOMB irradiation, the other interfacial HfSi4 was oxidized via direct dissociation. When oxidation proceeded at the Si(111) substrate via excess SOMB irradiation, volatile Si atoms were emitted from the interfacial SiO2/Si-strained layers. When the volatile Si atoms were trapped in the overlayers, the HfO2 overlayers were converted into completely oxidized Hf silicate layers. However, when the volatile Si atoms passed through the HfO2 overlayers, they reacted with the impinging O2, and the outermost SiO2 deposition layers were formed on HfO2 (or Hf silicate) layers.

3D ring artifacts removal algorithm combined low-rank tensor decomposition with spatial-sequential total variation regularization and its application in phase-contrast microtomography.

High-resolution synchrotron radiation X-ray phase contrast microtomography (PC-μCT) images often suffer from severe ring artifacts, which are mainly caused by undesirable responses of detector elements. In the medical imaging field, the existence of ring artifacts can lead to degraded visual quality and can directly affect diagnosis accuracy. Thus, removing or at least effectively reducing ring artifacts is indispensable. The existing ring artifacts removal algorithms mainly focus on two-dimensional (matrix-based) priors, and these algorithms fail to consider correlations hidden in sequential computed tomography (CT) images. This paper proposed a novel three-dimensional (tensor-based) ring artifacts removal algorithm for synchrotron radiation X-ray PC-μCT images. In the sinogram domain, ring artifacts manifest as vertical stripe artifacts. From an image decomposition perspective, a degraded sinogram can be decomposed into a stripe artifacts component and an underlying clean sinogram component. The proposed algorithm is designed to detect and remove stripe artifacts from a degraded sinogram by fully identifying the characteristics of the two components. Specifically, for the stripe artifacts component, tensor Tucker decomposition is used to describe its low-rank character. For the underlying clean sinogram component, spatial-sequential total variation regularization is adopted to enhance the piecewise smoothness. Moreover, the Frobenius norm term is further used to model Gaussian noise. An efficient augmented Lagrange multiplier method is designed to solve the proposed optimization model. The proposed method is evaluated utilizing both simulations and real data containing different ring artifacts patterns. In the simulations, the human chest CT images are used for evaluating the proposed method. We compare the peak signal-to-noise ratio (PSNR), structural similarity (SSIM), and mean absolute error (MAE) results of our algorithm with the Naghia's method, the RRRTV method, the wavelet-FFT method, and the SDRSD-GIF method. The proposed method was also evaluated on real data from rat liver samples and rat tooth samples. Our proposed method outperforms the competing methods in terms of both qualitative and quantitative evaluation results. Additionally, the 3D visualization results were presented to make the ring artifacts removal effect more intuitive. The experimental results on simulations and real data clearly demonstrated that the proposed algorithm can significantly improve the quality of PC-μCT images compared with the existing popular algorithms, and it has great potential to promote the application of high-resolution imaging for visualizing biological tissues.

Internal 3D cracks evolution and the toughening mechanisms of the hierarchical structures in Strombus gigas shell

Strombus gigas shell is a lightweight, high-strength and high-toughness biocomposite material. In-depth exploration of its internal microstructure characteristics and the corresponding strengthening and toughening mechanism is of great significance to the design of high-performance composite materials. Here, the high-resolution synchrotron radiation X-ray computed tomography technology was adopted to carry out the in-situ three-dimensional investigation on the deformation and fracture evolution of the internal crossed-lamellar hierarchical structures of the Strombus gigas shell during the tensile process. In the experiment, some important three-dimensional crack initiation and propagation evolution phenomena were observed, such as the multi-point bursting, progressive propagation and spatial network arrangement of cracks and the reverse ‘C’-shaped cracks, which may have great contribution to the load-bearing capacity and toughness of the shell. According to the mechanical analysis of the visualized evolutionary information of the deformation and fracture of hierarchical microstructures, a strengthening and toughening regulation mechanisms that driven by the local stress concentration, and guided by the hierarchical structure and weak interface was proposed. This study may have a positive guiding significance for exploring and learning the toughening design strategy of lightweight composites.

Three-dimensional structural measurement and material identification of an all-solid-state lithium-ion battery by X-Ray nanotomography and deep learning

Three-dimensional measuring method of the material distribution of an all-solid-state lithium-ion battery (ASSLiB) cathode, by synchrotron radiation high-resolution X-ray computational tomography (nanotomography, nano-CT) and deep learning is proposed in this study. The cathode of the ASSLiB comprised materials with high X-ray absorption coefficients, such as LiCoO 2 and LiNi 0.5 Co 0.2 Mn 0.3 O 2 . Such high absorption coefficients imparted difficulties in obtaining a high-resolution, high-contrast image and in identifying materials with conventional CT value method. The method proposed in this study was effective in acquiring a high-resolution image with fewer artifacts and measured the heavy materials at a high signal-to-noise ratio. We used deep learning with a customized U-net, enabling high accuracy and ultra-high-speed material identification. Using this method, constituent materials were successfully identified in three dimensions. This material identification technique showed great potential for application to other techniques such as focused ion beam–scanning electron microscopy. • High resolution imaging of ASSLiB is conducted with synchrotron radiation X-ray nano-CT. • Material identification technique for a CT image of ASSLiB by deep learning (U-net) is proposed. • The U-net segmented CT images at low computational cost and ultra-high speed • The segmentation approach can also be applied to other observation techniques

Sub-trabecular strain evolution in human trabecular bone

To comprehend the most detrimental characteristics behind bone fractures, it is key to understand the material and tissue level strain limits and their relation to failure sites. The aim of this study was to investigate the three-dimensional strain distribution and its evolution during loading at the sub-trabecular level in trabecular bone tissue. Human cadaver trabecular bone samples were compressed in situ until failure, while imaging with high-resolution synchrotron radiation X-ray tomography. Digital volume correlation was used to determine the strains inside the trabeculae. Regions without emerging damage were compared to those about to crack. Local strains in close vicinity of developing cracks were higher than previously reported for a whole trabecular structure and similar to those reported for single isolated trabeculae. Early literature on bone fracture strain thresholds at the tissue level seem to underestimate the maximum strain magnitudes in trabecular bone. Furthermore, we found lower strain levels and a reduced ability to capture detailed crack-paths with increased image voxel size. This highlights the dependence between the observed strain levels and the voxel size and that high-resolution is needed to investigate behavior of individual trabeculae. Furthermore, low trabecular thickness appears to be one predictor of developing cracks. In summary, this study investigated the local strains in whole trabecular structure at sub-trabecular resolution in human bone and confirmed the high strain magnitudes reported for single trabeculae under loading and, importantly extends its translation to the whole trabecular structure.

Comparing CALPHAD predictions with high energy synchrotron radiation X-ray diffraction measurements during in situ annealing of Al0.3CoCrFeNi high entropy alloy

High-entropy alloys (HEAs) offer the unique ability to tailor microstructures through thermal processing techniques. One family of alloys of interest is AlxCoCrFeNi, where x varies from 0.0 to 2.0 molar fraction which allows for a transition from face-centered cubic (FCC) to body-centered cubic (BCC) crystal structure, as well as the formation of various secondary phases, such as B2, sigma, and L12. In this study, we focus on the Al0.3CoCrFeNi HEA. Based on CALPHAD simulations, the Al0.3CoCrFeNi HEA consists of the following phases from highest to lowest temperature: a) FCC at high temperature, followed by b) B2 precipitation in an FCC matrix, c) then B2 and σ phase co-precipitation in an FCC matrix, d) then B2, σ phase, and L12 phase in an FCC matrix, and finally e) B2, σ phase, and L12 phase in a BCC matrix at low temperature. The purpose of our study is to compare phases observed using high-energy synchrotron radiation X-ray diffraction measurements during in situ annealing with the equilibrium phases predicted using CALPHAD. Phase evolution and dissolution are discussed and compared with the CALPHAD simulation predictions. Our experimental results matched well with the CALPHAD predictions of the phase evolution for the B2 phase, however, the phase dissolution of L12 and σ phases was incomplete, which is likely only observable using high resolution synchrotron radiation X-ray diffraction. Better CALPHAD models are needed as well as longer annealing times due to the complexity of achieving phase equilibrium in multi-phase HEAs.

A new approach to correlate the defect population with the fatigue life of selective laser melted Ti-6Al-4V alloy

Microstructural features and defects arising from selective laser melting (SLM) determine the in-service performance of additively manufactured near-net-shape components. Here the grain type, shape, size and distribution were characterized using electron backscattered diffraction (EBSD). High-resolution synchrotron radiation X-ray computed tomography (CT) was used to quantify the population, morphology and dimensions of porosity and lack of fusion defects. For SLM Ti-6Al-4V alloy, the larger-sized defects in comparison with the α grains are more important for crack initiation, typically leading to poor fatigue resistance and a pronounced variation in fatigue life. The fatigue strength was then evaluated in terms of the defect population using a combination of the statistics of extremes and the Murakami model. Finally, an extended Kitagawa-Takahashi fatigue diagram was established within the framework of defect-tolerant design, which includes a classical safe-life region and the defect-determined lifetime in the finite life region.

Compositional and structural analysis of Fukushima-derived particulates using high-resolution x-ray imaging and synchrotron characterisation techniques

Both the three-dimensional internal structure and elemental distribution of near-field radioactive fallout particulate material released during the March 2011 accident at the Fukushima Daiichi Nuclear Power Plant is analysed using combined high-resolution laboratory and synchrotron radiation x-ray techniques. Results from this study allow for the proposition of the likely formation mechanism of the particles, as well as the potential risks associated with their existence in the environment, and the likely implications for future planned reactor decommissioning. A suite of particles is analyzed from a locality 2 km from the north-western perimeter of the site – north of the primary contaminant plume in an area formerly attributed to being contaminated by fallout from reactor Unit 1. The particles are shown to exhibit significant structural similarities; being amorphous with a textured exterior, and containing inclusions of contrasting compositions, as well as an extensive internal void volume – bimodal in its size distribution. A heterogeneous distribution of the various elemental constituents is observed inside a representative particle, which also exhibited a Fukushima-derived radiocesium (134Cs, 135Cs and 137Cs) signature with negligible natural Cs. We consider the structure and composition of the particle to suggest it formed from materials associated with the reactor Unit 1 building explosion, with debris fragments embedded into the particles surface. Such a high void ratio, comparable to geological pumice, suggests such material formed during a rapid depressurisation and is potentially susceptible to fragmentation through attrition.

Strain engineering on the metal-insulator transition of VO2/TiO2 epitaxial films dependent on the strain state of vanadium dimers

In this letter, a series of vanadium dioxide (VO2) epitaxial films were deliberately deposited on TiO2 substrates with different orientations [(001), (110), and (101)], in an attempt to gain insights into the strained VO2 epitaxial film. We found in-plane [100] and [1-10] directions, obviously anisotropic metal-insulator transition (MIT) in (110)-oriented VO2 films. In combination with synchrotron radiation high-resolution x-ray diffraction characterizations, electronic transport data reveal that the critical temperature of MIT depends on the strain state of the dimeric vanadium atomic chain along the c axis of the rutile phase. The anisotropy of MIT is closely related to the orientation of the VO2 films, which is caused by the varied orientation configuration of V-V atomic chain dimerization in the films. Soft x-ray absorption spectroscopy results further indicate that this anisotropy may be driven by the directional hybridization of O 2p and V 3d orbitals with respect to the orientation of VO2 thin films. The polarization-dependent V L-edge and O K-edge XAS data suggest that the elongation of the apical V-O bond length increases the p-d orbital overlap; thus, the energy level of the d// orbital is raised relative to that of the π* orbital. These anisotropic MIT behaviors will help us to understand how the strain engineering depends on the strain state of vanadium dimers in VO2 films.

Tuning the interfaces in the ruthenium-nickel/carbon nanocatalysts for enhancing catalytic hydrogenation performance

The ruthenium-nickel bimetallic nanoparticles supported on carbon black (Ru-Ni/C) with various Ru and Ni loadings, while keeping a constant Ru/Ni atomic ratio (51/49), were synthesized at ambient temperature by liquid reduction with hydrazine hydrate as reducing agent and galvanic replacement reaction approaches. Different Ru-Ni interfaces (Ru-Ni-NiO with 1.250 wt% or 0.630 wt% Ru, and RuO2-NiO with 0.160 wt% Ru) were formed after being annealed in N2 at 380 °C for 3 h. Several techniques, including powder X-ray diffraction (XRD), transmission electron microscopy (TEM), high resolution TEM (HRTEM) and synchrotron radiation X-ray absorption spectroscopy (XAS) and in-situ XAS (in hydrogen) have been employed for structural characterization. It was found that most Ru atoms and a small amount of Ni atoms at the Ru-Ni-NiO interface were reduced, leading to the occurrence of hydrogen spillover and hence synergy effect of Ru, Ni and NiO active sites. However, such a synergy was not observed at the RuO2-NiO interface. The catalytic properties of the Ru-Ni/C nanocatalysts in the hydrogenation of benzene reaction were significantly improved due to the presence of particular Ru-Ni-NiO interface.

Strain-stress study of AlxGa1\u2212xN/AlN heterostructures on c-plane sapphire and related optical properties

This work presents a systematic study of stress and strain of AlxGa1−xN/AlN with composition ranging from GaN to AlN, grown on a c-plane sapphire by metal-organic chemical vapor deposition, using synchrotron radiation high-resolution X-ray diffraction and reciprocal space mapping. The c-plane of the AlxGa1−xN epitaxial layers exhibits compressive strain, while the a-plane exhibits tensile strain. The biaxial stress and strain are found to increase with increasing Al composition, although the lattice mismatch between the AlxGa1−xN and the buffer layer AlN gets smaller. A reduction in the lateral coherence lengths and an increase in the edge and screw dislocations are seen as the AlxGa1−xN composition is varied from GaN to AlN, exhibiting a clear dependence of the crystal properties of AlxGa1−xN on the Al content. The bandgap of the epitaxial layers is slightly lower than predicted value due to a larger tensile strain effect on the a-axis compared to the compressive strain on the c-axis. Raman characteristics of the AlxGa1−xN samples exhibit a shift in the phonon peaks with the Al composition. The effect of strain on the optical phonon energies of the epitaxial layers is also discussed.

The Kitagawa-Takahashi fatigue diagram to hybrid welded AA7050 joints via synchrotron X-ray tomography

The relationship between the microstructural nature and fatigue resistance was explored for laser welded AA7050-T7451. Based on high-resolution synchrotron radiation X-ray micro computed tomography, it is found that the large surface defects are a controlling factor in fatigue crack initiation. Besides, fine equiaxed grain zone (FQZ) near the fusion line appears to the failure site of hybrid laser welded joints. Particularly for gas pores-free at the weld surface, such FQZ might play a crucial role in degrading the service strength. Research results show that the evolution in microstructure, element and defects due to welding deteriorates the hardness, tensile strength and fatigue properties. Modified Murakami equation and Kitagawa-Takahashi diagram were finally established to correlate the fatigue strength with defects, which provides an important reference to assess the joints.

High-quality thulium iron garnet films with tunable perpendicular magnetic anisotropy by off-axis sputtering \u2013 correlation between magnetic properties and film strain

Thulium iron garnet (TmIG) films with perpendicular magnetic anisotropy (PMA) were grown on gadolinium gallium garnet (GGG) (111) substrates by off-axis sputtering. High-resolution synchrotron radiation X-ray diffraction studies and spherical aberration-corrected scanning transmission electron microscope (Cs-corrected STEM) images showed the excellent crystallinity of the films and their sharp interface with GGG. Damping constant of TmIG thin film was determined to be 0.0133 by frequency-dependent ferromagnetic resonance (FMR) measurements. The saturation magnetization (Ms) and the coercive field (Hc) were obtained systematically as a function of the longitudinal distance (L) between the sputtering target and the substrate. A 170% enhancement of PMA field (H⊥) was achieved by tuning the film composition to increase the tensile strain. Moreover, current-induced magnetization switching on a Pt/TmIG structure was demonstrated with an ultra-low critical current density (jc) of 2.5 × 106 A/cm2, an order of magnitude smaller than the previously reported value. We were able to tune Ms, Hc and H⊥ to obtain an ultra-low jc of switching the magnetization, showing the great potential of sputtered TmIG films for spintronics.

Polymorph separation induced by angle distortion and electron delocalization effect via orbital modification inVO2epitaxial thin films

Since Morin discovered that vanadium dioxide $(\mathrm{V}{\mathrm{O}}_{2})$ undergoes a reversible and dramatic structural phase transition coupled with an abrupt metal-insulator transition, extensive attention has been paid to $\mathrm{V}{\mathrm{O}}_{2}$ due to its importance in fundamental condensed state physics and its potential technological applications. Here, we observed that the precipitated phases of $\mathrm{V}{\mathrm{O}}_{2}$ (insulating and metallic polymorphs) could be controlled by relaxing the dimerization of the vanadium-vanadium (V-V) atomic chain. In particular, the monoclinic metallic phase can be stabilized even at room temperature with the assistance of the angle-distortion-induced $(\ensuremath{\beta}={120}^{\ensuremath{\circ}})$ metallization through symmetry matching between the $\mathrm{V}{\mathrm{O}}_{2}$ epitaxial thin films and the (0001)-oriented sapphire substrates. Concomitantly, the insulating phase $(\text{M}1,\ensuremath{\beta}=122.{6}^{\ensuremath{\circ}})$ that separates from the metallic matrix may supply another driving force for stabilizing the metallic phase, as indicated by scattering-type scanning near-field optical infrared microscopy and further confirmed by synchrotron radiation high-resolution x-ray diffraction characterizations. Soft x-ray absorption spectroscopy results showed that the orbital features of the monoclinic metallic phase are analogous to those of the high-temperature metallic rutile $\mathrm{V}{\mathrm{O}}_{2}$ (R) phase. First-principles calculations further demonstrate the angle-distortion-induced reduction of the V-V atomic dimerization, which enhances the electron delocalization and thus the conductivity. Therefore, the angle distortion results in the metallic monoclinic phase and stabilizes it with the assistance of the nanoscale insulating $\mathrm{V}{\mathrm{O}}_{2}$ (M1) domains at room temperature. These results are of great importance for understanding the contributions of various polymorphs to the metal-insulator transition and for the design of novel artificially heterointerfacial devices based on $\mathrm{V}{\mathrm{O}}_{2}$ nanoscale polymorphs.

Iron and niobium based additives in magnesium hydride: Microstructure and hydrogen storage properties

In this study, powder mixtures of MgH2 + 2 mol.% X, with X = Nb, Nb2O5, NbF5, Fe, Fe2O3, FeF3, were processed by mechanical milling at liquid nitrogen temperature (cryomilling). The effect of additives on crystalline structure, thermal properties and hydrogen storage properties of the mixtures were investigated. Morphological investigations indicated a heterogeneous particle size distribution of the powder mixtures and a fine dispersion of additive particles (FeF3) in the MgH2 matrix. High resolution synchrotron radiation X-ray diffraction (SR-XRD) data followed by Rietveld refinements showed a significant reduction on crystallite size for the samples containing fluorides (11 nm) in comparison with the pure MgH2 sample (29 nm). This was related to the mechanical behavior of fluorides during milling with MgH2, which act as a lubricant, dispersing and/or cracking agent during milling, and thus helping to further reduce MgH2 particle size. DSC analysis revealed that fluorides (NbF5, FeF3) are much more effective than oxides (Nb2O5, Fe2O3) and the transition metals (Nb and Fe), respectively, in reduction the desorption temperature. Furthermore, Nb2O5 is more efficient than Fe2O3. Finally, the best results for desorption kinetics were observed for the fluorides: NbF5 and FeF3 (equivalent effect and consistent to the DSC analysis) followed by the oxides: Nb2O5, Fe2O3 and Nb. The addition of Fe was not efficient in comparison with the pure cryomilled sample.

Real internal microstructure based key mechanism analysis on the micro-damage process of short fibre-reinforced composites.

In this work, the underlying micro-damage mechanisms of randomly oriented short fibre-reinforced composites were revealed based on real internal microstructural characteristics obtained by high-resolution (0.7 μm/pixel) synchrotron radiation X-ray computed tomography (SR-CT). The special ‘pore dominant micro-damage processes’ were directly observed through SR-CT three-dimensional reconstructed images, which were different from the well-known ‘fibre breakage dominant failure mode’. The mechanisms of pore formation and pore evolution were further investigated on the basis of the microstructural parameters extracted from the SR-CT results. On one hand, the pore formation mechanism caused by shear stress concentration was proposed by combining the shear-lag model with the microstructural parameters obtained from the experiment, including the fibre length and orientation angle. On the other hand, the ‘fibre-end aggregation-induced pore connection’ mode of crack initiation was proposed through a composites model, which considered the parameters of real internal microstructure, including the critical value of the distance between neighbouring fibre ends and the number of neighbouring fibre ends. The study indicated that the shear stress concentration was significant in the region with a large number of neighbouring fibre ends, thus causing pore connection and crack initiation.

Research Update: Strain and composition effects on ferromagnetism of Mn0.05Ge0.95 quantum dots

Mn0.05Ge0.95 quantum dots (QDs) samples were grown by molecular beam epitaxy on Si substrates and 15-nm-thick fully strained Si0.8Ge0.2 virtual substrates, respectively. The QDs samples grown on the Si0.8Ge0.2 virtual substrates show a significant ferromagnetism with a Curie temperature of 227 K, while the QDs samples grown on the Si substrates are non-ferromagnetic. Microstructures of the QDs samples were characterized by high resolution transmission electron microscopy and synchrotron radiation X-ray diffraction. Interdependence between microstructure and ferromagnetism of Mn-doped Ge QDs was investigated. For the QDs sample grown on the strained Si0.8Ge0.2 virtual substrate, although the ferromagnetic phase Mn5Ge3 clusters were found to be formed in small dome-shaped dots, the significant ferromagnetism observed in that sample is attributed to ferromagnetic phase Mn-doped large dome-shaped Ge QDs, rather than to the ferromagnetic phase Mn5Ge3 clusters. The fully strained Si0.8Ge0.2 virtual substrates would result in a residual strain into the QDs and an increase in Ge composition in the QDs. Both consequences favor the formations of ferromagnetic phase Mn-doped Ge QDs from points of view of quantum confinement effect as well as Mn doping at substitutional sites.