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Eingeladener Vortrag
- nein (1)
The mechanism of action of zirconium permanent modifiers on graphite surfaces was investigated in order to understand its influence on the analytical signal in atomic and molecular absorption spectrometry (AAS/MAS). For this, the molecule formation of CaF was studied, which is used for the indirect analytical determination of fluorine in high-resolution continuum source graphite furnace molecular absorption spectrometry (HR-CS-GFMAS). The kinetics of this reaction was established by monitoring its molecular spectrum at different atomisation temperatures. An Arrhenius plot showed a pseudo-first order reaction with respect to fluorine (n = 1). An intermediate state was isolated, and its structure was elucidated by spectroscopic methods: scanning electron microscopy with energy dispersive X-ray spectroscopy (SEMEDX), X-ray photoelectron spectroscopy (XPS), X-ray absorption spectroscopy (XANES and EXAFS), and Raman microspectroscopy. We propose here a mechanism, where ZrO2 acts as a heterogeneous catalyst: after a pyrolytic step, an intermediate state of ZrO(OCaF) is activated, and at higher temperatures, CaF(g) is released from the zirconium-coated graphite surface. No evidence of the formation of zirconium carbide was found. Consequently, as the CaF formation is catalysed by a heterogeneous catalyst, surface modifications with ZrO2 nanoparticles and ZrO xerogels were investigated in order to increase the surface area. Their influence was evaluated in the molecule formation of CaF, CaCl, CaBr, and CaI. Graphite furnace modification with zirconium oxide nanoparticles proves to be the best choice for fluorine analysis with a signal enhancement of more than eleven times with respect a non-coated graphite furnace. However, the influence of zirconium modifications in the analytical signals of Cl, and I is lower than the F signals or even negative in case of the Br. Understanding zirconium modifiers as heterogeneous catalysts offers a new perspective to AAS and MAS, and reveals the potential of surface analytical methods for development of improved permanent modifiers and graphite furnace coatings.
Our ability to produce and transform engineered materials over the past 150 years is responsible for our high standards of living today, especially in the developed economies. Yet, we must carefully think of the effects our addiction to creating and using materials at this fast rate will have on the future generations. The way we currently make and use materials detrimentally affects the planet Earth, creating many severe environmental problems. It affects the next generations by putting in danger the future of economy, energy, and climate. We are at the point where something must drastically change, and it must change NOW. We must create more sustainable materials alternatives using natural raw materials and inspiration from Nature while making sure not to deplete important resources, i.e. in competition with the food chain supply. We must use less materials, eliminate the use of toxic materials and create a circular materials economy where reuse and recycle are priorities. We must develop sustainable methods for materials recycling and encourage design for disassembly. We must look across the whole materials life cycle from raw resources till end of life and apply thorough life cycle assessments based on reliable and relevant data to quantify sustainability.
Substitution of tungsten carbide by niobium carbide as cutting materials and for wear protection
(2016)
Several phases, like Nb₄ C₃ , Nb₆C₅ and other short and long range ordered phases occur in the region of homogeneity of NbCₓ (0.75 ≤ x ≤ 1.0) in the binary phase diagram. Properties, like micro-hardness, hot hardness, sliding wear resistance, elastic modulus and toughness can be tailored by the C/Nb ratio, the addition of secondary carbides and the type of binder. Supporting results from different grades with varying C/Nb ratio or binder types were illuminated. Thus, the NbC system offers to producers a wider process window, than WC. The impact of these tailored properties on sliding wear and cutting performance was illuminated by tribological and machining results.
Niobium is today largely available. NbC can be synthesized by carbothermal conversion of Nb₂O₅ or be metallurgically grown and leached out, provides comparably low friction in many relevant tribo-contacts and displays low wear. NbC and Nb₂O₅ have so far no REACH classification related to human toxicology and are not listed as substances of very high concern contrary to WO₃ and Co₃ O₄ .
Niobium is today largely available. The initial NbC grade was substoichiometric, SPS sintered and cobalt bonded (NbC0.88-12Co SPS). The NiMo-bonded stoichiometric NbC1.0 grades enable the subtituion of cobalt by nickel, SPS by conventional sintering and NbC0.88 by NbC1.0 in view of functional properties. Nickel bonded NbC grades have improved toughnesses versus cobalt bonded NbC grades, but lose hardness. NiMo and NiMo2C bonded NbC1.0 grades compensated the loss in hardness while keeping the toughness.
A fast and simple method for sulfur quantification in crude oils was developed by using high-resolution continuum source graphite furnace molecular absorption spectrometry (HR-CS-GFMAS). For this, heavy crude oil samples were prepared as microemulsion (shake) and injected into a graphite furnace (shut). Finally, the concentration of sulfur was determined by monitoring in situ the transient molecular spectrum of GeS at wavelength 295.205nm after adding a germanium solution as molecular forming agent (and go). Zirconium dioxide in the form of nanoparticles (45–55nm) was employed as a permanent modifier of the graphite furnace. Calibration was done with an aqueous solution standard of ammonium sulfate, and a characteristic mass (m0) of 7.5ng was achieved. The effectiveness of the proposed method was evaluated analizing, ten heavy crude oil samples with Sulfur amounts ranging between 0.3 and 4.5% as well as two NIST standard reference materials, 1620c and 1622e. Results were compared with those obtained by routine ICP-OES analysis, and no statistical relevant differences were found.
Most studies about the interaction of nanoparticles (NPs) with cells have focused on how the physicochemical properties of NPs will influence their uptake by cells. However, much less is known about their potential excretion from cells. However, to control and manipulate the number of NPs in a cell, both cellular uptake and excretion must be studied quantitatively. Monitoring the intracellular and extracellular amount of NPs over time (after residual noninternalized NPs have been removed) enables one to disentangle the influences of cell proliferation and exocytosis, the major pathways for the reduction of NPs per cell. Proliferation depends on the type of cells, while exocytosis depends in addition on properties of the NPs, such as their size. Examples are given herein on the role of these two different processes for different cells and NPs.
Research and development of WC grades is 90 years ahead of niobium carbide-based hard materials, which showed already as light-weight and unexplored material a very high potential for many technical applications, especially for wear protection and machining. NbC evoluted recently from lab scale to pilot scale, especially in areas where established WC-based materials are causing economic, environmental or technical concerns. Benchmark trials of NbC-based hard metals indicated already a favorable performance in machining of steel components.