Structural relaxation in layered, non-stoichiometric Fe7S8.

In this study, we investigate the kinetics of the enantiotropic solid-solid ß-transition in Fe7S8 pyrrhotite, which presents a prominent example of a metal-nonmetal compound with layered crystal structure. The low-temperature (4C) and high-temperature (1C) modifications differ in their crystallographic unit-cell dimension, vacancy distribution, and magnetic ordering in the crystal lattice. Fast differential scanning calorimetry (FDSC) reveals that cooling of the paramagnetic 1C phase below the transformation temperature Tß = 597 K, which is also the Curie temperature, generates a metastable phase that transforms into the ferrimagnetic 4C phase with high vacancy order upon further annealing below Tß. Upon fast cooling, the low-temperature modification shows an energetically excited phase with higher entropy that relaxes towards the equilibrated pyrrhotite polymorph. The kinetics of the superheating and the structural relaxation as obtained from FDSC experiments provide deeper insight into the stability of Fe7S8 polymorphs. This may pave a new path to decipher in detail the kinetics of solid-solid phase transformations and the long-term lifespan of defects in Earth and synthetic materials.

Metastable quasicrystal-induced nucleation in a bulk glass-forming liquid.

This study presents a unique Mg-based alloy composition in the Mg-Zn-Yb system which exhibits bulk metallic glass, metastable icosahedral quasicrystals (iQCs), and crystalline approximant phases in the as-cast condition. Microscopy revealed a smooth gradual transition from glass to QC. We also report the complete melting of a metastable eutectic phase mixture (including a QC phase), generated via suppression of the metastable-to-stable phase transition at high heating rates using fast differential scanning calorimetry (FDSC). The melting temperature and enthalpy of fusion of this phase mixture could be measured directly, which unambiguously proves its metastability in any temperature range. The kinetic pathway from liquid state to stable solid state (an approximant phase) minimizes the free-energy barrier for nucleation through an intermediate state (metastable QC phase) because of its low solid-liquid interfacial energy. At high undercooling of the liquid, where diffusion is limited, another approximant phase with near-liquid composition forms just above the glass-transition temperature. These experimental results shed light on the competition between metastable and stable crystals, and on glass formation via system frustration associated with the presence of several free-energy minima.

Cation diffusion patterns across the magneto-structural transition in Fe7S8.

Migration of atoms in solids during diffusion-dependent reactions is relatively fast and generally not directly recordable in experiments. Here we present an experimental framework that includes fast differential scanning calorimetry to resolve cation-migration paths in crystalline solids using the reversible magneto-structural transition of 4C to 1C pyrrhotite as a testbed. The transition between these two polymorphic Fe7S8 phases at about 600 K is a diffusive process of vacancies, respectively of Fe in octahedral interstitial sites within a hexagonal close-packed lattice of sulfur, and it coincides with the Curie temperature of 4C pyrrhotite. The Fe cations migrate along three kinds of diffusion paths, and their enthalpy contributions to the total reaction enthalpy are taken to define the diffusion patterns in the endothermic reaction and the exothermic back-reaction, respectively. Our experimental findings provide insight into the potential of diffusion patterns to disentangle ordering mechanisms in solids.

Monopole-Induced Emergent Electric Fields in Ferromagnetic Nanowires.

We predict that complete magnetization reversal in simple metallic ferromagnetic nanoparticles is directly linked to the pair creation of topological point defects in the form of hedgehog-antihedgehog pairs. These dynamical point defects move at exceptionally high speeds in excess of 1500 m/s, faster than any other known magnetic object. Their rapid motion generates unprecedented solenoidal emergent fields on the order of megavolts per meter, in analogy to the magnetic field of a moving electric charge, providing a striking example that a moving hedgehog constitutes an emergent magnetic monopole.

Enhancement of the intrinsic fluorescence of adenine using aluminum nanoparticle arrays.

This study demonstrates the metal-enhanced fluorescence of adenine using aluminum nanoparticle arrays in the deep UV range. It achieves the reproducible intensity enhancement of intrinsic fluorescence up to 80 on well-defined aluminum nanoparticle arrays at 257 nm excitation. In addition to a high signal enhancement, a strong modification of the fluorescence emission spectrum of adenine is observed. This study illustrates that the label-free detection of DNA bases and proteins that have low intrinsic fluorescence and absorption bands in the deep UV range can be facilitated using aluminum nanostructures.

Towards deep-UV surface-enhanced resonance Raman spectroscopy of explosives: ultrasensitive, real-time and reproducible detection of TNT.

We report ultrasensitive and label-free detection of 2,4,6-trinitrotoluene (TNT) deposited by drop coating using deep-ultraviolet surface-enhanced resonance Raman scattering (DUV-SERRS). Well-defined aluminum nanoparticle arrays as the SERRS substrate at 257 nm excitation wavelength enabled highly reproducible and real-time detection of TNT down to the detection limit of the attogram level in quantity. This extreme sensitivity can be further improved by optimization of the nanostructured substrates. DUV-SERRS promises to have a large impact on public safety and security, as it can be readily extended to other explosives and hazardous materials.

Energy Absorption and Beam Damage during Microfocus Synchrotron X-ray Diffraction.

In this study, we combine in situ fast differential scanning calorimetry (FDSC) with synchrotron X-ray measurements to study simultaneously the structure and thermophysical properties of materials. Using the example of the organic compound BCH-52, we show that the X-ray beam can heat the sample and induce a shift of the heat-flow signal. The aim of this paper is to investigate the influence of radiation on sample behavior. The calorimetric data is used to quantify the absorbed beam energy and, together with the diffraction data, reveal an irreversible damage of the sample. The results are especially important for materials with high absorption coefficients and for high-energy X-ray and electron beams. Our findings illustrate that FDSC combined with X-ray diffraction is a suitable characterization method when beam damage must be minimized.

Human Body-Fluid-Assisted Fracture of Zinc Alloys as Biodegradable Temporary Implants: Challenges, Research Needs and Way Forward.

Alloys of magnesium, zinc or iron that do not contain toxic elements are attractive as construction material for biodegradable implants, i.e., the type of implants that harmlessly dissolve away within the human body after they have completed their intended task. The synergistic influence of mechanical stress and corrosive human body fluid can cause sudden and catastrophic fracture of bioimplants due to phenomena such as stress corrosion cracking (SCC) and corrosion fatigue (CF). To date, SCC and CF of implants based on Zn have scarcely been investigated. This article is an overview of the challenges, research needs and way forward in understanding human body-fluid-assisted fractures (i.e., SCC and CF) of Zn alloys in human body fluid.

The combined effect of zinc and calcium on the biodegradation of ultrahigh-purity magnesium implants.

Magnesium (Mg)-based implants are promising candidates for orthopedic interventions, because of their biocompatibility, good mechanical features, and ability to degrade completely in the body, eliminating the need for an additional removal surgery. In the present study, we synthesized and investigated two Mg-based materials, ultrahigh-purity ZX00 (Mg-Zn-Ca; <0.5 wt% Zn and <0.5 wt% Ca, in wt%; Fe-content <1 ppm) and ultrahigh-purity Mg (XHP-Mg, >99.999 wt% Mg; Fe-content <1 ppm), in vitro and in vivo in juvenile healthy rats to clarify the effect of the alloying elements Zn and Ca on mechanical properties, microstructure, cytocompatibility and degradation rate. Potential differences in bone formation and bone in-growth were also assessed and compared with state-of-the-art non-degradable titanium (Ti)-implanted, sham-operated, and control (non-intervention) groups, using micro-computed tomography, histology and scanning electron microscopy. At 6 and 24 weeks after implantation, serum alkaline phosphatase (ALP), calcium (Ca), and Mg level were measured and bone marrow stromal cells (BMSCs) were isolated for real-time PCR analysis. Results show that ZX00 implants have smaller grain size and superior mechanical properties than XHP-Mg, and that both reveal good biocompatibility in cytocompatibilty tests. ZX00 homogenously degraded with an increased gas accumulation 12 and 24 weeks after implantation, whereas XHP-Mg exhibited higher gas accumulation already at 2 weeks. Serum ALP, Ca, and Mg levels were comparable among all groups and both Mg-based implants led to similar relative expression levels of Alp, Runx2, and Bmp-2 genes at weeks 6 and 24. Histologically, Mg-based implants are superior for new bone tissue formation and bone in-growth compared to Ti implants. Furthermore, by tracking the sequence of multicolor fluorochrome labels, we observed higher mineral apposition rate at week 2 in both Mg-based implants compared to the control groups. Our findings suggest that (i) ZX00 and XHP-Mg support bone formation and remodeling, (ii) both Mg-based implants are superior to Ti implants in terms of new bone tissue formation and osseointegration, and (iii) ZX00 is more favorable due to its lower degradation rate and moderate gas accumulation.

Deep-UV surface-enhanced resonance Raman scattering of adenine on aluminum nanoparticle arrays.

We report the ultrasensitive detection of adenine using deep-UV surface-enhanced resonance Raman scattering on aluminum nanostructures. Well-defined Al nanoparticle arrays fabricated over large areas using extreme-UV interference lithography exhibited sharp and tunable plasmon resonances in the UV and deep-UV wavelength ranges. Theoretical modeling based on the finite-difference time-domain method was used to understand the near-field and far-field optical properties of the nanoparticle arrays. Raman measurements were performed on adenine molecules coated uniformly on the Al nanoparticle arrays at a laser excitation wavelength of 257.2 nm. With this technique, less than 10 amol of label-free adenine molecules could be detected reproducibly in real time. Zeptomole (~30,000 molecules) detection sensitivity was readily achieved proving that deep-UV surface-enhanced resonance Raman scattering is an extremely sensitive tool for the detection of biomolecules.

Atomic structure evolution related to the Invar effect in Fe-based bulk metallic glasses.

The Invar effect is universally observed in Fe-based bulk metallic glasses. However, there is limited understanding on how this effect manifests at the atomic scale. Here, we use in-situ synchrotron-based high-energy X-ray diffraction to study the structural transformations of (Fe71.2B24Y4.8)96Nb4 and (Fe73.2B22Y4.8)95Mo5 bulk metallic glasses around the Curie temperature to understand the Invar effect they exhibit. The first two diffraction peaks shift in accordance with the macroscopically measured thermal expansion, which reveals the Invar effect. Additionally, the nearest-neighbor Fe-Fe pair distance correlates well with the macroscopic thermal expansion. In-situ X-ray diffraction is thus able to elucidate the Invar effect in Fe-based metallic glasses at the atomic scale. Here, we find that the Invar effect is not just a macroscopic effect but has a clear atomistic equivalent in the average Fe-Fe pair distance and also shows itself in higher-order atomic shells composed of multiple atom species.

Implant degradation of low-alloyed Mg-Zn-Ca in osteoporotic, old and juvenile rats.

Implant removal is unnecessary for biodegradable magnesium (Mg)-based implants and, therefore, the related risk for implant-induced fractures is limited. Aging, on the other hand, is associated with low bone-turnover and decreased bone mass and density, and thus increased fracture risk. Osteoporosis is accompanied by Mg deficiency, therefore, we hypothesized that Mg-based implants may support bone formation by Mg2+ ion release in an ovariectomy-induced osteoporotic rat model. Hence, we investigated osseointegration and implant degradation of a low-alloyed, degrading Mg-Zn-Ca implant (ZX00) in ovariectomy-induced osteoporotic (Osteo), old healthy (OH), and juvenile healthy (JH) groups of female Sprague Dawley rats via in vivo micro-computed tomography (µCT). For the Osteo rats, we demonstrate diminished trabecular bone already after 8 weeks upon ovariectomy and significantly enhanced implant volume loss, with correspondingly pronounced gas formation, compared to the OH and JH groups. Sclerotic rim development was observed in about half of the osteoporotic rats, suggesting a prevention from foreign-body and osteonecrosis development. Synchrotron radiation-based µCT confirmed lower bone volume fractions in the Osteo group compared to the OH and JH groups. Qualitative histological analysis additionally visualized the enhanced implant degradation in the Osteo group. To date, ZX00 provides an interesting implant material for young and older healthy patients, but it may not be of advantage in pharmacologically untreated osteoporotic conditions. STATEMENT OF SIGNIFICANCE: Magnesium-based implants are promising candidates for treatment of osteoporotic fractures because of their biodegradable, biomechanical, anti-bacterial and bone regenerative properties. Here we investigate magnesium‒zinc‒calcium implant materials in a rat model with ovariectomy-induced osteoporosis (Osteo group) and compare the related osseointegration and implant degradation with the results obtained for old healthy (OH) and juvenile healthy (JH) rats. The work applied an appropriate disease model for osteoporosis and focused in particular on long-term implant degradation for different bone conditions. Enhanced implant degradation and sclerotic rim formation was observed in osteoporotic rats, which illustrates that the setting of different bone models generates significantly modified clinical outcome. It further illustrated that these differences must be taken into account in future biodegradable implant development.

X-ray Diffraction Computed Nanotomography Applied to Solve the Structure of Hierarchically Phase-Separated Metallic Glass.

The structure of matter at the nanoscale, in particular that of amorphous metallic alloys, is of vital importance for functionalization. With the availability of synchrotron radiation, it is now possible to visualize the internal features of metallic samples without physically destroying them. Methods based on computed tomography have recently been employed to explore the local features. Tomographic reconstruction, while it is relatively uncomplicated for crystalline materials, may generate undesired artifacts when applied to featureless amorphous or nanostructured metallic alloys. In this study we show that X-ray diffraction computed nanotomography can provide accurate details of the internal structure of a metallic glass. We demonstrate the power of the method by applying it to a hierarchically phase-separated amorphous sample with a small volume fraction of crystalline inclusions, focusing the X-ray beam to 500 nm and ensuring a sub-micrometer 2D resolution via the number of scans.

3D nanoscale analysis of bone healing around degrading Mg implants evaluated by X-ray scattering tensor tomography.

The nanostructural adaptation of bone is crucial for its biocompatibility with orthopedic implants. The bone nanostructure also determines its mechanical properties and performance. However, the bone's temporal and spatial nanoadaptation around degrading implants remains largely unknown. Here, we present insights into this important bone adaptation by applying scanning electron microscopy, elemental analysis, and small-angle X-ray scattering tensor tomography (SASTT). We extend the novel SASTT reconstruction method and provide a 3D scattering reciprocal space map per voxel of the sample's volume. From this reconstruction, parameters such as the thickness of the bone mineral particles are quantified, which provide additional information on nanostructural adaptation of bone during healing. We selected a rat femoral bone and a degrading ZX10 magnesium implant as model system, and investigated it over the course of 18 months, using a sham as control. We observe that the bone's nanostructural adaptation starts with an initially fast interfacial bone growth close to the implant, which spreads by a re-orientation of the nanostructure in the bone volume around the implant, and is consolidated in the later degradation stages. These observations reveal the complex bulk bone-implant interactions and enable future research on the related biomechanical bone responses. STATEMENT OF SIGNIFICANCE: Traumatic bone injuries are among the most frequent causes of surgical treatment, and often require the placement of an implant. The ideal implant supports and induces bone formation, while being mechanically and chemically adapted to the bone structure, ensuring a gradual load transfer. While magnesium implants fulfill these requirements, the nanostructural changes during bone healing and implant degradation remain not completely elucidated. Here, we unveil these processes in rat femoral bones with ZX10 magnesium implants and show different stages of bone healing in such a model system.

MgZnCa glasses without clinically observable hydrogen evolution for biodegradable implants.

Corrosion is normally an undesirable phenomenon in engineering applications. In the field of biomedical applications, however, implants that 'biocorrode' are of considerable interest. Deploying them not only abrogates the need for implant-removal surgery, but also circumvents the long-term negative effects of permanent implants. In this context magnesium is an attractive biodegradable material, but its corrosion is accompanied by hydrogen evolution, which is problematic in many biomedical applications. Whereas the degradation and thus the hydrogen evolution of crystalline Mg alloys can be altered only within a very limited range, Mg-based glasses offer extended solubility for alloying elements plus a homogeneous single-phase structure, both of which may alter corrosion behaviour significantly. Here we report on a distinct reduction in hydrogen evolution in Zn-rich MgZnCa glasses. Above a particular Zn-alloying threshold (approximately 28 at.%), a Zn- and oxygen-rich passivating layer forms on the alloy surface, which we explain by a model based on the calculated Pourbaix diagram of Zn in simulated body fluid. We document animal studies that confirm the great reduction in hydrogen evolution and reveal the same good tissue compatibility as seen for crystalline Mg implants. Thus, the glassy Mg(60+x)Zn(35-x)Ca5 (0 < or = x < or = 7) alloys show great potential for deployment in a new generation of biodegradable implants.

Magnetic metamaterials in the blue range using aluminum nanostructures.

We report an experimental and theoretical study of the optical properties of two-dimensional arrays of aluminum nanoparticle in-tandem pairs. Plasmon resonances and effective optical constants of these structures are investigated, and strong magnetic response as well as negative permeability is observed down to 400 nm wavelength. Theoretical calculations based on the finite-difference time-domain method are performed for various particle dimensions and lattice parameters, and are found to be in good agreement with the experimental findings. The results show that metamaterials operating across the whole visible wavelength range are feasible.

Multistep Crystallization and Melting Pathways in the Free-Energy Landscape of a Au-Si Eutectic Alloy.

Crystals do eventually melt if they are heated to their characteristic melting point. However, this is practically only the case for high-temperature stable crystals, whereas low-temperature metastable crystals generally transform, before melting, into a more stable solid during heating. Here, it is illustrated that low-temperature crystals can, however, be melted via fast differential scanning calorimetry (FDSC), even in metallic systems where nucleation and growth kinetics are rapid. For a Au-Si eutectic alloy, various metastable and stable solid states, i.e., (Au-α), (Au-ß), γ, and (Au-Si), which form under well-controlled conditions and melt at high heating rates by preventing the metastable-to-stable solid phase transition, are isolated. It is demonstrated that Au81.4Si18.6 can fully melt at various temperatures, i.e., 294 °C, 312 °C, 352 °C, and 363 °C, with differing melting enthalpies ranging from 6.52 to 9.83 kJ mol-1. The melting and crystallization paths of the metastable solids are determined by constructing an energy-temperature diagram. This approach advances the general understanding of nucleation in metallic and other systems, and is expected to contribute to the detailed understanding of thermophysical phenomena that occur at spatially reduced dimensions and/or short time scales, for example in thin-film deposition, nanomaterials production, or additive manufacturing.

Unconventional magnetization textures and domain-wall pinning in Sm-Co magnets.

Some of the best-performing high-temperature magnets are Sm-Co-based alloys with a microstructure that comprises an [Formula: see text] matrix and magnetically hard [Formula: see text] cell walls. This generates a dense domain-wall-pinning network that endows the material with remarkable magnetic hardness. A precise understanding of the coupling between magnetism and microstructure is essential for enhancing the performance of Sm-Co magnets, but experiments and theory have not yet converged to a unified model. Here, transmission electron microscopy, atom probe tomography, and nanometer-resolution off-axis electron holography have been combined with micromagnetic simulations to reveal that the magnetization state in Sm-Co magnets results from curling instabilities and domain-wall pinning effects at the intersections of phases with different magnetic hardness. Additionally, this study has found that topologically non-trivial magnetic domains separated by a complex network of domain walls play a key role in the magnetic state by acting as nucleation sites for magnetization reversal. These findings reveal previously hidden aspects of magnetism in Sm-Co magnets and, by identifying weak points in the microstructure, provide guidelines for improving these high-performance magnetic materials.

Structured nanoscale metallic glass fibres with extreme aspect ratios.

Micro- and nanoscale metallic glasses offer exciting opportunities for both fundamental research and applications in healthcare, micro-engineering, optics and electronics. The scientific and technological challenges associated with the fabrication and utilization of nanoscale metallic glasses, however, remain unresolved. Here, we present a simple and scalable approach for the fabrication of metallic glass fibres with nanoscale architectures based on their thermal co-drawing within a polymer matrix with matched rheological properties. Our method yields well-ordered and uniform metallic glasses with controllable feature sizes down to a few tens of nanometres, and aspect ratios greater than 1010. We combine fluid dynamics and advanced in situ transmission electron microscopy analysis to elucidate the interplay between fluid instability and crystallization kinetics that determines the achievable feature sizes. Our approach yields complex fibre architectures that, combined with other functional materials, enable new advanced all-in-fibre devices. We demonstrate in particular an implantable metallic glass-based fibre probe tested in vivo for a stable brain-machine interface that paves the way towards innovative high-performance and multifunctional neuro-probes.

A lean magnesium-zinc-calcium alloy ZX00 used for bone fracture stabilization in a large growing-animal model.

Over the last decade, demand has increased for developing new, alternative materials in pediatric trauma care to overcome the disadvantages associated with conventional implant materials. Magnesium (Mg)-based alloys seem to adequately fulfill the vision of a homogeneously resorbable, biocompatible, load-bearing and functionally supportive implant. The aim of the present study is to introduce the high-strength, lean alloy Mg‒0.45Zn‒0.45Ca, in wt% (ZX00), and for the first time investigate the clinical applicability of screw osteosynthesis using this alloy that contains no rare-earth elements. The alloy was applied in a growing sheep model with osteotomized bone (simulating a fracture) and compared to a non-osteotomy control group regarding degradation behavior and fracture healing. The alloy exhibits an ultimate tensile strength of 285.7 ± 3.1 MPa, an elongation at fracture of 18.2 ± 2.1%, and a reduced in vitro degradation rate compared to alloys containing higher amounts of Zn. In vivo, no significant difference between the osteotomized bone and the control group was found regarding the change in screw volume over implantation time. Therefore, it can be concluded that the fracture healing process, including its effects on the surrounding area, has no significant influence on degradation behavior. There was also no negative influence from hydrogen-gas formation on fracture healing. Despite the proximal and distal screws showing chronologically different gas release, the osteotomy showed complete consolidation. STATEMENT OF SIGNIFICANCE: Conventional implants involve several disadvantages in pediatric trauma care. Magnesium-based alloys seem to overcome these issues as discussed in the recent literature. This study evaluates the clinical applicability of high-strength lean Mg‒0.45Zn‒0.45Ca (ZX00) screws in a growing-sheep model. Two groups, one including a simulated fracture and one group without fracture, underwent implantation of the alloy and were compared to each other. No significant difference regarding screw volume was observed between the groups. There was no negative influence of hydrogen-gas formation on fracture healing and a complete fracture consolidation was found after 12 weeks for all animals investigated.