Transmission X-ray Microscopy Research Articles

Learning heterogeneous reaction kinetics from X-ray videos pixel by pixel

Reaction rates at spatially heterogeneous, unstable interfaces are notoriously difficult to quantify, yet are essential in engineering many chemical systems, such as batteries1 and electrocatalysts2. Experimental characterizations of such materials by operando microscopy produce rich image datasets3–6, but data-driven methods to learn physics from these images are still lacking because of the complex coupling of reaction kinetics, surface chemistry and phase separation7. Here we show that heterogeneous reaction kinetics can be learned from in situ scanning transmission X-ray microscopy (STXM) images of carbon-coated lithium iron phosphate (LFP) nanoparticles. Combining a large dataset of STXM images with a thermodynamically consistent electrochemical phase-field model, partial differential equation (PDE)-constrained optimization and uncertainty quantification, we extract the free-energy landscape and reaction kinetics and verify their consistency with theoretical models. We also simultaneously learn the spatial heterogeneity of the reaction rate, which closely matches the carbon-coating thickness profiles obtained through Auger electron microscopy (AEM). Across 180,000 image pixels, the mean discrepancy with the learned model is remarkably small (<7%) and comparable with experimental noise. Our results open the possibility of learning nonequilibrium material properties beyond the reach of traditional experimental methods and offer a new non-destructive technique for characterizing and optimizing heterogeneous reactive surfaces.

Morphological and lipid metabolism alterations in macrophages exposed to model environmental nanoplastics traced by high-resolution synchrotron techniques.

The release of nanoplastics (NPs) in the environment is a significant health concern for long-term exposed humans. Although their usage has certainly revolutionized several application fields, at nanometer size, NPs can easily interact at the cellular level, resulting in potential harmful effects. Micro/Nanoplastics (M/NPs) have a demonstrated impact on mammalian endocrine components, such as the thyroid, adrenal gland, testes, and ovaries, while more investigations on prenatal and postnatal exposure are urgently required. The number of literature studies on the NPs' presence in biological samples is increasing. However, only a few offer a close study on the model environmental NP-immune system interaction exploited by advanced microscopy techniques. The present study highlights substantial morphological and lipid metabolism alterations in human M1 macrophages exposed to labeled polypropylene and polyvinyl chloride nanoparticles (PP and PVC NPs) (20 μg/ml). The results are interpreted by advanced microscopy techniques combined with standard laboratory tests and fluorescence microscopy. We report the accurate detection of polymeric nanoparticles doped with cadmium selenide quantum dots (CdSe-QDs NPs) by following the Se (L line) X-ray fluorescence emission peak at higher sub-cellular resolution, compared to the supportive light fluorescence microscopy. In addition, scanning transmission X-ray microscopy (STXM) imaging successfully revealed morphological changes in NP-exposed macrophages, providing input for Fourier transform infrared (FTIR) spectroscopy analyses, which underlined the chemical modifications in macromolecular components, specifically in lipid response. The present evidence was confirmed by quantifying the lipid droplet (LD) contents in PP and PVC NPs-exposed macrophages (0-100 μg/ml) by Oil Red O staining. Hence, even at experimental NPs' concentrations and incubation time, they do not significantly affect cell viability; they cause an evident lipid metabolism impairment, a hallmark of phagocytosis and oxidative stress.

Operando Microscopy of Model Electrocatalysts during Oxygen Evolution Reaction

In situ characterization of electrochemical processes in model materials are central to fundamental electrochemistry as they provide precise potential-dependent quantities that can be used to accurately assess theoretical models and predictions. As such, structural evolution of materials under highly oxidizing conditions represents a particular challenge. To gain the necessary insight into the surface and bulk behavior, one should combine advanced in situ characterization techniques with well-defined materials that are essential for modeling.In this talk, I will discuss how a combination of in situ microscopy techniques can provide insight into the surface and bulk behavior of electrocatalysts during electrocatalytic water splitting (OER). Specifically, I will show how operando electrochemical atomic force microscopy (EC-AFM) can be used to record nanoscale changes in the surface morphology during anodic corrosion of the perovskite SrIrO3 surface. I will also discuss how operando EC-AFM can be combined with operando transmission X-ray microscopy and scanning electrochemical cell technique to probe the evolution and reactivity of single particles of Co(OH)2.

Bifunctional Oxygen Electrocatalysis on Manganese Oxide

Limited supply of precious metals impedes the scale up of electrolyzer production. To enable 100s of GWs of PEM electrolyzer capacity by 2030, iridium supply must grow by more than 10x.[1] Alternatively, catalysts made of cheaper, more abundant manganese could relieve these constraints, if engineered to have comparable activity and stability. The unique bifunctional OER/ORR activity of Mn oxide could also enable electrolyzers that both produce and consume fuel with a single catalyst. Yet rational design of Mn oxide catalysts requires a better understanding of the structural and chemical motifs that lead to high bifunctional performance.In this talk, we will discuss our investigation of the bifunctional OER & ORR activity of Mn oxide and its unusual pH dependence. Our model system, 𝛼-KxMnO2, is among the best reported Mn oxide catalysts for both the OER and the ORR, with ORR activity matching that of Pt.[2] While the OER activity of Mn oxide has been shown to increase at higher pH,[3] we will show that its ORR activity improves as well. We will discuss our attempts to understand this phenomenon with operando scanning transmission x-ray microscopy (STXM), which enables spectroscopic investigation of single catalyst particles during reaction with spatial resolution down to 25 nm. Complementary surface DFT calculations provide further evidence for identification of the active crystal facets and insights into the pH-dependency of the OER & ORR mechanisms. We will discuss the implications of this work on the design of bidirectional electrolyzers with low-cost, non-precious metal catalysts.[1] IRENA. Green Hydrogen Cost Reduction. 2020 [2] Meng, Y. et al. J. Am. Chem. Soc. 2014, 136 (32), 11452–11464.[3] Takashima, T. et al. J. Am. Chem. Soc. 2012, 134 (3), 1519–1527.

A Drive Towards Elemental Simplicity in Cathode Design by Controlling Grain Growth Behavior

Sodium-ion battery technologies are emerging as an alternative to lithium-ion batteries by utilizing the earth abundant, widely distributed, and low-cost sodium resources. Among different types of sodium ion cathodes, transition metal based layered oxide cathodes have a superior edge due to their comparatively higher energy density, lower cost, environment friendly raw materials, and similar synthesis chemistry as the already commercialized lithium-ion battery cathode materials. They also enable the incorporation of iron, an abundant, low-cost, and environmentally benign element, replacing the toxic and expensive cobalt.In such layered oxide-based cathodes, transition metals exhibit heterogenous elemental and oxidation state distribution at different depths of the particles (e.g., from the surface to bulk) which can influence the stability, mechanical integrity, and electrochemical performance of these particles to a significant extent. The inherent local structural and electronic state heterogeneity developed in these materials during synthesis can modulate the charge distribution heterogeneity and consequent phase transitions during cycling, ultimately controlling the battery performance.In this work, a sodium transition metal layered oxide cathode is synthesized using a co-precipitation method followed by high temperature calcination under different calcination durations. Calcining the material at different conditions lead to the formation of particles with different morphologies and grain growth behavior. Using electron microscopy and Xray diffraction techniques, the grain growth behavior at different stages of calcination is studied. This will guide the design of particles with better morphologies and grain orientation which demonstrate improved electrochemical performance. Transition metal distribution and oxidation state change at different depths of the particles are probed using synchrotron based Xray absorption spectroscopy and three-dimensional Transmission Xray microscopy. The particles are probed at the surface, subsurface and deep into the bulk, which show heterogeneity in the distribution of transition metal oxidation state and provide insight into the phase transitions during calcination. This study can pave the way for better understanding of phase evolution during synthesis and improved design of cathode particle morphology and composition by identifying and eliminating the detrimental phases occurring during different stages of calcination.

Interfacial Challenge for Solid-State Lithium Batteries- Liquid Addition

All solid-state lithium batteries with garnet electrolytes (Li7La3Zr2O12, LLZO) are promising energy storage devices that have gained increasing attention due to their huge potential towards non-flammability and higher energy density. However, reported solid-state lithium batteries cannot achieve the projected energy density (> 500 Wh/kg at the cell level) mainly due to insufficient contact and poor compatibility between LLZO and electrodes. The use of liquid electrolytes in small quantities has been suggested as a component in the quasi-solid hybrid electrolytes to address these two issues. However, the working principle of liquid electrolytes added as the interface inside the batteries is not clear yet.This study added 10L carbonate-based liquid electrolyte between LLZO and LiNi0.6Mn0.6Co0.2O2 (NMC 622) cathode. The assembled Li|LLZO|NMC 622 cell exhibited an initial discharge capacity of 168 mAh g-1 with a capacity retention ratio of ~82 % after 28 cycles. Scanning Transmission X-ray Microscopy revealed the reaction of LE with garnet and NMC 622. More importantly, the LE decomposed and solidified during the cycling process. Decomposed LE participated in the formation of a newly-identified solid-liquid electrolyte interface (SLEI) just after the 1st cycle. Furthermore, the X-ray Absorption Spectroscopy results indicated that the SLEI consisted predominantly of LiF, LaF3, Li2O, and Li2CO3 species.Overall, this study proved the solidification of liquid electrolytes at the garnet/cathode interface. The formation of SLEI effectively suppressed the degradation of the garnet electrolyte and stabilized the battery cycling performance. More efforts are required to optimize the liquid and establish a more stable SLEI that could expand the cycling life of the batteries.

STXM – scanning transmission X-ray microscopy

STXM – scanning transmission X-ray microscopy

Mapping Heterogeneity of Pristine and Aged Li- and N-Mnhcf Cathode by Synchrotron-Based Energy-Dependent Full Field Transmission X-ray Microscopy.

Manganese hexacyanoferrate is a promising cathode material for lithium and sodium ion batteries, however, it suffers of capacity fading during the cycling process. To access the structural and functional characteristics at the nanometer scale, fresh and cycled electrodes are extracted and investigated by transmission soft X-ray microscopy, which allows chemical characterization with spatial resolution from position-dependent x-ray spectra at the Mn L-, Fe L- and N K-edges. Furthermore, soft X-rays prove to show superior sensitivity toward Fe, compare to hard X-rays. Inhomogeneities within the samples are identified, increasing in the aged electrodes, more dramatically in the Li-ion system, which explains the poorer cycle life as Li-ion cathode material. Local spectra, revealing different oxidation states over the sample with strong correlation between the Fe L-edge, Mn L-edge, and N K-edge, imply a coupling between redox centers and an electron delocalization over the host framework.

Dynamic fracture processes in hydrogen embrittled iron

Mechanistic understanding of hydrogen embrittlement is critical to the transport and storage of hydrogen as a sustainable fuel. Experimental observation of dynamic fracture processes in hydrogen environments has been challenging. Here, in-situ transmission X-ray microscopy is used to image polycrystalline iron foils that are concurrently strained and electrochemically charged with hydrogen. Using this technique, voids and microcracks down to ∼30 nm in size are identified at or near the crack tip and tracked as strain is increased. We observe both hydrogen-induced transgranular failure and hydrogen-induced intergranular failure with distinct fracture processes. We find that transgranular fracture occurs through the formation of sharp branched structures at the main crack tip that are reminiscent of slip band formation. This is followed by void growth and coalescence, and interaction with secondary cracks that lead to propagation of the main crack. Intergranular fracture is found to occur through void coalescence along grain boundaries, along with significant secondary cracking near the crack tip. The crack growth rate is greater for void-mediated intergranular failure than for slip-mediated transgranular failure. Additionally, the removal of hydrogen results in recovered ductility for a crack initially propagated under hydrogen charging.

Direct observation of Néel-type skyrmions and domain walls in a ferrimagnetic DyCo3 thin film

Isolated magnetic skyrmions are stable, topologically protected spin textures that are at the forefront of research interests today due to their potential applications in information technology. A distinct class of skyrmion hosts are rare earth - transition metal (RE-TM) ferrimagnetic materials. To date, the nature and the control of basic traits of skyrmions in these materials are not fully understood. We show that for an archetypal ferrimagnetic material DyCo3 that exhibits a strong perpendicular anisotropy, the ferrimagnetic skyrmion size can be tuned by an external magnetic field. Moreover, by taking advantage of the high spatial resolution of scanning transmission X-ray microscopy (STXM) and utilizing a large x-ray magnetic linear dichroism (XMLD) contrast that occurs naturally at the RE resonant edges, we resolve the nature of the magnetic domain walls of ferrimagnetic skyrmions. We demonstrate that through this method one can easily discriminate between Bloch and Néel type domain walls for each individual skyrmion. For all isolated ferrimagnetic skyrmions, we observe that the domain walls are of Néel-type. This key information is corroborated with results of micromagnetic simulations and allows us to conclude on the nature of the Dzyaloshinskii-Moriya interaction (DMI) which concurs to the stabilisation of skyrmions in this ferrimagnetic system. Establishing that an intrinsic DMI occurs in RE-TM materials will also be beneficial towards a deeper understanding of chiral spin texture control in ferrimagnetic materials.

Operando ultra-high-resolution X-ray microscopy of lithium anodes with separator interactions

Lithium (Li) metal is an attractive anode material candidate for high-energy-density battery systems that could enable challenging electrification applications, such as flight and heavy-duty vehicles. However, the formation of porous deposits and dendrites during cycling cause capacity loss and internal short-circuit risks. Here, we use high-resolution in-situ/operando Zernike phase contrast X-ray microscopy to directly visualize the lithium electrodeposition process inside a coin cell with a commercial separator. The nucleation and subsequent lithium electrodeposition were imaged by transmission X-ray microscopy (TXM) at 150 nm spatial resolution and <2 min temporal resolution. The resulting lithium deposits were then reconstructed into three-dimensional (3D) volumes by computed tomography (CT), revealing the Li structures above, at, and below the anode/separator interface. Distinct nucleation and deposition mechanisms were observed under varied cell temperatures, charging current density, and electrolyte composition. This work demonstrates the unique strengths of combining TXM and CT imaging techniques: the dynamic evolution of lithium electrodeposition and the comprehensive morphology of the resulting structure were characterized together. Furthermore, our results indicate the importance of in-situ/operando characterization of systems in commercially-relevant configurations in developing practical dendrite mitigation strategies.

Nitrogen-Rich Organic Matter Formation and Stabilization in Iron Ore Tailings: A Submicrometer Investigation.

Organic matter (OM) formation and stabilization are critical processes in the eco-engineered pedogenesis of Fe ore tailings, but the underlying mechanisms are unclear. The present 12 month microcosm study has adopted nanoscale secondary ion mass spectrometry (NanoSIMS) and synchrotron-based scanning transmission X-ray microscopy (STXM) techniques to investigate OM formation, molecular signature, and stabilization in tailings at micro- and nanometer scales. In this system, microbial processing of exogenous isotopically labeled OM demonstrated that 13C labeled glucose and 13C/15N labeled plant biomass were decomposed, regenerated, and associated with Fe-rich minerals in a heterogeneous pattern in tailings. Particularly, when tailings were amended with plant biomass, the 15N-rich microbially derived OM was generated and bound to minerals to form an internal organo-mineral association, facilitating further OM stabilization. The organo-mineral associations were primarily underpinned by interactions of carboxyl, amide, aromatic, and/or aliphatic groups with weathered mineral products derived from biotite-like minerals in fresh tailings (i.e., with Fe2+ and Fe3+) or with Fe3+ oxyhydroxides in aged tailings. The study revealed microbial OM generation and subsequent organo-mineral association in Fe ore tailings at the submicrometer scale during early stages of eco-engineered pedogenesis, providing a basis for the development of microbial based technologies toward tailings' ecological rehabilitation.

Combined Electrochemical, XPS, and STXM Study of Lithium Nitride as a Protective Coating for Lithium Metal and Lithium-Sulfur Batteries.

Li3N is an excellent protective coating material for lithium electrodes with very high lithium-ion conductivity and low electronic conductivity, but the formation of stable and homogeneous coatings is technically very difficult. Here, we show that protective Li3N coatings can be simply formed by the direct reaction of electrodeposited lithium electrodes with N2 gas, whereas using battery-grade lithium foil is problematic due to the presence of a native passivation layer that hampers that reaction. The protective Li3N coating is effective at preventing lithium dendrite formation, as found from unidirectional plating and plating-stripping measurements in Li-Li cells. The Li3N coating also efficiently suppresses the parasitic reactions of polysulfides and other electrolyte species with the lithium electrode, as demonstrated by scanning transmission X-ray microscopy, X-ray photoelectron spectroscopy, and optical microscopy. The protection of the lithium electrode against corrosion by polysulfides and other electrolyte species, as well as the promotion of smooth deposits without dendrites, makes the Li3N coating highly promising for applications in lithium metal batteries, such as lithium-sulfur batteries. The present findings show that the formation of Li3N can be achieved with lithium electrodes covered by a secondary electrolyte interface layer, which proves that the in situ formation of Li3N coatings inside the batteries is attainable.

Physicochemical characterization of free troposphere and marine boundary layer ice-nucleating particles collected by aircraft in the eastern North Atlantic

Abstract. Atmospheric ice nucleation impacts the hydrological cycle and climate by modifying the radiative properties of clouds. To improve our predictive understanding of ice formation, ambient ice-nucleating particles (INPs) need to be collected and characterized. Measurements of INPs at lower latitudes in a remote marine region are scarce. The Aerosol and Cloud Experiments in the Eastern North Atlantic (ACE-ENA) campaign, in the region of the Azores islands, provided the opportunity to collect particles in the marine boundary layer (MBL) and free troposphere (FT) by aircraft during the campaign's summer and winter intensive operation period. The particle population in samples collected was examined by scanning transmission X-ray microscopy with near-edge X-ray absorption fine structure spectroscopy. The identified INPs were analyzed by scanning electron microscopy with energy-dispersive X-ray analysis. We observed differences in the particle population characteristics in terms of particle diversity, mixing state, and organic volume fraction between seasons, mostly due to dry intrusion events during winter, as well as between the sampling locations of the MBL and FT. These differences are also reflected in the temperature and humidity conditions under which water uptake, immersion freezing (IMF), and deposition ice nucleation (DIN) proceed. Identified INPs reflect typical particle types within the particle population on the samples and include sea salt, sea salt with sulfates, and mineral dust, all associated with organic matter, as well as carbonaceous particles. IMF and DIN kinetics are analyzed with respect to heterogeneous ice nucleation rate coefficients, Jhet, and ice nucleation active site density, ns, as a function of the water criterion Δaw. DIN is also analyzed in terms of contact angles following classical nucleation theory. Derived MBL IMF kinetics agree with previous ACE-ENA ground-site INP measurements. FT particle samples show greater ice nucleation propensity compared to MBL particle samples. This study emphasizes that the types of INPs can vary seasonally and with altitude depending on sampling location, thereby showing different ice nucleation propensities, which is crucial information when representing mixed-phase cloud and cirrus cloud microphysics in models.

Detailing the influence of PEO-coated biodegradable Mg-based implants on the lacuno-canalicular network in sheep bone: A pilot study.

An increasing prevalence of bone-related injuries and aging geriatric populations continue to drive the orthopaedic implant market. A hierarchical analysis of bone remodelling after material implantation is necessary to better understand the relationship between implant and bone. Osteocytes, which are housed and communicate through the lacuno-canalicular network (LCN), are integral to bone health and remodelling processes. Therefore, it is essential to examine the framework of the LCN in response to implant materials or surface treatments. Biodegradable materials offer an alternative solution to permanent implants, which may require revision or removal surgeries. Magnesium alloys have resurfaced as promising materials due to their bone-like properties and safe degradation in vivo. To further tailor their degradation capabilities, surface treatments such as plasma electrolytic oxidation (PEO) have demonstrated to slow degradation. For the first time, the influence of a biodegradable material on the LCN is investigated by means of non-destructive 3D imaging. In this pilot study, we hypothesize noticeable variations in the LCN caused by altered chemical stimuli introduced by the PEO-coating. Utilising synchrotron-based transmission X-ray microscopy, we have characterised morphological LCN differences around uncoated and PEO-coated WE43 screws implanted into sheep bone. Bone specimens were explanted after 4, 8, and 12 weeks and regions near the implant surface were prepared for imaging. Findings from this investigation indicate that the slower degradation of PEO-coated WE43 induces healthier lacunar shapes within the LCN. However, the stimuli perceived by the uncoated material with higher degradation rates induces a greater connected LCN better prepared for bone disturbance.

Photodetection Properties of CdS/Si Heterojunction Prepared by Pulsed Laser Ablation in DMSO Solution for Optoelectronic Application.

The high-quality n-type CdS on a p-type Si (111) photodetector device was prepared for the first time by a one-pot method based on an ns laser ablation method in a liquid medium. Cadmium target was ablated in DMSO solution, containing sulfur precursor, and stirred, assisting in 1D-growth, to create the sulfide structure as CdS nano-ropes form, followed by depositing on the Si-substrate by spin coating. The morphological, structural, and optical characteristics of the CdS structure were examined using X-ray diffraction, transmission, and scanning electron microscopy, photoluminescence, and UV-VIS spectroscopy. From X-ray diffraction analysis, the growing CdS spheres have a good crystal nature, with a high purity and desired c-axis orientation along the (002) plane, and the crystallinity was around 30 nm. According to optical characterization, high transparency was found in the visible-near-infrared areas of the electromagnetic spectrum, and the CdS spheres have a direct optical energy band gap of 3.2 eV. After that, the CdS/Si hetero-structured device was found to be improved remarkably after adding CdS. It showed that the forward current is constantly linear, while the dark current is around 4.5 µA. Up to a bias voltage of 4 V, there was no breakdown, and the reverse current of the heterojunctions somewhat increased with reverse bias voltage, while the photocurrent reached up to 580 and 690 µA for using 15 and 30 W/cm2 light power, respectively. Additionally, the ideal factors for CdS/Si heterojunction were 3.1 and 3.3 for 15 and 30 W/cm2 light power, respectively. These results exhibited high performance compared to the same heterojunction produced by other techniques. In addition, this opens the route for obtaining more enhancements of these values based on the changing use of sulfide structures in the heterojunction formation.

Domain wall motion at low current density in a synthetic antiferromagnet nanowire

The current-driven motion of magnetic domain walls (DWs) is the working principle of magnetic racetrack memories. In this type of spintronic technology, high current densities are used to propel DW motion in magnetic nanowires, causing significant wire heating that corresponds to wasted energy. Synthetic antiferromagnets are known to show very fast DW motion at high current densities, but lower current densities around onset of motion have received less attention. Here we use scanning transmission x-ray microscopy to study the response of DWs in a SAF multilayer to short current pulses. We observe that the DWs depin at A m−2 and move more quickly in response to 5 ns duration current pulses than in comparable multilayers that lack antiferromagnetic coupling. The results suggest that DWs in SAF structures are superior to conventional Néel DWs for low energy consumption racetrack technologies.

Scanning transmission X-ray microscopy at the Advanced Light Source

Over 50 years of development, synchrotron based X-ray microscopy has become a routine and powerful tool for the analysis of nanoscale structure and chemistry in many areas of science. Scanning X-ray microscopy is particularly well suited to the study of chemical and magnetic states of matter and has become available at most synchrotron light sources using a variety of optical schemes, detectors and sample environments. The Advanced Light Source at Lawrence Berkeley National Laboratory has an extensive program of soft X-ray scanning microscopy which supports a broad range of scientific research using a suite of advanced tools for high spatio-temporal resolution and control of active materials. Instruments operating within an energy range between 200–2500 eV with spatial resolution down to 7 nm and sub 20 picosecond time resolution are available. These capabilities can be routinely used in combination with a variety of sample stimuli, including gas or fluid flow, temperature control from 100 to 1200 K, DC bias and pulsed or continuous microwave excitation. We present here a complete survey of our instruments, their most advanced capabilities and a perspective on how they complement each other to solve complex problems in energy, materials and environmental science.

Electrodeposited Ni-P electrodes: An effect of amorphous structure on the electrochemical behavior and electrocatalytic activity in the hydrogen oxidation reaction in alkaline media

Glassy carbon supported Ni/GC and amorphous Ni-P/GC electrodes were prepared by potentiostatic electrodeposition. The catalysts have been characterized by X-ray powder diffraction, transmission and scanning electron microscopy, and cyclic voltammetry. Particular attention has been paid to the influence of electrochemical oxidation on the electrochemical behavior of Ni-P/GC and Ni/GC electrodes in alkaline media as well as the activity of these electrodes in the hydrogen oxidation reaction (HOR). It was found that the oxidation treatment changes the properties of Ni/GC electrode due to the formation of active Ni/NiOx surface sites, while insignificantly affecting the performance of Ni-P/GC sample. The unordinary behavior of electrodeposited Ni-P/GC samples is tentatively attributed to their amorphous structure and the formation of nickel phosphate under high anodic potentials, which prevents the formation of irreversible Ni oxides.

Development of a Bioreactor-Coupled Flow-Cell Setup for 3D In Situ Nanotomography of Mg Alloy Biodegradation.

Functional materials feature hierarchical microstructures that define their unique set of properties. The prediction and tailoring of these require a multiscale knowledge of the mechanistic interaction of microstructure and property. An important material in this respect is biodegradable magnesium alloys used for implant applications. To correlate the relationship between the microstructure and the nonlinear degradation process, high-resolution in situ three-dimensional (3D) imaging experiments must be performed. For this purpose, a novel experimental flow cell is presented which allows for the in situ 3D-nano imaging of the biodegradation process of materials with nominal resolutions below 100 nm using nanofocused hard X-ray radiation from a synchrotron source. The flow cell setup can operate under adjustable physiological and hydrodynamic conditions. As a model material, the biodegradation of thin Mg-4Ag wires in simulated body fluid under physiological conditions and a flow rate of 1 mL/min is studied. The use of two full-field nanotomographic imaging techniques, namely transmission X-ray microscopy and near-field holotomography, is compared, revealing holotomography as the superior imaging technique for this purpose. Additionally, the importance of maintaining physiological conditions is highlighted by the preliminary results. Supporting measurements using electron microscopy to investigate the chemical composition of the samples after degradation are performed.