Long-term in vivo degradation of Mg-Zn-Ca elastic stable intramedullary nails and their influence on the physis of juvenile sheep.

The use of bioresorbable magnesium (Mg)-based elastic stable intramedullary nails (ESIN) is highly promising for the treatment of pediatric long-bone fractures. Being fully resorbable, a removal surgery is not required, preventing repeated physical and psychological stress for the child. Further, the osteoconductive properties of the material support fracture healing. Nowadays, ESIN are exclusively implanted in a non-transphyseal manner to prevent growth discrepancies, although transphyseal implantation would often be required to guarantee optimized fracture stabilization. Here, we investigated the influence of trans-epiphyseally implanted Mg-Zinc (Zn)-Calcium (Ca) ESIN on the proximal tibial physis of juvenile sheep over a period of three years, until skeletal maturity was reached. We used the two alloying systems ZX10 (Mg-1Zn-0.3Ca, in wt%) and ZX00 (Mg-0.3Zn-0.4Ca, in wt%) for this study. To elaborate potential growth disturbances such as leg-length differences and axis deviations we used a combination of in vivo clinical computed tomography (cCT) and ex vivo micro CT (µCT), and also performed histology studies on the extracted bones to obtain information on the related tissue. Because there is a lack of long-term data regarding the degradation performance of magnesium-based implants, we used cCT and µCT data to evaluate the implant volume, gas volume and degradation rate of both alloying systems over a period of 148 weeks. We show that transepiphyseal implantation of Mg-Zn-Ca ESIN has no negative influence on the longitudinal bone growth in juvenile sheep, and that there is no axis deviation observed in all cases. We also illustrate that 95 % of the ESIN degraded over nearly three years, converging the time point of full resorption. We thus conclude that both, ZX10 and ZX00, constitute promising implant materials for the ESIN technique.

The role of zinc in the biocorrosion behavior of resorbable Mg‒Zn‒Ca alloys.

Zinc- and calcium-containing magnesium alloys, denominated ZX alloys, excel as temporary implant materials because of their composition made of physiologically essential minerals and lack of commonly used rare-earth alloying elements. This study documents the specific role of nanometric intermetallic particles (IMPs) on the in vitro and in vivo biocorrosion behavior of two ZX-lean alloys, Mg‒Zn1.0‒Ca0.3 (ZX10) and Mg‒Zn1.5‒Ca0.25 (ZX20) (in wt.%). These alloys were designed according to thermodynamic considerations by finely adjusting the nominal Zn content towards microstructures that differ solely in the type of phase composing the IMPs: ZX10, with 1.0 wt.% Zn, hosts binary Mg2Ca-phase IMPs, while ZX20, with 1.5 wt.% Zn, hosts ternary IM1-phase IMPs. Electrochemical methods and the hydrogen-gas evolution method were deployed and complemented by transmission electron microscopy analyses. These techniques used in concert reveal that the Mg2Ca-type IMPs anodically dissolve preferentially and completely, while the IM1-type IMPs act as nano-cathodes, facilitating a faster dissolution of ZX20 compared to ZX10. Additionally, a dynamically increasing cathodic reactivity with progressing dissolution was observed for both alloys. This effect is explained by redeposits of Zn on the corroding surface, which act as additional nano-cathodes and facilitate enhanced cathodic reaction kinetics. The higher degradation rate of ZX20 was verified in vivo via micro-computed tomography upon implantation of both materials into femurs of Sprague DawleyⓇ rats. Both alloys were well integrated with direct bone‒implant contact observable 4 weeks post operationem, and an appropriately slow and homogeneous degradation could be observed with no adverse effects on the surrounding tissue. The results suggest that both alloys qualify as new temporary implant materials, and that a minor adjustment of the Zn content may function as a lever for tuning the degradation rate towards desired applications. STATEMENT OF SIGNIFICANCE: In Mg‒Zn‒Ca (ZX)-lean alloys Zn is the most electropositive element, and thus requires special attention in the investigation of biocorrosion mechanisms acting on these alloys. Even a small increase of only 0.5 wt.% Zn is shown to accelerate the biodegradation rate in both simulated body conditions and in vivo. This is possible due to Zn's role in influencing the type of intermetallic particles (IMPs) in these alloys. These IMPs in turn, even though minute in size, are shown to govern the biocorrosion behavior on the macroscopic scale. The deep understanding gained in this study on the role of Zn and of the IMP type it governs is crucial to ensuring a safe and controllable implant degradation.

Collective antiskyrmion-mediated phase transition and defect-induced melting in chiral magnetic films.

Magnetic phase transitions are a manifestation of competing interactions whose behavior is critically modified by defects and becomes even more complex when topological constraints are involved. In particular, the investigation of skyrmions and skyrmion lattices offers insight into fundamental processes of topological-charge creation and annihilation upon changing the magnetic state. Nonetheless, the exact physical mechanisms behind these phase transitions remain unresolved. Here, we show numerically that it is possible to collectively reverse the polarity of a skyrmion lattice in a field-induced first-order phase transition via a transient antiskyrmion-lattice state. We thus propose a new type of phase transformation where a skyrmion lattice inverts to another one due to topological constraints. In the presence of even a single defect, the process becomes a second-order phase transition with gradual topological-charge melting. This radical change in the system's behavior from a first-order to a second-order phase transition demonstrates that defects in real materials could prevent us from observing collective topological phenomena. We have systematically compared ultra-thin films with isotropic and anisotropic Dzyaloshinskii-Moriya interactions (DMIs), and demonstrated a nearly identical behavior for such technologically relevant interfacial systems.

The relation between local structural distortion and the low-temperature magnetic anomaly in Fe7S8.

Structural defects on an atomic level can crucially impact the magnetic properties of a material. We study this phenomenon by means of magnetometry and powder neutron diffraction on a stoichiometric, monoclinic pyrrhotite (Fe7S8), which is a classic omission structure with a magnetic anomaly at about 30 K. The initial structural distortion of the pyrrhotite at 300 K caused by the vacancy arrangement decreases upon cooling, and simultaneous to the magnetic anomaly the anisotropic contraction of the unit cell homogenizes the covalency of the Fe-Fe bonds with lengths less than 3.0 Å and the Fe-S-Fe bond angles. These changes on the atomic level affect the spin-orbit coupling and the super-exchange interactions in Fe7S8, and trigger the low-temperature magnetic anomaly within a crystallographically stable system.

Comparison of a resorbable magnesium implant in small and large growing-animal models.

Fracture treatment in children needs new implant materials to overcome disadvantages associated with removal surgery. Magnesium-based implants constitute a biocompatible and bioresorbable alternative. In adults and especially in children, implant safety needs to be evaluated. In children the bone turnover rate is higher and implant material might influence growth capacity, and the long-term effect of accumulated particles or ions is more critical due to the host's prolonged post-surgery lifespan. In this study we aimed to investigate the degradation behavior of ZX00 (Mg-0.45Zn-0.45Ca; in wt.%) in a small and a large animal model to find out whether there is a difference between the two models (i) in degradation rate and (ii) in bone formation and in-growth. Our results 6, 12 and 24 weeks after ZX00 implantation showed no negative effects on bone formation and in-growth, and no adverse effects such as fibrotic or sclerotic encapsulation. The degradation rate did not significantly differ between the two growing-animal models, and both showed slow and homogeneous degradation performance. Our conclusion is that small animal models may be sufficient to investigate degradation rates and provide preliminary evidence on bone formation and in-growth of implant materials in a growing-animal model. STATEMENT OF SIGNIFICANCE: The safety of implant material is of the utmost importance, especially in children, who have enhanced bone turnover, more growth capacity and longer postoperative lifespans. Magnesium (Mg)-based implants have long been of great interest in pediatric orthopedic and trauma surgery, due to their good biocompatibility, biodegradability and biomechanics. In the study documented in this manuscript we investigated Mg-Zn-Ca implant material without rare-earth elements, and compared its outcome in a small and a large growing-animal model. In both models we observed bone formation and in-growth which featured no adverse effects such as fibrotic or sclerotic encapsulation, and slow homogeneous degradation performance of the Mg-based implant material.

Monotropic polymorphism in a glass-forming metallic alloy.

This study investigates the crystallization and phase transition behavior of the amorphous metallic alloy Au70Cu5.5Ag7.5Si17. This alloy has been recently shown to exhibit a transition of a metastable to a more stable crystalline state, occurring via metastable melting under strong non-equilibrium conditions. Such behavior had so far not been observed in other metallic alloys. In this investigation fast differential scanning calorimetry (FDSC) is used to explore crystallization and the solid-liquid-solid transition upon linear heating and during isothermal annealing, as a function of the conditions under which the metastable phase is formed. It is shown that the occurrence of the solid-liquid-solid transformation in FDSC depends on the initial conditions; this is explained by a history-dependent nucleation of the stable crystalline phase. The microstructure was investigated by scanning and transmission electron microscopy and x-ray diffraction. Chemical mapping was performed by energy dispersive x-ray spectrometry. The relationship between the microstructure and the phase transitions observed in FSDC is discussed with respect to the possible kinetic paths of the solid-liquid-solid transition, which is a typical phenomenon in monotropic polymorphism.

Long-term in vivo degradation behavior and near-implant distribution of resorbed elements for magnesium alloys WZ21 and ZX50.

UNLABELLED: We report on the long-term effects of degrading magnesium implants on bone tissue in a growing rat skeleton using continuous in vivo micro-Computed Tomography, histological staining and Laser Ablation Inductively Coupled Plasma Mass Spectrometry (LA-ICP-MS). Two different magnesium alloys-one rapidly degrading (ZX50) and one slowly degrading (WZ21)-were used to evaluate the bone response and distribution of released Mg and Y ions in the femur of male Sprague-Dawley rats. Regardless of whether the alloy degrades rapidly or slowly, we found that bone recovers restitutio ad integrum after complete degradation of the magnesium implant. The degradation of the Mg alloys generates a significant increase in Mg concentration in the cortical bone near the remaining implant parts, but the Mg accumulation disappears after the implant degrades completely. The degradation of the Y-containing alloy WZ21 leads to Y enrichment in adjacent bone tissues and in newly formed bone inside the medullary space. Locally high Y concentrations suggest migration not only of Y ions but also of Y-containing intermetallic particles. However, after the full degradation of the implant the Y-enrichment disappears almost completely. Hydrogen gas formation and ion release during implant degradation did not harm bone regeneration in our samples. STATEMENT OF SIGNIFICANCE: Magnesium is generally considered to be one of the most attractive base materials for biodegradable implants, and many magnesium alloys have been optimized to adjust implant degradation. Delayed degradation, however, generates prolonged presence in the organism with the risk of foreign body reactions. While most studies so far have only ranged from several weeks up to 12months, the present study provides data for complete implant degradation and bone regeneration until 24months, for two magnesium alloys (ZX50, WZ21) with different degradation characteristics. µCT monitoring, histological staining and LA-ICP-MS illustrate the distribution of the elements in the neighboring bony tissues during implant degradation, and reveal in particular high concentrations of the rare-earth element Yttrium.

Solid-solid phase transitions via melting in metals.

Observing solid-solid phase transitions in-situ with sufficient temporal and spatial resolution is a great challenge, and is often only possible via computer simulations or in model systems. Recently, a study of polymeric colloidal particles, where the particles mimic atoms, revealed an intermediate liquid state in the transition from one solid to another. While not yet observed there, this finding suggests that such phenomena may also occur in metals and alloys. Here we present experimental evidence for a solid-solid transition via the formation of a metastable liquid in a 'real' atomic system. We observe this transition in a bulk glass-forming metallic system in-situ using fast differential scanning calorimetry. We investigate the corresponding transformation kinetics and discuss the underlying thermodynamics. The mechanism is likely to be a feature of many metallic glasses and metals in general, and may provide further insight into phase transition theory.

Clustered field evaporation of metallic glasses in atom probe tomography.

Field evaporation of metallic glasses is a stochastic process combined with spatially and temporally correlated events, which are referred to as clustered evaporation (CE). This phenomenon is investigated by studying the distance between consecutive detector hits. CE is found to be a strongly localized phenomenon (up to 3nm in range) which also depends on the type of evaporating ions. While a similar effect in crystals is attributed to the evaporation of crystalline layers, CE of metallic glasses presumably has a different - as yet unknown - physical origin. The present work provides new perspectives on quantification methods for atom probe tomography of metallic glasses.

Magnesium from bioresorbable implants: Distribution and impact on the nano- and mineral structure of bone.

Biocompatibility is a key issue in the development of new implant materials. In this context, a novel class of biodegrading Mg implants exhibits promising properties with regard to inflammatory response and mechanical properties. The interaction between Mg degradation products and the nanoscale structure and mineralization of bone, however, is not yet sufficiently understood. Investigations by synchrotron microbeam x-ray fluorescence (µXRF), small angle x-ray scattering (µSAXS) and x-ray diffraction (µXRD) have shown the impact of degradation speed on the sites of Mg accumulation in the bone, which are around blood vessels, lacunae and the bone marrow. Only at the highest degradation rates was Mg found at the implant-bone interface. The Mg inclusion into the bone matrix appeared to be non-permanent as the Mg-level decreased after completed implant degradation. µSAXS and µXRD showed that Mg influences the hydroxyl apatite (HAP) crystallite structure, because markedly shorter and thinner HAP crystallites were found in zones of high Mg concentration. These zones also exhibited a contraction of the HAP lattice and lower crystalline order.

Reaction of bone nanostructure to a biodegrading Magnesium WZ21 implant - A scanning small-angle X-ray scattering time study.

Understanding the implant-bone interaction is of prime interest for the development of novel biodegrading implants. Magnesium is a very promising material in the class of biodegrading metallic implants, owing to its mechanical properties and excellent immunologic response during healing. However, the influence of degrading Mg implants on the bone nanostructure is still an open question of crucial importance for the design of novel Mg implant alloys. This study investigates the changes in the nanostructure of bone following the application of a degrading WZ21 Mg implant (2wt% Y, 1wt% Zn, 0.25wt% Ca and 0.15wt% Mn) in a murine model system over the course of 15months by small angle X-ray scattering. Our investigations showed a direct response of the bone nanostructure after as little as 1month with a realignment of nano-sized bone mineral platelets along the bone-implant interface. The growth of new bone tissue after implant resorption is characterized by zones of lower mineral platelet thickness and slightly decreased order in the stacking of the platelets. The preferential orientation of the mineral platelets strongly deviates from the normal orientation along the shaft and still roughly follows the implant direction after 15months. We explain our findings by considering geometrical, mechanical and chemical factors during the process of implant resorption. STATEMENT OF SIGNIFICANCE: The advancement of surgical techniques and the increased life expectancy have caused a growing demand for improved bone implants. Ideally, they should be bio-resorbable, support bone as long as necessary and then be replaced by healthy bone tissue. Magnesium is a promising candidate for this purpose. Various studies have demonstrated its excellent mechanical performance, degradation behaviour and immunologic properties. The structural response of bone, however, is not well known. On the nanometer scale, the arrangement of collagen fibers and calcium mineral platelets is an important indicator of structural integrity. The present study provides insight into nanostructural changes in rat bone at different times after implant placement and different implant degradation states. The results are useful for further improved magnesium alloys.

Crystal-Like Rearrangements of Icosahedra in Simulated Copper-Zirconium Metallic Glasses and their Effect on Mechanical Properties.

Indications of the Cu2Zr Laves phase are observed in MD simulations of amorphous Cu64Zr36 upon isothermal holding just above the glass transition temperature. The structural evolution towards Cu2Zr is accompanied by an increase in the fraction of Cu-centered icosahedra, which demonstrates that a large icosahedral fraction does not just indicate structural relaxation. The crystal-like regions generate an increase in strength and Young's modulus, and a stronger localized shear band. A universal relation between the fraction of full icosahedra and their interconnectivity is found, and both can be modified simultaneously via changes of temperature or strain.

Influence of trace impurities on the in vitro and in vivo degradation of biodegradable Mg-5Zn-0.3Ca alloys.

The hydrogen evolution method and animal experiments were deployed to investigate the effect of trace impurity elements on the degradation behavior of high-strength Mg alloys of type ZX50 (Mg-5Zn-0.3Ca). It is shown that trace impurity elements increase the degradation rate, predominantly in the initial period of the tests, and also increase the material's susceptibility to localized corrosion attack. These effects are explained on the basis of the corrosion potential of the intermetallic phases present in the alloys. The Zn-rich phases present in ZX50 are nobler than the Mg matrix, and thus act as cathodic sites. The impurity elements Fe and Mn in the alloy of conventional purity are incorporated in these Zn-rich intermetallic phases and therefore increase their cathodic efficiency. A design rule for circumventing the formation of noble intermetallic particles and thus avoiding galvanically accelerated dissolution of the Mg matrix is proposed.

Diffusion on demand to control precipitation aging: application to Al-Mg-Si alloys.

We demonstrate experimentally that a part-per-million addition of Sn solutes in Al-Mg-Si alloys can inhibit natural aging and enhance artificial aging. The mechanism controlling the aging is argued to be vacancy diffusion, with solutes trapping vacancies at low temperature and releasing them at elevated temperature, which is supported by a thermodynamic model and first-principles computations of Sn-vacancy binding. This "diffusion on demand" solves the long-standing problem of detrimental natural aging in Al-Mg-Si alloys, which is of great scientific and industrial importance. Moreover, the mechanism of controlled buffering and release of excess vacancies is generally applicable to modulate diffusion in other metallic systems.

In vivo degradation performance of micro-arc-oxidized magnesium implants: a micro-CT study in rats.

Biodegradable Mg alloys are of great interest for osteosynthetic applications because they do not require surgical removal after they have served their purpose. In this study, fast-degrading ZX50 Mg-based implants were surface-treated by micro-arc oxidation (MAO), to alter the initial degradation, and implanted along with untreated ZX50 controls in the femoral legs of 20 male Sprague-Dawley rats. Their degradation was monitored by microfocus computed tomography (µCT) over a total observation period of 24weeks, and histological analysis was performed after 4, 12 and 24weeks. While the MAO-treated samples showed almost no corrosion in the first week, they revealed an accelerated degradation rate after the third week, even faster than that of the untreated ZX50 implants. This increase in degradation rate can be explained by an increase in the surface-area-to-volume ratio of MAO-treated implants, which degrade inhomogeneously via localized corrosion attacks. The histological analyses show that the initially improved corrosion resistance of the MAO implants has a positive effect on bone and tissue response: The reduced hydrogen evolution (due to reduced corrosion) makes possible increased osteoblast apposition from the very beginning, thus generating a stable bone-implant interface. As such, MAO treatment appears to be very interesting for osteosynthetic implant applications, as it delays implant degradation immediately after implantation, enhances fracture stabilization, minimizes the burden on the postoperatively irritated surrounding tissue and generates good bone-implant connections, followed by accelerated degradation in the later stage of bone healing.

Probing shear-band initiation in metallic glasses.

In situ acoustic emission monitoring is shown to capture the initiation of shear bands in metallic glasses. A model picture is inferred from stick-slip flow in granular media such that the origin of acoustic emission is attributed to a mechanism of structural dilatation. By employing a quantitative approach, the critical volume change associated with shear-band initiation in a metallic glass is estimated to be a few percent only. This result agrees with typical values of excess free volume found in the supercooled liquid regime near the glass transition temperature.

Interaction-induced partitioning and magnetization jumps in the mixed-spin oxide FeTiO3-Fe2O3.

In this study we report on jumps in the magnetic moment of the hemo-ilmenite solid solution (x)FeTiO(3)-(1-x)Fe(2)O(3) above Fe(III) percolation at low temperature (T<3 K). The first jumps appear at 2.5 K, one at each side of the magnetization loop, and their number increases with decreasing temperature and reaches 5 at T=0.5 K. The jumps occur after field reversal from a saturated state and are symmetrical in the trigger field and intensity with respect to the field axis. Moreover, an increase of the sample temperature by 2.8% at T=2.0 K indicates the energy released after the ignition of the magnetization jump, as the spin-currents generated by the event are dissipated in the lattice. The magnetization jumps are further investigated by Monte Carlo simulations, which show that these effects are a result of magnetic interaction-induced partitioning on a sublattice level.

Electric and magnetic resonances in arrays of coupled gold nanoparticle in-tandem pairs.

We present an experimental and theoretical study on the optical properties of arrays of gold nanoparticle in-tandem pairs (nanosandwiches). The well-ordered Au pairs with diameters down to 35 nm and separation distances down to 10 nm were fabricated using extreme ultraviolet (EUV) interference lithography. The strong near-field coupling of the nanoparticles leads to electric and magnetic resonances, which can be well reproduced by Finite-Difference Time-Domain (FDTD) calculations. The influence of the structural parameters, such as nanoparticle diameter and separation distance, on the hybridized modes is investigated. The energy and lifetimes of these modes are studied, providing valuable physical insight for the design of novel plasmonic structures and metamaterials.