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Nickel-Catalyzed Carbonylative Synthesis of Functionalized Alkyl Iodides

2018, Peng, J.-B., Wu, F.-P., Xu, C., Qi, X., Ying, J., Wu, X.-F.

Chemistry; Catalysis; Organic Synthesis © 2018 The Author(s)Functionalized alkyl iodides are important compounds in organic chemistry and biology. In this communication, we developed an interesting nickel-catalyzed carbonylative synthesis of functionalized alkyl iodides from aryl iodides and ethers. With Mo(CO)6 as the solid CO source, both cyclic and acyclic ethers were activated, which is also a challenging topic in organic synthesis. Functionalized alkyl iodides were prepared in moderate to excellent yields with outstanding functional group tolerance. Besides the high value of the obtained products, all the atoms from the starting materials were incorporated in the final products and the reaction had high atom efficiency as well.

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Mechanical performance and corrosion behaviour of Zr-based bulk metallic glass produced by selective laser melting

2020, Deng, L., Gebert, A., Zhang, L., Chen, H.Y., Gu, D.D., Kühn, U., Zimmermann, M., Kosiba, K., Pauly, S.

Nearly fully dense, glassy Zr52.5Cu17.9Ni14.6Al10Ti5 bulk specimens were fabricated by selective laser melting (SLM) and their behaviour during compressive loading, during wear testing and in a corrosive medium was investigated. Their performance was compared with as-cast material of the same composition. The additively manufactured samples exhibit a yield strength around 1700 MPa combined with a plastic strain of about 0.5% after yielding despite the residual porosity of 1.3%, which is distributed uniformly in the samples. The propagation of shear bands in the bulk metallic glass prepared by SLM was studied. The specific wear rate and the worn surfaces demonstrated that similar wear mechanisms are active in the SLM and the as-cast samples. Hence, manufacturing the glass in layers does not adversely affect the wear properties. The same holds for the corrosion tests, which were carried out in 0.01 M Na2SO4 and 0.1 M NaCl electrolyte. The anodic polarization curves of SLM samples and as-cast samples revealed a similar corrosion behaviour. However, the SLM samples have a slightly reduced susceptibility to pitting corrosion and exhibit an improved surface healing ability, which might be attributed to an improved homogeneity of the additively manufactured glass.

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Screening of microbial communities associated with endive lettuce during postharvest processing on industrial scale

2018, Fröhling, A., Rademacher, A., Rumpold, B., Klocke, M., Schlüter, O.

In this study, the composition of the microbial community on endive lettuce (Cichorium endivia) was evaluated during different postharvest processing steps. Microbial community structure was characterized by culture-dependent and culture-independent methods. Endive lettuce was sampled exemplarily at four different stages of processing (raw material, cut endive lettuce, washed endive lettuce, and spin-dried (ready to pack) endive lettuce) and analysed by plate count analysis using non-selective and selective agar plates with subsequent identification of bacteria colonies by matrix-assisted laser desorption/ionization time-of light mass spectrometry (MALDI-TOF MS). Additionally, terminal-restriction fragment length polymorphism (TRFLP) analysis and 16S rRNA gene nucleotide sequence analysis were conducted. The results revealed structural differences in the lettuce microbiomes during the different processing steps. The most predominant bacteria on endive lettuce were detected by almost all methods. Bacterial species belonging to the families Pseudomonadaceae, Enterobacteriaceae, Xanthomonadaceae, and Moraxellaceae were detected in most of the examined samples including some unexpected potentially human pathogenic bacteria, especially those with the potential to build resistance to antibiotics (e.g., Stenotrophomonas maltophilia (0.9 % in cut sample, 0.4 % in spin-dried sample), Acinetobacter sp. (0.6 % in raw material, 0.9 % in cut sample, 0.9 % in washed sample, 0.4 % in spin-dried sample), Morganella morganii (0.2 % in cut sample, 3 % in washed sample)) revealing the potential health risk for consumers. However, more seldom occurring bacterial species were detected in varying range by the different methods. In conclusion, the applied methods allow the determination of the microbiome's structure and its dynamic changes during postharvest processing in detail. Such a combined approach enables the implementation of tailored control strategies including hygienic design, innovative decontamination techniques, and appropriate storage conditions for improved product safety.

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Round robin comparison on quantitative nanometer scale magnetic field measurements by magnetic force microscopy

2020, Hu, X., Dai, G., Sievers, S., Fernández-Scarioni, A., Corte-León, H., Puttock, R., Barton, C., Kazakova, O., Ulvr, M., Klapetek, P., Havlíček, M., Nečas, D., Tang, Y., Neu, V., Schumacher, H.W.

Magnetic force microscopy (MFM) can be considered as a standard tool for nano-scale investigation of magnetic domain structures by probing the local stray magnetic field landscape of the measured sample. However, this generally provides only qualitative data. To quantify the stray magnetic fields, the MFM system must be calibrated. To that end, a transfer function (TF) approach was proposed, that, unlike point probe models, fully considers the finite extent of the MFM tip. However, albeit being comprehensive, the TF approach is not yet well established, mainly due to the ambiguities concerning the input parameters and the measurement procedure. Additionally, the calibration process represents an ill-posed problem which requires a regularization that introduces further parameters. In this paper we propose a guideline for quantitative stray field measurements by standard MFM tools in ambient conditions. All steps of the measurement and calibration procedure are detailed, including reference sample and sample under test (SUT) measurements and the data analysis. The suitability of the reference sample used in the present work for calibrated measurements on a sub-micron scale is discussed. A specific regularization approach based on a Pseudo-Wiener Filter is applied and combined with criteria for the numerical determination of a unique regularization parameter. To demonstrate the robustness of such a defined approach, a round robin comparison of magnetic field measurements was conducted by four laboratories. The guideline, the reference sample and the results of the round robin are discussed.

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Electrical and magnetic properties of NiTiO3 nanoparticles synthesized by the sol-gel synthesis method and microwave sintering

2019, Pavithra, C., Madhuri, W.

In this paper, we focused on microwave sintered NiTiO3 nanoparticles synthesized via sol-gel method. The crystal structure was determined by the X-ray diffraction. Vibrational bands related to Ni-O and Ti-O bands were confirmed using the Fourier transform infrared spectrum. These NiTiO3 ceramics obeyed semiconductor behavior of Arrhenius type. The activation energy was found to be 0.04 μeV. The M-H curve exhibited superparamagnetic behavior at room temperature.

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Investigation of constitutive relationship and dynamic recrystallization behavior of 22MnB5 during hot deformation

2019, Xu, Y., Birnbaum, P., Pilz, S., Zhuang, X., Zhao, Z., Kräusel, V.

In order to analyze the softening behavior of 22MnB5 steel and further predict the constitutive relationship during hot sheet metal forming, a series of isothermal hot compression tests were conducted at the temperature range of 800–950 °C and strain rate range of 0.01–0.8 s−1 on BAEHR 805 A/D thermo-mechanical simulator system. Based on the friction corrected flow curves, the characteristic strain and stress of dynamic recrystallization (DRX) were derived from the Kocks-Mecking plots and expressed as a function of Zener-Hollomon parameter. Moreover, a physical constitutive model considering work hardening (WH), dynamic recovery (DRV) and DRX as well as corresponding JMAK-type DRX kinetics were developed. The results showed that the established physical equations can accurately predict the flow behavior with a correlation coefficient of 0.997 and average absolute relative error of 3.89%. Optical observation of the microstructure after hot compression revealed that the established DRX kinetics accurately reflects the reality, and then a Zener-Hollomon parameter dependent dynamic recrystallized grain size model was developed. Furthermore, EBSD analysis was carried out to study the effect of deformation conditions on martensite morphology and the results show that a lower temperature and higher strain rate lead to a finer martensite packet while the martensite block width becomes larger under the higher strain rate.

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Rejuvenation through plastic deformation of a La-based metallic glass measured by fast-scanning calorimetry

2020, Meylan, C.M., Orava, J., Greer, A.L.

We explore the glassy states achievable after a metallic glass is formed on liquid quenching. Samples of La55Al25Ni20 (at.%) metallic glass (rod and ribbon) are studied. The extent of structural relaxation at room temperature is characterized for this low-glass-transition temperature glass. Plastic deformation (uniaxial compression) rejuvenates the glass to states of higher enthalpy characteristic of glass formation at high cooling rate. Deformation increases the heterogeneity of the glass, widening the spectrum of relaxation times. The extent of rejuvenation in samples of low aspect ratio is compared with that under conditions of high constraint in notched samples. The deformation-induced rejuvenation is particularly susceptible to reduction on subsequent ageing. Fast-scanning calorimetry is useful in characterizing the dynamics of structural relaxation. The shadow glass transition is more evident on fast heating, and is observed in this glass for the first time. A new excess exothermic effect is observed before the glass transition.

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Phase formation of a biocompatible Ti-based alloy under kinetic constraints studied via in-situ high-energy X-ray diffraction

2020, Kosiba, K., Rothkirch, A., Han, J., Deng, L., Escher, B., Wang, G., Kühn, U., Bednarcik, J.

The biocompatible Ti40Cu34Pd14Zr10Sn2 bulk metallic glass was rapidly heated, also known as flash-annealed, at varying heating rates up to 1579 K/s. Thereby, the phase formation was characterized via advanced in-situ high-energy X-ray diffraction. It has been found that the evolving kinetic constraints can be used as a tool to deliberately alter the crystalline phase formation. This novel processing route permits to select phases to crystallize to a predefined fraction and, thus, to potentially design the microstructure of materials according to a specified property-profile. Consequently, flash-annealing poses a unique synthesis route to design materials with, for instance, good biomechanical compatibility.

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Microstructure and elastic deformation behavior of β-type Ti-29Nb-13Ta-4.6Zr with promising mechanical properties for stent applications

2019, Plaine, A.H., Silva, M.R.D., Bolfarini, C.

In this paper, an attempt was made to combine theoretical composition design and thermo-mechanical treatments to produce a metastable β-type titanium alloy with mechanical compatibility for self-expandable stent applications. Metastable β-type Ti-29Nb-13Ta-4.6â»Zr (wt.%) thin-wires with an elastic modulus of 46â»GPa and a yield strength of 920â»MPa were successfully fabricated by cold rolling and low temperature aging. This combination of high yield strength and comparatively low elastic modulus resulted in enhanced elastic recoverable strain of 1.9%, which is much higher than that of the conventional metallic stent materials. The microstructure responsible for the much sought-after mechanical properties was observed to be mainly consisted of a homogeneous distribution of nanometer-sized α-precipitates in a β-phase matrix obtained via a spinodal decomposition of the pre-existed α″-martensite phase through α″â»→â»α″ leanâ»+â»α″ richâ»→â»αâ»+â»β. The α-precipitates increase the strength of the material by hindering the motion of dislocations (spinodal hardening) while the β-matrix with relatively low content of β-stabilizers gives rise to the observed low elastic modulus. More broadly, these findings could be extended to developing advanced metastable β-type titanium alloys for implant and other engineering applications.

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Predicting the dominating factors during heat transfer in magnetocaloric composite wires

2020, Krautz, M., Beyer, L., Funk, A., Waske, A., Weise, B., Freudenberger, J., Gottschall, T.

Magnetocaloric composite wires have been studied by pulsed-field measurements up to μ0ΔH = 10 T with a typical rise time of 13 ms in order to evaluate the evolution of the adiabatic temperature change of the core, ΔTad, and to determine the effective temperature change at the surrounding steel jacket, ΔTeff, during the field pulse. An inverse thermal hysteresis is observed for ΔTad due to the delayed thermal transfer. By numerical simulations of application-relevant sinusoidal magnetic field profiles, it can be stated that for field-frequencies of up to two field cycles per second heat can be efficiently transferred from the core to the outside of the jacket. In addition, intense numerical simulations of the temperature change of the core and jacket were performed by varying different parameters, such as frequency, heat capacity, thermal conductivity and interface resistance in order to shed light on their impact on ΔTeff at the outside of the jacket in comparison to ΔTad provided by the core.