Long-term behaviour of Nb and Cr nitrides nanostructured coatings under steam at 650°C. Mechanistic considerations.

There is an increasing demand for steam power plants to operate in super-critical conditions i.e. temperatures in excess of 600°C. Under these conditions creep resistant ferritic steels oxidize and therefore require coatings in order to last. Physical vapor deposition and especially High Power Impulse Magnetron Sputtering deposited CrN/NbN nano-scale multilayer coatings with a 2.45 Cr/Nb ratio showed excellent performance when exposed to 650 °C in pure steam environment up to 2,000 h. However the role of Nb in offering protection is unclear. In order to study the long term behaviour of this type of coatings as well as to determine the influence of Nb on their oxidation resistance, a CrN/NbN coating with a 1.16 Cr/Nb ratio was studied for 12,650 h. The coating is hard, well adhered and resistant to environmental corrosion, which are properties required in particular for coatings to be applied on turbine blades. The coating also protects P92 from steam oxidation at 650º C, however coating growth defects influence significantly the oxidation resistance. The long-time exposure allowed to study the protection/ degradation mechanisms provided by this type of ceramic coatings. It was found that oxide nodules grow due to the presence of coating defect originated from substrate defects. Moreover, the higher Nb CrN/NbN coating slowly oxidizes, consuming the coating to a large extent after 12,650 h. As a result, protective oxides containing Cr and Nb are developed, remaining well attached to the substrate for at least the test duration, and preventing further substrate oxidation by steam. Interestingly, thin voids present in the as deposited coating self-heal by forming Cr rich oxides, which block steam to reach the substrate

Vacuum tribological behaviour of self lubricant quasicrystalline composite coatings

High temperature resistant self-lubricant coatings are needed in space vehicles for components that operate at high temperatures and/or under vacuum. Thick composite lubricant coatings containing quasicrystalline alloys (QC) as the hard phase for wear resistance, have been deposited by thermal spray. The coatings also comprise lubricating materials (silver and BaF2-CaF2 eutectic) and NiCr as the tough component. This paper describes the vacuum tribological properties of TH103, a coating belonging to this family, with excellent microstructural quality. The coating was deposited by HVOF and tested under vacuum on a pin-on-disc tribometer. Different loads, linear speeds and pin materials were studied. The pin scars and disc wear tracks were characterized by EDS-SEM. A minimum mean steady friction coefficient of 0.32 was obtained employing a X-750 Ni superalloy pin in vacuum conditions under 10 N load and 15 cm/s linear speed, showing moderate wear of the disc and low wear of the pin

Vacuum Tribological Behaviour of Self-Lubricating Quasicrystalline Composite Coatings

High-temperature-resistant self-lubricating coatings are needed in space vehicles for components that operate at high temperatures and/or under vacuum. Thick composite lubricant coatings containing quasicrystalline alloys as the hard phase for wear resistance can be deposited by a thermal spray technique. The coatings also contain lubricating materials (silver and BaF2CaF2 eutectic) and NiCr as the tough component. This paper describes the vacuum tribological properties of TH103, a coating of this type, with a very good microstructural quality. The coating was deposited by high-velocity oxygen fuel spraying and tested under vacuum using a pin-on-disc tribometer. Different loads, linear speeds, and pin materials were studied. The pin scars and disc wear tracks were characterised using a combination of scanning electron microscopy and energy dispersive spectrometry. A minimum mean steady friction coefficient of 0.32 was obtained when employing an X750 Ni superalloy pin in vacuum conditions under 10 N load and 15 cm/s linear speed, showing moderate wear of the disc and low wear of the pi

Revealing the CO Coverage Driven C-C Coupling Mechanism for Electrochemical CO₂ Reduction on Cu₂O Nanocubes via Operando Raman Spectroscopy

Electrochemical reduction of carbon dioxide (CO2RR) is an attractive route to close the carbon cycle and potentially turn CO2 into valuable chemicals and fuels. However, the highly selective generation of multicarbon products remains a challenge, suffering from poor mechanistic understanding. Herein, we used operando Raman spectroscopy to track the potential-dependent reduction of Cu2O nanocubes and the surface coverage of reaction intermediates. In particular, we discovered that the potential-dependent intensity ratio of the Cu–CO stretching band to the CO rotation band follows a volcano trend similar to the CO2RR Faradaic efficiency for multicarbon products. By combining operando spectroscopic insights with Density Functional Theory, we proved that this ratio is determined by the CO coverage and that a direct correlation exists between the potential-dependent CO coverage, the preferred C–C coupling configuration, and the selectivity to C2+ products. Thus, operando Raman spectroscopy can serve as an effective method to quantify the coverage of surface intermediates during an electrocatalytic reaction

Absence of CO2 electroreduction on copper, gold and silver electrodes without metal cations in solution

The electrocatalytic reduction of carbon dioxide is widely studied for the sustainable production of fuels and chemicals. Metal ions in the electrolyte influence the reaction performance, although their main role is under discussion. Here we studied CO2 reduction on gold electrodes through cyclic voltammetry and showed that, without a metal cation, the reaction does not take place in a pure 1 mM H2SO4 electrolyte. We further investigated the CO2 reduction with and without metal cations in solution using scanning electrochemical microscopy in the surface-generation tip-collection mode with a platinum ultramicroelectrode as a CO and H2 sensor. CO is only produced on gold, silver or copper if a metal cation is added to the electrolyte. Density functional theory simulations confirmed that partially desolvated metal cations stabilize the CO2– intermediate via a short-range electrostatic interaction, which enables its reduction. Overall, our results redefine the reaction mechanism and provide definitive evidence that positively charged species from the electrolyte are key to stabilize the crucial reaction intermediate.Horizon 2020(H2020)722614-ELCORELCatalysis and Surface Chemistr

Iterative determination of clinical beam phase space from dose measurements

Monte Carlo (MC) method can accurately compute the dose produced by medical linear accelerators. However, these calculations require a reliable description of the electron and/or photon beams delivering the dose, the phase space (PHSP), which is not usually available. A method to derive a phase space model from reference measurements that does not heavily rely on a detailed model of the accelerator head is presented. The iterative optimization process extracts the characteristics of the particle beams which best explains the reference dose measurements in water and air, given a set of constrain

The rates of adult neurogenesis and oligodendrogenesis are linked to cell cycle regulation through p27-dependent gene repression of SOX2

Cell differentiation involves profound changes in global gene expression that often has to occur in coordination with cell cycle exit. Because cyclin-dependent kinase inhibitor p27 reportedly regulates proliferation of neural progenitor cells in the subependymal neurogenic niche of the adult mouse brain, but can also have effects on gene expression, we decided to molecularly analyze its role in adult neurogenesis and oligodendrogenesis. At the cell level, we show that p27 restricts residual cyclin-dependent kinase activity after mitogen withdrawal to antagonize cycling, but it is not essential for cell cycle exit. By integrating genome-wide gene expression and chromatin accessibility data, we find that p27 is coincidentally necessary to repress many genes involved in the transit from multipotentiality to differentiation, including those coding for neural progenitor transcription factors SOX2, OLIG2 and ASCL1. Our data reveal both a direct association of p27 with regulatory sequences in the three genes and an additional hierarchical relationship where p27 repression of Sox2 leads to reduced levels of its downstream targets Olig2 and Ascl1. In vivo, p27 is also required for the regulation of the proper level of SOX2 necessary for neuroblasts and oligodendroglial progenitor cells to timely exit cell cycle in a lineage-dependent manne

Long-term behaviour of Nb and Cr nitrides nanostructured coatings under steam at 650°C. Mechanistic considerations.

There is an increasing demand for steam power plants to operate in super-critical conditions i.e. temperatures in excess of 600°C. Under these conditions creep resistant ferritic steels oxidize and therefore require coatings in order to last. Physical vapor deposition and especially High Power Impulse Magnetron Sputtering deposited CrN/NbN nano-scale multilayer coatings with a 2.45 Cr/Nb ratio showed excellent performance when exposed to 650 °C in pure steam environment up to 2,000 h. However the role of Nb in offering protection is unclear. In order to study the long term behaviour of this type of coatings as well as to determine the influence of Nb on their oxidation resistance, a CrN/NbN coating with a 1.16 Cr/Nb ratio was studied for 12,650 h. The coating is hard, well adhered and resistant to environmental corrosion, which are properties required in particular for coatings to be applied on turbine blades. The coating also protects P92 from steam oxidation at 650º C, however coating growth defects influence significantly the oxidation resistance. The long-time exposure allowed to study the protection/ degradation mechanisms provided by this type of ceramic coatings. It was found that oxide nodules grow due to the presence of coating defect originated from substrate defects. Moreover, the higher Nb CrN/NbN coating slowly oxidizes, consuming the coating to a large extent after 12,650 h. As a result, protective oxides containing Cr and Nb are developed, remaining well attached to the substrate for at least the test duration, and preventing further substrate oxidation by steam. Interestingly, thin voids present in the as deposited coating self-heal by forming Cr rich oxides, which block steam to reach the substrate

Performance of HIPIMS deposited CrN/NbN nanostructured coatings exposed to 650°C in pure steam environment

In the current work, 4 µm thick CrN/NbN coating utilising nanoscale multilayer structure with bi-layer thickness of ∆ = 2.9 nm has been used to protect 9 wt. % Cr steels such as P92 widely used in steam power plants. The uniquely layered coatings have a combination of nitrides of chromium and niobium which are not only resistant to aqueous corrosion and corrosion-erosion and have excellent tribological properties, but also have oxidation resistance in dry air up to a temperature of 850°C. The novel High Power Impulse Magnetron Sputtering (HIPIMS) deposition technology has been used to deposit CrN/NbN with enhanced adhesion (critical load of scratch adhesion LC2 = 80 N) and a very dense microstructure as demonstrated by Transmission Electron Microscopy (TEM) imaging. These superior coating properties are achieved due to the unique high metal ion content (up to 90%) in the HIPIMS plasma, which allows particle acceleration and trajectory control by external electrical and magnetic fields thus delivering highly energetic material flux on the condensing surface. P92 bare and coated samples were oxidised at 650 °C in 100% steam atmosphere up to 2000 h, in order to simulate the future operation conditions of steam turbines employed in power plants. The oxidation kinetics was evaluated by mass gain measurements. Under these conditions CrN/NbN provided reliable protection of the P92 steel. The paper also discusses the effect of growth defects and high temperature crack formation analysed by Scanning Electron Microscopy and Focused Ion Beam-Scanning Electron Microscopy techniques (SEM and FIB-SEM, respectively) on the high temperature corrosion resistance in pure steam atmosphere thus revealing the coatings potential failure mechanisms. Keywords : Thin films, Nitrides, Nano structures, Sputterin