6 Materialchemie
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- MALDI-TOF MS (4)
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- Laser-induced periodic surface structures (LIPSS) (3)
- MALDI TOF MS (3)
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A route to a ZrF4 catalyst active in room temperature Friedel–Crafts and dehydrofluorination reactions was developed via a fluorolytic sol–gel route, which was followed by a postfluorination step using a stream of CHClF2. The behaviour of different Zr(IV) precursors in a sol–gel reaction with anhydrous isopropanol/HF solution was investigated. The subsequent post-fluorination step was optimised in its temperature ramp and confirmed the necessity of a fluorination of the generated xerogels to obtain catalytic activity. The process is discussed in the context of the analysis of the materials using Brunauer–Emmett–Teller analysis (BET), powder X-ray diffraction (XRD), infrared spectroscopy (IR), thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). The local structure of the amorphous catalyst was elucidated by extended X-ray absorption fine structure spectroscopy (EXAFS).
A cobalt(III) complex, [Co(L)3](DMF) (1) of Schiff base ligand HL, 2-((E)-(benzylimino)methyl)-4-bromophenol is prepared and single crystal X-ray structural analysis have also been performed. The structures of complex 1 showed hexa-coordinated mononuclear systems that adopt octahedral geometry. The complex has also exhibited the supramolecular networks through non-covalent interactions like H-bonding, C–Hπ stacking. Moreover, the complex 1 is very effective in the catalytic fixation of carbon dioxide in propergyl alcohols to produce α-alkylidene cyclic carbonates. The catalytic production of α-alkylidene cyclic carbonates have been carried out through carboxylative cyclization of propargyl alcohols using CO2 balloon of 1 atm pressure at 80 ◦C. Solvent free condition (green synthesis) made this catalytic protocol eco-friendly towards the environment. Utilizing various substrates of propargyl alcohols moderate to high percentage yield (62–95%) of respective α-alkylidene cyclic carbonates product have been isolated over this catalytic reaction. Besides, the theoretical calculations (DFT) was performed for the prediction of probable mechanism of the catalytic reaction
Corrosion behaviour of AlCrFe2Ni2Mox (x = 0.0, 0.1, 0.15, 0.3 and 0.6) high-entropy alloys was investigated in a 0.1 M H2SO4 solution. Passive films formed upon anodic polarisation, built of Al-based inner layer and (Cr, Fe, Mo)-based outer layer, had good protective properties. In particular, they prevented corrosion of the (Al, Ni)-rich BCC-B2 phase, which was observed under open-circuit conditions. Moderate amounts of Mo, up to x = 0.3, positively affected the passivation ability of AlCrFe2Ni2. Significant changes in microstructure and phase composition of the alloy at higher Mo concentrations (x = 0.6) resulted in deterioration of its corrosion resistance.
A corrosion study is performed on six variations of titanium grade 5 (Ti6Al4V) samples. Samples are prepared in different conditions by variation of preanodization, postanodization, and picosecond-laser (ps-laser) surface treatment, while polished and anodized samples serve as reference. Microcones and nanosized periodic surface features are successfully produced on Ti6Al4V samples. The morphology and topography of the structures are visualized by scanning electron microscopy and white light interference microscopy. Furthermore, the relative electrochemically active surface area (ECSA) is determined for the ps-laser-treated samples. It is determined that the preanodized and laser-treated sample has 3.5 times larger ECSA than a polished sample, and that the laser-treated sample has 4.1 times larger area. Moreover, Tafel analysis is performed to determine the corrosion properties of the samples. It is shown that the corrosion resistance improves for both laser-structured samples after the anodization. To further study the surface of the samples, electrochemical impedance spectroscopy measurements are conducted. The study indicates that the ps-laser-treated and anodized Ti6Al4V is suitable to be used for the fabrication of bone screws and plates due to its improved corrosion resistance as compared to nonanodized samples.
Glycolide was polymerized in bulk with two cyclic catalysts − 2,2-dibutyl-2-stanna-1,3-dithiolane (DSTL) and 2-stanna-1,3-dioxa-4,5,6,7-dibenzepane (SnBiph). The monomer/initiator ratio, temperature (140 – 180 °C) and time (1–––4 days) were varied. The MALDI TOF mass spectra exclusively displayed peaks of cyclic polyglycolide (PGA) and revealed an unusual “saw-tooth pattern” in the mass range below m/z 2 500 suggesting formation of extended ring crystallites. The DSC measurements indicated increasing crystallinity with higher temperature and longer time, and after annealing for 4 d at 160 °C a hitherto unknown and unexpected glass transition was found in the temperature range of 170–185 °C. Linear PGAs prepared by means of metal alkoxides under identical conditions did not show the afore-mentioned features of the cyclic PGAs, neither in the mass spectra nor in the DSC measurements. All PGAs were also characterized by SAXS measurements, which revealed relatively small L-values suggesting formation of thin crystallites in all cases with little influence of the reaction conditions.
The cleaning of aged silk fibers poses a common challenge in the conservation of textiles, since traditional cleaning techniques often yield unsatisfactory results or even harm objects. In this regard, cleaning objects with laser radiation is a promising addition to the range of available methods. Due to it being contactless, even brittle and touch-sensitive objects with disfiguring or harmful soiling could potentially be cleaned and therefore made accessible for research and presentation. Examples of treatment have sometimes shown spectacular results. Still there is some skepticism concerning the safety of this treatment for textile materials, which has been strengthened through previous 532 nm wavelength nanosecond laser cleaning studies on silk fibers. Taking these published results into account, the range of examined laser parameters has been extended in this study, from 532 nm nanosecond laser to 1064 nm nanosecond and even 800 nm femtosecond laser, reevaluating the effect of this treatment on the fibers. The physicochemical processes taking place on the silk fibers when cleaning with lasers are complex and still not fully understood. The aim of this project was therefore to bring more clarification about potential effects of those processes on the condition of silk samples treated with a set of different parameters for wavelength, pulse duration, energy density and number of pulses per spot. It also looks at the influence of the presence of soiling on the results. The analysis of potential effects was then carried out using statistical methods and advanced analytics. Scanning electron microscopy, Fourier-transform infrared spectroscopy and colorimetry technology provided the required insights to better assess the effects. Results show that laser cleaning of silk fibers, like most other conventional cleaning techniques, is not completely without risk, but knowing what the possible effects are helps making decisions on whether the benefits of the technique used justify these risks.
Crystalline materials that exhibit reversible mechanical responses upon exposure to external stimuli have garnered significant attention owing to their potential applications in various fields. Herein, we report a crystal of (2Z,2′Z)-2,2′-(1,4-phenylene)bis(3-(4-bromophenyl)acrylonitrile) (DSBr), which displays simultaneous elasto-plastic behaviour and reversible thermosalient effects. While elasto-plastic behaviour is attributed to underlying packing features, reversible thermosalient expansion is attributed to uniaxial expansion mediated by heat. Exceptional length increase and contraction upon cooling is due to the restorative nature of weak interactions through a cooperative effect. The cooperative movement of molecules is reflected in the unidirectional expansion of the habit plane. Thermosalient reversible expansion–contraction in elasto-plastic crystals have not been discussed in the literature so far. Detailed analysis reported herein provides a comprehensive understanding of the underlying mechanism of flexibility and thermosalient responses. This crystal's unique blend of reversible thermal expansion with flexibility holds substantial promise for applications in flexible thermal actuators.
Reliable measurement of the size of polydisperse, complex-shaped commercial nanopowders is a difficult but necessary task, e.g., for regulatory requirements and toxicity risk assessment. Suitable methods exist for the accurate characterization of the size of non-aggregated, stabilized, spherical and monodisperse nanoparticles. In contrast, industrial nanoscale powders usually require dedicated sample preparation procedures developed for the analysis method of choice. These nano-powders tend to agglomerate and/or aggregate, a behavior which in combination with an innate broad particle size distribution and irregular shape often significantly alters the achievable accuracy of the measured size parameters. The present study systematically tests two commercially available nanoscale powders using different sample preparation methods for correlative analysis by scanning electron microscopy, dynamic light scattering, Brunauer–Emmet–Teller method and differential mobility analysis. One focus was set on the sample preparation by embedding nanoparticles in carbon-based hot-mounting resin. Literature on this topic is scarce and the accuracy of the data extracted from cross sections of these particles is unclearly stated. In this paper systematic simulations on the deviation of the size parameters of well-defined series of nanoparticles with different shapes from the nominal value were carried out and the contributing factors are discussed.
The plastic value chain, central part of modern living, caused environmental pollution and bioaccumulation of plastic nanoparticles (PNPs). Their ubiquitous presence in different environmental and biological compartments has become a serious threat to human health and ecosystems. Frequently used plastic materials such as polypropylene (PP), polystyrene (PS) and polyethylene (PE) have been detected in the form of PNPs in the food chain, soil, water and air, as well as in human feces and blood. In this study, we aimed to provide novel insights in endocrine disrupting properties of PNPs using in vitro estrogen receptor (ER) transactivation assay. The effects of PP-NPs, PE-NPs and PS-NPs and their mixture on T47D-KBluc cell line stably transfected with luciferase as reporter enzyme was evaluated by means of cytotoxicity, cellular uptake and ER activation. Tested dose range for PNPs was 0.001 – 10 mg/L. Both cellular uptake and cytotoxicity for all PNPs was found to be dose-dependent. Only the highest dose of PP-NPs and PE-NPs induced apoptosis and cell death, while PS-NPs were not cytotoxic in tested dose range. For tested concentrations, PP-NPs and PE-NPs showed significant agonistic activity on ER, while PS-NPs cannot be considered ER active. When, applied as mixture, PNP demonstrated additive toxicity effects compared to the effect of each individual PNPs. Additivity was also observed for ER agonistic effect of PNPs mixture according to the benchmark dose-addition modelling approach. This study provides missing science-based evidence on endocrine disrupting effects of PE-NPs, PP-NPs, PS-NPs and their mixtures and highlights the importance of considering unintentional, aggregate and combined exposure to different PNPs in risk management.
A giant Zn segregation transition is revealed using CALPHAD-integrated density-based modeling of segregation into Fe grain boundaries (GBs). The results show that above a threshold of only a few atomic percent Zn in the alloy, a substantial amount of up to 60 at.% Zn can segregate to the GB. We found that the amount of segregation abruptly increases with decreasing temperature, while the Zn content in the alloy required for triggering the segregation transition decreases. Direct evidence of the Zn segregation transition is obtained using high-resolution scanning transmission electron microscopy. Base on the model, we trace the origin of the segregation transition back to the low cohesive energy of Zn and a miscibility gap in Fe-Zn GB, arising from the magnetic ordering effect, which is confirmed by ab-initio calculations. We also show that the massive Zn segregation resulting from the segregation transition greatly assists with liquid wetting and reduces the work of separation along the GB. The current predictions suggest that control over Zn segregation, by both alloy design and optimizing the galvanization and welding processes, may offer preventive strategies against liquid metal embrittlement.