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 ( 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 Mg60+xZn35−xCa5 (0≤x≤7) alloys show great potential for deployment in a new generation of biodegradable implants.
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.
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
and 20,000 K s
, respectively; for the CHG they are 4000 K s
and 6000 K s
. 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.
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.
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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.
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.
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Mg-based biodegradable materials are considered promising candidates in the paediatric field due to their favourable mechanical and biological properties and their biodegrading ...potential that makes a second surgery for implant removal unnecessary. In many cases the surgical fixation technique requires a crossing of the growth plate by the implant in order to achieve an adequate fragment replacement or fracture stabilisation. This study investigates the kinetics of slowly and rapidly degrading Mg alloys in a transphyseal rat model, and also reports on their dynamics in the context of the physis and consecutive bone growth. Twenty-six male Sprague–Dawley rats received either a rapidly degrading (ZX50; n = 13) or a slowly degrading (WZ21; n = 13) Mg alloy, implanted transphyseal into the distal femur. The contralateral leg was drilled in the same manner and served as a direct sham specimen. Degradation behaviour, gas formation, and leg length were measured by continuous in vivo micro CT for up to 52 weeks, and additional high-resolution µCT (HRS) scans and histomorphological analyses of the growth plate were performed. The growth plate was locally destroyed and bone growth was significantly diminished by the fast degradation of ZX50 implants and the accompanying release of large amounts of hydrogen gas. In contrast, WZ21 implants showed homogenous and moderate degradation performance, and the effect on bone growth did not differ significantly from a single drill-hole defect.
This study is the first that reports on the effects of degrading magnesium implants on the growth plate in a living animal model. The results show that high evolution of hydrogen gas due to rapid Mg degradation can damage the growth plate substantially. Slow degradation, however, such as seen for WZ21 alloys, does not affect the growth plate more than drilling alone, thus meeting one important prerequisite for deployment in paediatric osteosynthesis.
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.
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.
Salt printing, infiltration, and leaching enable structured porosity in otherwise intractable materials. Rheologically engineered suspensions of salt particles allow for direct ink writing of complex‐shaped structures displaying porosity at the micro‐ to macroscale. Metal infiltration of these 3D printed structures followed by salt leaching generates Mg scaffolds with exquisite control of the pore size, shape, and local material distribution.
A design strategy deployed in developing new biodegradable Mg–Y–Zn alloys is summarized and the key factors influencing their suitability for medical applications are described. The Mg–Y–Zn alloys ...reveal microstructural features and mechanical characteristics expected to be appropriate for vascular intervention applications. The focus of this article lies in the evaluation of the degradation performance and biological response of the alloys with respect to their potential as implant materials (stents). The degradation characteristics analyzed by immersion testing and electrochemical impedance spectroscopy in simulated physiological media reveal slow and homogeneous degradation. In vitro cell tests using human umbilical vein endothelial cells indicate good cytocompatibility on the basis of the alloys’ eluates (extracts). Animal studies carried out with pigs on Mg–2Y–1Zn (in wt.%) reveal an auspicious in vivo performance. Evaluation of preparations derived from implants in various types of tissues indicates homogeneous degradation and only limited gas formation during in vivo testing. The characteristics of the tissue reactions indicate good biocompatibility. The new Mg–Y–Zn alloys show an interesting combination of preferred microstructural, mechanical, electrochemical and biological properties, which make them very promising for degradable implant applications.
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.
Dealloying of intermetallic nanoprecipitates governs the electrochemical reactivity of multicomponent Mg alloys. TEM‐based analyses allow the direct observation of intermetallic‐particle (IMP) dealloying at the nanoscale. Electrochemically active Ca preferentially dissolves, while electrochemically more noble Zn is cathodically protected. Zn enrichment leads to a gradual ennoblement of the IMP concomitant with its enhancing cathodic reactivity.
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