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.

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.

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.

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.

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.

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.

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.

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.

Size-dependent diffusion controls natural aging in aluminium alloys.

A key question in materials science is how fast properties evolve, which relates to the kinetics of phase transformations. In metals, kinetics is primarily connected to diffusion, which for substitutional elements is enabled via mobile atomic-lattice vacancies. In fact, non-equilibrium vacancies are often required for structural changes. Rapid quenching of various important alloys, such as Al- or Mg-alloys, results for example in natural aging, i.e. slight movements of solute atoms in the material, which significantly alter the material properties. In this study we demonstrate a size effect of natural aging in an AlMgSi alloy via atom probe tomography with near-atomic image resolution. We show that non-equilibrium vacancy diffusional processes are generally stopped when the sample size reaches the nanometer scale. This precludes clustering and natural aging in samples below a certain size and has implications towards the study of non-equilibrium diffusion and microstructural changes via microscopy techniques.

Biocorrosion Zoomed In: Evidence for Dealloying of Nanometric Intermetallic Particles in Magnesium Alloys.

Biodegradable magnesium alloys generally contain intermetallic phases on the micro- or nanoscale, which can initiate and control local corrosion processes via microgalvanic coupling. However, the experimental difficulties in characterizing active degradation on the nanoscale have so far limited the understanding of how these materials degrade in complex physiological environments. Here a quasi-in situ experiment based on transmission electron microscopy (TEM) is designed, which enables the initial corrosion attack at nanometric particles to be accessed within the first seconds of immersion. Combined with high-resolution ex situ cross-sectional TEM analysis of a well-developed corrosion-product layer, mechanistic insights into Mg-alloys' degradation on the nanoscale are provided over a large range of immersion times. Applying this methodology to lean Mg-Zn-Ca alloys and following in detail the dissolution of their nanometric Zn- and Ca-rich particles the in statu nascendi observation of intermetallic-particle dealloying is documented for magnesium alloys, where electrochemically active Ca and Mg preferentially dissolve and electropositive Zn enriches, inducing the particles' gradual ennoblement. Based on electrochemical theory, here, the concept of cathodic-polarization-induced dealloying, which controls the dynamic microstructural changes, is presented. The general prerequisites for this new dealloying mechanism to occur in multicomponent alloys and its distinction to other dealloying modes are also discussed.

Exceptional Strengthening of Biodegradable Mg-Zn-Ca Alloys through High Pressure Torsion and Subsequent Heat Treatment.

In this study, two biodegradable Mg-Zn-Ca alloys with alloy content of less than 1 wt % were strengthened via high pressure torsion (HPT). A subsequent heat treatment at temperatures of around 0.45 Tm led to an additional, sometimes even larger increase in both hardness and tensile strength. A hardness of more than 110 HV and tensile strength of more than 300 MPa were achieved in Mg-0.2Zn-0.5Ca by this procedure. Microstructural analyses were conducted by scanning and transmission electron microscopy (SEM and TEM, respectively) and atom probe tomography (APT) to reveal the origin of this strength increase. They indicated a grain size in the sub-micron range, Ca-rich precipitates, and segregation of the alloying elements at the grain boundaries after HPT-processing. While the grain size and segregation remained mostly unchanged during the heat treatment, the size and density of the precipitates increased slightly. However, estimates with an Orowan-type equation showed that precipitation hardening cannot account for the strength increase observed. Instead, the high concentration of vacancies after HPT-processing is thought to lead to the formation of vacancy agglomerates and dislocation loops in the basal plane, where they represent particularly strong obstacles to dislocation movement, thus, accounting for the considerable strength increase observed. This idea is substantiated by theoretical considerations and quenching experiments, which also show an increase in hardness when the same heat treatment is applied.

3D Printing of Salt as a Template for Magnesium with Structured Porosity.

Porosity is an essential feature in a wide range of applications that combine light weight with high surface area and tunable density. Porous materials can be easily prepared with a vast variety of chemistries using the salt-leaching technique. However, this templating approach has so far been limited to the fabrication of structures with random porosity and relatively simple macroscopic shapes. Here, a technique is reported that combines the ease of salt leaching with the complex shaping possibilities given by additive manufacturing (AM). By tuning the composition of surfactant and solvent, the salt-based paste is rheologically engineered and printed via direct ink writing into grid-like structures displaying structured pores that span from the sub-millimeter to the macroscopic scale. As a proof of concept, dried and sintered NaCl templates are infiltrated with magnesium (Mg), which is typically highly challenging to process by conventional AM techniques due to its highly oxidative nature and high vapor pressure. Mg scaffolds with well-controlled, ordered porosity are obtained after salt removal. The tunable mechanical properties and the potential to be predictably bioresorbed by the human body make these Mg scaffolds attractive for biomedical implants and demonstrate the great potential of this additive technique.

Towards refining microstructures of biodegradable magnesium alloy WE43 by spark plasma sintering.

Microstructural refinement of magnesium (Mg) alloys is beneficial for mechanical and corrosion properties, both of which are critical for their successful application as temporary implant materials. One method of achieving a refined microstructure is through rapid solidification via gas-atomization-powder production. In this study we investigated spark plasma sintering (SPS) as a potential processing method for maintaining this refined microstructure while achieving a range of porosities up to full densification. We characterized the microstructural evolution as a function of sintering temperature from 250 to 450 °C for the alloy WE43 using multi-scale correlative microscopy techniques, including light microscopy and scanning and transmission electron microscopy-based methods. The spatial distribution of the two major alloying elements, neodymium (Nd) and yttrium (Y), was determined and the intermetallic phases they form identified using energy dispersive X-ray spectroscopy in conjunction with electron diffraction. The gas-atomized powder microstructure consists of Mg-rich dendrites and a percolating interdendritic Mg-Nd-Y ternary phase with structure Mg14Nd2Y, surrounded by a high Nd and Y content in solid solution. This microstructure is maintained up to a sintering temperature of 350 °C, while with higher sintering temperatures segregation of Nd and Y dominates. The percolating ternary phase breaks up into faceted globular precipitates with structure Mg5Nd, which is isomorphous to Mg14Nd2Y. Y comes out of solution and migrates to previous powder-particle surfaces, possibly forming Y2O3. Sample densities ranged from 64 to 100% for sintering temperatures of 250 to 450 °C, respectively, and the grain size remained constant at about 10 µm. SPS is demonstrated to be an attractive alternative method for processing Mg alloys to a wide range of porosities and fine microstructures. The microstructural refinement achieved by SPS holds the potential for slow and homogeneous corrosion. STATEMENT OF SIGNIFICANCE: This study presents the impact spark plasma sintering (SPS) has on the microstructure of WE43, a magnesium alloy used for biodegradable implants. SPS is of great interest in this context as it is scalable, rapid, and has the potential for tuning density while maintaining a refined microstructure. The microstructure and density are explored from the gas-atomized powder to the densified material using electron microscopy and chemical mapping from the macro- to the nano-level. The insights gained reveal an original evolution of rare-earth element distribution with an isomorphous chemistry change, while the microstructure develops from the non-equilibrium state (powder) towards an equilibrium structure upon sintering. This study, including measurements of mechanical performance, sets the premises of SPS for the fabrication of Mg-based implants with tunable characteristics.

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.

Laser additive manufacturing of biodegradable magnesium alloy WE43: A detailed microstructure analysis.

WE43, a magnesium alloy containing yttrium and neodymium as main alloying elements, has become a well-established bioresorbable implant material. Implants made of WE43 are often fabricated by powder extrusion and subsequent machining, but for more complex geometries laser powder bed fusion (LPBF) appears to be a promising alternative. However, the extremely high cooling rates and subsequent heat treatment after solidification of the melt pool involved in this process induce a drastic change in microstructure, which governs mechanical properties and degradation behaviour in a way that is still unclear. In this study we investigated the changes in the microstructure of WE43 induced by LPBF in comparison to that of cast WE43. We did this mainly by electron microscopy imaging, and chemical mapping based on energy-dispersive X-ray spectroscopy in conjunction with electron diffraction for the identification of the various phases. We identified different types of microstructure: an equiaxed grain zone in the center of the laser-induced melt pool, and a lamellar zone and a partially melted zone at its border. The lamellar zone presents dendritic lamellae lying on the Mg basal plane and separated by aligned Nd-rich nanometric intermetallic phases. They appear as globular particles made of Mg3Nd and as platelets made of Mg41Nd5 occurring on Mg prismatic planes. Yttrium is found in solid solution and in oxide particles stemming from the powder particles' shell. Due to the heat influence on the lamellar zone during subsequent laser passes, a strong texture developed in the bulk material after substantial grain growth. STATEMENT OF SIGNIFICANCE: Additively manufactured magnesium alloys have the potential of providing a major breakthrough in bone-reconstruction surgery by serving as biodegradable porous scaffold material. This study is the first to report in detail on the microstructure development of the established magnesium alloy WE43 fabricated by the additive manufacturing process of Laser Powder Bed Fusion (LPBF). It presents unique microstructural features which originate from the laser-melting process. An in situ transmission electron microscopy heating experiment further demonstrates the development of two distinct intermetallic phases in additively manufactured WE43 alloys. While one forms already during solidification, the other precipitates due to the ongoing heat treatment during LPBF processing.

Existence of multiple critical cooling rates which generate different types of monolithic metallic glass.

Via fast differential scanning calorimetry using an Au-based glass as an example, we show that metallic glasses should be classified into two types of amorphous/monolithic glass. The first type, termed self-doped glass (SDG), forms quenched-in nuclei or nucleation precursors upon cooling, whereas in the so-called chemically homogeneous glass (CHG) no quenched-in structures are found. For the Au-based glass investigated, the critical cooling and heating rates for the SDG are 500 K s-1 and 20,000 K s-1, respectively; for the CHG they are 4000 K s-1 and 6000 K s-1. The similarity in the critical rates for CHG, so far not reported in literature, and CHG's tendency towards stochastic nucleation underline the novelty of this glass state. Identifying different types of metallic glass, as is possible by advanced chip calorimetry, and comparing them with molecular and polymeric systems may help to elaborate a more generalized glass theory and improve metallic glass processing.

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.