Archaeological findings prove the appearance and use of birch bark tar since the Middle Palaeolithic. The production and use of birch bark tar and pine wood tar has overlapped since at least the late Neolithic, but probably for much longer. The reliable chemical identification of such archaeological tar residues can offer valuable insights into, for example, ancient technical complexity, trade and culture. In this context, the scarcity of these mainly organic residue findings in the archaeological record bears the need for non-destructive analytical tools. However, there is currently no systematic proposed way for this purpose. We aim here to verify the organic nature and test the reliability of the identification of archaeological pine wood tar and birch bark tar with a combination of SEM-EDS, FTIR microspectroscopy in reflectance mode and XRD. We examined a set of experimental adhesive replicas of pine tar and birch tar in pristine form, but also after a three-year-long weathering experiment. Additionally, we studied a set of archaeological samples, consisting of Mesolithic bone/antler points with adhering hafting residues, form the Dutch North Sea. This research shows that degradation negatively influences the reliable verification and identification of the organic residue constituents significantly. SEM-EDS as a starting point of analysis verifies the residue's organic nature, but it cannot be used to identify birch or pine tar. XRD can identify crystalline additives in the adhesive mixture, like ochre and wax, as well as phases related to the artefact's environment of burial and provenance. Micro-FTIR is also capable of verifying the organic matter of the residue constituents. The differentiation of birch and pine tars is hindered by vibrational modes occurring in neighbouring wavenumbers for both tars, and by the limited research on degradation markers indicative of thermal treatment to prove tar production. Until reference collections also account for degradation and include a wide variety of adhesives, results of FTIR collected in reflectance mode are best treated with some caution.

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Evidence of different compound resin-based adhesives is present in South Africa from at least 77000 years ago. Ancient glue production is considered one of the oldest known highly complex technologies, requiring advanced technological and mental abilities. However, our current knowledge of adhesive materials, recipes, and uses in South Africa is limited by the lack of in-depth analysis and molecular characterization of residues. To deepen our knowledge of past adhesive technology, we performed a detailed multi-analytical analysis (use-wear, XRD, μ-CT, IR spectroscopy, GC-MS) of 30 Later Stone Age tools with adhesive remains from Steenbokfontein Cave, South Africa. At the site, tools made of various rocks were hafted with compound adhesives, and we identified three recipes: 1) resin/tar of Widdringtonia or Podocarpus species combined with hematite; 2) resin/tar of Widdringtonia or Podocarpus species mixed with hematite and another plant exudate; 3) resin/tar without hematite. The studied scrapers were used in hide-working activities, and the studied cutting tools were used to work animal and soft plant matters. All scrapers display evidence of intense resharpening and were discarded when no longer useable. The combination of different methods for residue analysis reveals the flexibility of adhesive technology at Steenbokfontein. Despite the consistent use of conifer resin/tar throughout the sequence, we observed that other ingredients were added or excluded independently of the tools’ raw materials and functions. Our results highlight the long-lasting tradition of using adhesive material from conifer species but also the adaptability and flexibility of adhesive traditions. The systematic application of this multi-analytical approach to Pleistocene adhesives will be useful to better characterise adhesive traditions and enhance the debate on the technological, cognitive, and behavioural implications of this technology.@en

In this study, we experimentally screen a promising class of intermetallic alloys for the electrochemical reduction of CO₂ toward hydrocarbon products. Based on previous DFT-based screening papers, combinations of strongly CO-binding metals such as iron, cobalt, and nickel with weakly CO-binding metals such as gallium, aluminium or zinc were selected as potentially promising catalytic materials. Despite the challenging production of these alloys, we report a general two-step synthesis method for intermetallic alloys and discuss the specific synthesis conditions that must be taken into account when synthesising these materials. After their synthesis, we use a recently developed differential electrochemical mass spectrometry (DEMS) setup to rapidly quantify the CO₂ reduction products over a range of potentials. Almost all newly developed intermetallic catalysts are shown to produce methane and ethylene, while the CoSn catalyst showed higher selectivity towards formate production. However, all tested catalysts mostly produced hydrogen and only reduce CO₂ to a small extent, despite the favourable computational screening results. We discuss possible reasons for this discrepancy and outline a more holistic approach for linking future DFT studies with experiments.

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The electrochemical dinitrogen reduction reaction (NRR) has recently gained much interest as it can potentially produce ammonia from renewable intermittent electricity and replace the Haber-Bosch process. Previous literature studies report Fe- and Mo-carbides as promising electrocatalysts for the NRR with activities higher than other metals. However, recent understanding of extraneous ammonia and nitrogen oxide contaminations have challenged previously published results. Here, we critically assess the NRR performance of several Fe- and Mo-carbides reported as promising by implementing a strict experimental protocol to minimize the effect of impurities. The successful synthesis of α-Mo₂C decorated carbon nanosheets, α-Mo₂C nanoparticles, θ-Fe₃C nanoparticles, and χ-Fe₅C₂ nanoparticles was confirmed by X-ray diffraction, scanning and transmission electron microscopy, and X-ray photoelectron and Mössbauer spectroscopy. After performing NRR chronoamperometric tests with the synthesized materials, the ammonia concentrations varied between 37 and 124 ppb and are in close proximity with the estimated ammonia background level. Notwithstanding the impracticality of these extremely low ammonia yields, the observed ammonia did not originate from the electrochemical nitrogen reduction but from unavoidable extraneous ammonia and NO_x impurities. These findings are in contradiction with earlier literature studies and show that these carbide materials are not active for the NRR under the employed conditions. This further emphasizes the importance of a strict protocol in order to distinguish between a promising NRR catalyst and a false positive.

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For Pd thin films, microstructural changes involved during hydrogen cycling provide the information needed to predict and optimize the film's mechanical strength. In this paper, a systematic study of the morphology, microstructure, texture, and stress has been performed on Pd thin films during hydrogen loading and deloading cycles at room temperature. Pd thin films of similar morphology were prepared by magnetron sputtering on substrates of different compliances, i.e., Si-oxide, Titanium (Ti) and Polyimide (PI). The evolution of the morphology, grain-orientation distribution (texture), state of stress, and dislocation densities are analyzed for each of the film substrate types for 20 hydrogen loading/deloading cycles. The lattice expansion and contraction caused by the transition from Pd to Pd-hydride and back result in a strong stress increase. This stress increase stabilizes after a few cycles by grain boundary motion that leads to a gradual enhancement of the (111) texture and changes in the dislocation density for Pd films that are strongly clamped on to an oxidized Si(100) wafer substrate with an intermediate layer (Ti or PI). For Pd on PI, the stress is also partly released by a crack-based (crack widening/growth/propagation) pathway. Pd films on Ti and PI do not buckle or blister after 20 hydrogen cycles. By providing a sufficiently compliant substrate the traditional problems of buckle-delamination of a film on a stiff substrate are mitigated.

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Copper is one of the most promising catalysts for the CO₂ reduction reaction (CO₂RR) due to its unique capability of producing multicarbon products in appreciable quantities. Most of the CO₂RR research efforts have been directed towards the development of new electrocatalysts to either increase product selectivities or decrease overpotentials. In contrast, only a few studies have systematically tested or benchmarked CO₂RR performances of electrocatalysts. In this paper, for the first time, the performances of five different polycrystalline copper foils purchased from different suppliers are benchmarked for their CO₂RR performance. Their differences are characterized in terms of microstructural features and the effect that these microstructural properties have on the electrocatalytic behavior during potentiostatic CO₂RR experiments are evaluated. It is shown that the potential applied is the dominant factor controlling CO₂RR selectivities, leading to the conclusion that microstructural properties of polycrystalline copper electrodes have a negligible effect on the outcome of CO₂RR experiments.

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It was recently discovered that vivianite (Fe₃(PO₄)₂.8H₂O) could be magnetically extracted from digested activated sludge which opened a new route for phosphorus recovery (Wijdeveld et al. 2022). While its formation in digested sludge is regularly reported, it is not yet studied for fresh, undigested activated sludge. In particular, the extent to which vivianite could form during sludge storage is missing. The current research showed that iron reduction was completed after 2–4 days of anaerobic storage, and the vivianite appeared to form quickly from the pool of reduced iron made available. After sludge thickening at the wastewater treatment plant (30 h retention time), around 11% of the iron was vivianite. With subsequent 1–3 days of anaerobic storage, this fraction increased to 50–55%. After this storage, almost all the vivianite that could potentially form did form. This research concluded that efficient vivianite formation can be achieved without a sludge digester, showing phosphorus recovery potential from undigested sludge via vivianite recovery. Besides, the recovery of vivianite from undigested sludge presents advantages like the reduction of the sludge to dispose of and mitigation of the vivianite scaling formation.

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An attachment has been developed for x-ray diffractometer systems equipped with a domed stage when using a 2D or 1D detector. It consists of a single screen in front of the detector positioned such that it blocks diffraction from the dome. This results in measured data free of disturbing spurious peaks and background, thereby greatly facilitating further data analysis. Its working principle is universally applicable and allows for all specimen orientation movements needed for x-ray diffraction measurements, including texture, stress, and mapping.

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In-situ resource utilization (ISRU) is increasingly acknowledged as an essential requirement for the construction of sustainable extra-terrestrial colonies. Even with decreasing launch costs, the ultimate goal of establishing colonies must be the usage of resources found at the destination of interest. Typical approaches towards ISRU are often constrained by the mass and energy requirements of transporting processing machineries, such as rovers and massive reactors, and the vast amount of consumables needed. Application of self-reproducing bacteria for the extraction of resources is a promising approach to reduce these pitfalls. In this work, the bacterium Shewanella oneidensis was used to reduce three different types of Lunar and Martian regolith simulants, allowing for the magnetic extraction of iron-rich materials. The combination of bacterial treatment and magnetic extraction resulted in a 5.8-times higher quantity of iron and 43.6% higher iron concentration compared to solely magnetic extraction. The materials were 3D printed into cylinders and the mechanical properties were tested, resulting in a 400% improvement in compressive strength in the bacterially treated samples. This work demonstrates a proof of concept for the on-demand production of construction and replacement parts in space exploration.

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Single-crystal copper films on sapphire have recently been reported upon in relation to graphene growth on these films. In the present paper the kinetics of the formation of single crystal copper films is investigated. We demonstrate the importance of heating the sapphire substrate in 1000 hPa oxygen, followed by a fast cooling prior to depositing the copper film. The importance of this treatment is tentatively explained by the dissolution of oxygen in sapphire and subsequent out-diffusion during recrystallization of the copper film to form a copper-oxide interface layer. Also, the importance of avoiding oxygen incorporation in the sputter deposited film is demonstrated.@en

The present work deals with oxide dispersion strengthened (ODS) Eurofer steel fabricated by powder metallurgy involving mechanical alloying and spark plasma sintering. A heat treatment route including normalising and tempering was applied to the as-produced steel, based on differential scanning calorimetry (DSC) measurement. The microstructure was characterised by scanning electron microscopy (SEM), electron backscattered diffraction (EBSD), electrolytic extraction, X-ray diffraction (XRD) and transmission electron microscopy (TEM). Thermodynamic calculations conducted using Thermo-Calc software were used to determine the precipitation conditions. The results show that the Vickers microhardness of the sample after the designed heat treatment is more uniform compared to the as-produced condition. A dual phase and bimodal microstructure is formed in the as-produced and tempered steels. M₂₃C₆ and M₆C carbides were found in the as-produced sample while only M₂₃C₆ carbides were observed in the tempered sample. The carbides dissolve and reprecipitate during the heat treatment, preferably at the grain boundaries. Nanosized Y₂O₃ particles were found to be homogenously distributed in the steel matrix, which is crucial for the mechanical properties. The dislocation density in the material is decreased significantly after the normalising and tempering treatment. A yield strength model was developed that includes the strengthening contributions of solid solutes, grain size, dislocation density and nanoparticles. Good agreement is obtained between the experimentally measured and theoretically calculated strength of the as-produced and tempered steels.

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The aim of this study was the development of radioactive holmium phosphate microspheres (HoPO₄-MS) with a high holmium content and that are stable in human serum for selective internal radiation therapy (SIRT) of liver cancer. To this end, holmium acetylacetonate microspheres (HoAcAc-MS) were prepared (34.2 ± 1.0 µm in diameter, holmium content of 46.2 ± 0.8 and density of 1.7 g/cm³) via an emulsification and solvent evaporation method. The concentration of HoAcAc in the organic solvent, the temperature of emulsification and the stirring speed were varied for the preparation of the HoAcAc-MS to obtain microspheres with different diameters ranging from 11 to 35 µm. Subsequently, the AcAc ligands of the HoAcAc-MS were replaced by phosphate ions by simply incubating neutron irradiated HoAcAc-MS in a phosphate buffer solution (0.116 M, pH 4.2) to yield radioactive HoPO₄-MS. The obtained microspheres were analyzed using different techniques such as SEM-EDS, ICP-OES and HPLC. The prepared HoPO₄-MS (29.5 ± 1.2 µm in diameter and a density of 3.1 g/cm³) present an even higher holmium content (52 wt%) than the HoAcAc-MS precursor (46 wt%). Finally, the stability of the HoPO₄-MS was tested by incubation in human serum at 37 °C which showed no visible changes of the microspheres morphology and only 0.1% of holmium release was observed during the 2 weeks period of incubation. In conclusion, this study shows that stable radioactive HoPO₄-MS can be prepared with suitable properties to be used for cancer therapy.

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The effect of Cr on the oxidation of Fe–Mn-based steels during isothermal annealing at different dew points was investigated. The Fe–Mn–Cr–(Si) phase diagrams for oxidizing environments were computed to predict the oxide phases. Various Fe–Mn steels with different concentrations of Cr and Si were annealed at 950 °C in a gas mixture of Ar or N₂ with 5 vol% H₂ and dew points ranging from − 45 to 10 °C. The identified oxide species after annealing match with those predicted based on the phase diagrams. (Mn,Fe)O is the only oxide phase formed during annealing of Fe–Mn binary steel alloys. Adding Cr leads to the formation of (Mn,Cr,Fe)₃O₄ spinel. The dissociation oxygen partial pressure of (Mn,Cr,Fe)₃O₄ in the Fe–Mn–Cr steels is lower than that of (Mn,Fe)O. The Si in the steels results in the formation (Mn,Fe)₂SiO₄, and increasing the Si concentration suppresses the formation of (Mn,Cr,Fe)₃O₄ and (Mn,Fe)O during annealing.

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Unencapsulated CIGS solar cells were simultaneously exposed to damp heat and illumination. In-situ monitoring of their electrical parameters demonstrated a rapid decrease of the efficiency, mainly driven by changes in the series and shunt resistances. The non-degraded and degraded solar cells were studied by SIMS and XRD to investigate the material changes leading to efficiency loss. SIMS showed the migration of sodium and potassium, likely leading to changes in the shunt resistance and output voltage. Extensive XRD measurements showed that molybdenum oxide was formed and that the in-plane stress in the ZnO:Al film increased. The stress increase is most likely due to the incorporation of species like hydroxide in the grain boundaries. These phenomena could lead to the observed increased series resistance in the solar cells.

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