Preparation and Characterization of Multilayer NiTi Coatings by a Thermal Plasma Process.

The deposition of multilayer coating of NiTi is carried out by a thermal plasma spraying process on a stainless steel substrate. The deposition of melted NiTi particles creates an adhesion layer on the substrate with the subsequent formation of multilayer coating with a certain thickness. Six layers of coating are created to achieve a certain thickness in terms of the sprayed sample. This paper aims to investigate multilayer NiTi coatings created through a thermal plasma process. The key variable feed rate was considered, as well as its effect on the microstructure characteristics. The shape memory effect associated with the coating properties was analyzed in detail. The variable feed rate was considered one of the most important parameters in the thermal plasma spraying process due to its ability to control the quality and compactness of the coating structure. The coatings were characterized by examining their microstructure, thermal, chemical, and microhardness. The indent marks were made/realized along the cross-section surface for the analysis of crack propagation resistance and wear properties. The coating's surface did not display segmentation crack lines. Nevertheless, the cross-sectional surfaces showed evidence of crack lines. There were eutectic zones of the interlamellar structure observed in the structure of the coating. The plasma-sprayed samples from thermo-mechanical analysis of the hysteresis curve provide strong confirmation of the shape memory effect.

(Sub)structure Development in Gradually Swaged Electroconductive Bars.

Copper generally exhibits high electrical conductivity but has poor mechanical properties. Although alloying can improve the latter characteristic, it usually leads to a decrease in electrical conductivity. To address this issue, a promising approach is to enhance the performance of copper while maintaining high electrical conductivity through optimized deformation processing, which refines the structure and increases mechanical properties. This paper focuses on assessing the effects of rotary swaging, a form of deformation processing, on microstructures and substructures of electroconductive copper bars. This analysis is complemented by experimental measurements of electrical conductivity. The results demonstrate that gradual swaging, i.e., applying different swaging ratios, influences the structure-forming processes and consequently affects the electrical conductivity. The increased electrical conductivity was found to be associated with the elongation of the grains in the direction of the electron movement.

Defect pairing in Fe-doped SnS van der Waals crystals: a photoemission and scanning tunneling microscopy study.

We investigate the effect of low concentrations of iron on the physical properties of SnS van der Waals crystals grown from the melt. By means of scanning tunneling microscopy (STM) and photoemission spectroscopy we study Fe-induced defects and observe an electron doping effect in the band structure of the native p-type SnS semiconductor. Atomically resolved and bias dependent STM data of characteristic defects are compared to ab initio density functional theory simulations of vacancy (VS and VSn), Fe substitutional (FeSn), and Fe interstitial (Feint) defects. While native SnS is dominated by acceptor-like VSn vacancies, our results show that Fe preferentially occupies donor-like interstitial Feint sites in close proximity to VSn defects along the high-symmetry c-axis of SnS. The formation of such well-defined coupled (VSn, Feint) defect pairs leads to local compensation of the acceptor-like character of VSn, which is in line with a reduction of p-type carrier concentrations observed in our Hall transport measurements.

Fiber Optic Sensor of Ammonia Gas Using Plasmonic Extraordinary Optical Transmission.

While standard surface plasmon resonance (bio) sensing, relaying on propagating surface plasmon polariton sensitivity on homogeneous metal/dielectric boundaries, represents nowadays a routine sensing technique, other alternatives, such as inverse designs with nanostructured plasmonic periodic hole arrays, have been far less studied, especially in the context of gas sensing applications. Here, we present a specific application of such a plasmonic nanostructured array for ammonia gas sensing, based on a combination of fiber optics, extraordinary optical transmission (EOT) effect, and chemo-optical transducer selectively sensitive to ammonia gas. The nanostructured array of holes is drilled in a thin plasmonic gold layer by means of focused ion beam technique. The structure is covered by chemo-optical transducer layer showing selective spectral sensitivity towards gaseous ammonia. Metallic complex of 5-(4'-dialkylamino-phenylimino)-quinoline-8-one dye soaked in polydimethylsiloxane (PDMS) matrix is used in place of the transducer. Spectral transmission of the resulting structure and its changes under exposition to ammonia gas of various concentrations is then interrogated by fiber optics tools. The observed VIS-NIR EOT spectra are juxtaposed to the predictions performed by the rigorous Fourier modal method (FMM), providing useful theoretical feedback to the experimental data, and ammonia gas sensing mechanism of the whole EOT system and its parameters are discussed.

Interfacial Adhesion of Thick NiTi Coating on Substrate Stainless Steel.

Interfacial adhesion of thick NiTi coating on substrate stainless steel is investigated here. NiTi coating was deposited on the substrate by using the thermal plasma spraying method. Deposition of NiTi coating was carried out by using various levels of input power under an Ar atmosphere. Multiple coating layers were deposited on the stainless steel surface for a specific thickness. The cross-section of the plasma-sprayed samples were prepared and characterized by using various techniques. The hardness of the coating layers on the surface and cross-section was examined. The thickness of the coating increased with the increase in power. No cracks were detected in the interface for the NiTi coating deposited at 12 kW power. However minor pores were observed at some regions along the interface at the sample prepared at 9 kW power. A good-quality coating layer was formed at the interface of the substrate. Primary phases of austenite and martensite were confirmed from the EBSD and XRD investigations. There was the presence of intermetallic and oxide phases in the coating layers. A less heat-affected zone of 10 µm of along the interface was confirmed without any diffusion of elements from the substrate to the coating layers. There was homogenous distribution elemental composition of Ni and Ti throughout the coating layers.

Diamond Coating Reduces Nuclear Fuel Rod Corrosion at Accidental Temperatures: The Role of Surface Electrochemistry and Semiconductivity.

If we want to decrease the probability of accidents in nuclear reactors, we must control the surface corrosion of the fuel rods. In this work we used a diamond coating containing <60% diamond and >40% sp2 "soft" carbon phase to protect Zr alloy fuel rods (ZIRLO®) against corrosion in steam at temperatures from 850 °C to 1000 °C. A diamond coating was grown in a pulse microwave plasma chemical vapor deposition apparatus and made a strong barrier against hydrogen uptake into ZIRLO® (ZIRLO) under all tested conditions. The coating also reduced ZIRLO corrosion in hot steam at 850 °C (for 60 min) and at 900 °C (for 30 min). However, the protective ability of the diamond coating decreased after 20 min in 1000 °C hot steam. The main goal of this work was to explain how diamond and sp2 "soft" carbon affect the ZIRLO fuel rod surface electrochemistry and semi conductivity and how these parameters influence the hot steam ZIRLO corrosion process. To achieve this goal, theoretical and experimental methods (scanning electron microscopy, Raman spectroscopy, electrochemical impedance spectroscopy, carrier gas hot extraction, oxidation kinetics, ab initio calculations) were applied. Deep understanding of ZIRLO surface processes and states enable us to reduce accidental temperature corrosion in nuclear reactors.

Enhancing electroanalytical performance of porous boron-doped diamond electrodes by increasing thickness for dopamine detection.

Novel porous boron-doped diamond (BDDporous)-based materials have attracted lots of research interest due to their enhanced detection ability and biocompatibility, favouring them for use in neuroscience. This study reports on morphological, spectral, and electrochemical characterisation of three BDDporous electrodes of different thickness given by a number of deposited layers (2, 3 and 5). These were prepared using microwave plasma-enhanced chemical vapour deposition on SiO2 nanofiber-based scaffolds. Further, the effect of number of layers and poly-l-lysine coating, commonly employed in neuron cultivation experiments, on sensing properties of the neurotransmitter dopamine in a pH 7.4 phosphate buffer media was investigated. The boron doping level of ∼2 × 1021 atoms cm-3 and increased content of non-diamond (sp2) carbon in electrodes with more layers was evaluated by Raman spectroscopy. Cyclic voltammetric experiments revealed reduced working potential windows (from 2.4 V to 2.2 V), higher double-layer capacitance values (from 405 µF cm-2 to 1060 µF cm-2), enhanced rates of electron transfer kinetics and larger effective surface areas (from 5.04 mm2 to 7.72 mm2), when the number of porous layers increases. For dopamine, a significant boost in analytical performance was recognized with increasing number of layers using square-wave voltammetry: the highest sensitivity of 574.1 µA µmol-1 L was achieved on a BDDporous electrode with five layers and dropped to 35.9 µA µmol-1 L when the number of layers decreased to two. Consequently, the lowest detection limit of 0.20 µmol L-1 was obtained on a BDDporous electrode with five layers. Moreover, on porous electrodes, enhanced selectivity for dopamine detection in the presence of ascorbic acid and uric acid was demonstrated. The application of poly-l-lysine coating on porous electrode surface resulted in a decrease in dopamine peak currents by 17% and 60% for modification times of 1 h and 15 h, respectively. Hence, both examined parameters, the number of deposited porous layers and the presence of poly-l-lysine coating, were proved to considerably affect the characteristics and performance of BDDporous electrodes.

Corrosion Properties of Mn-Based Alloys Obtained by Aluminothermic Reduction of Deep-Sea Nodules.

Deep-sea manganese nodules are polymetallic oxidic ores that can be found on a seabed. Aluminothermic reduction is one of the possibilities of manganese nodules processing. This process obtains the polymetallic alloy with a high content of Mn and a varying content of Al, depending on the ratio between aluminum and nodules. The corrosion behaviors of three experimental Mn-based alloys produced by aluminothermic reduction with a content of Mn > 50 wt % were studied. The electrochemical testing in potable water and model seawater was used to explain the corrosion mechanism of Mn-based alloys. The results showed that the corrosion rate of experimental Mn-based alloy decreases with the increase in aluminum content in both potable water and model seawater. It was observed that the uniform corrosion of experimental Mn-based alloys is changed with an increase in aluminum content in alloy to localized corrosion, which was caused by microcells in an environment of model seawater. In contrast, the formation of a semi-protective layer of corrosion products was observed on the surface of Mn-based alloys with a higher content of aluminum in potable water. Moreover, the pitting corrosion of tested Mn-based alloys was observed neither in potable water nor in model seawater.

Towards Rapid Fabrication of Superhydrophobic Surfaces by Multi-Beam Nanostructuring with 40,401 Beams.

Superhydrophobic surfaces attract a lot of attention due to many potential applications including anti-icing, anti-corrosion, self-cleaning or drag-reduction surfaces. Despite a list of attractive applications of superhydrophobic surfaces and demonstrated capability of lasers to produce them, the speed of laser micro and nanostructuring is still low with respect to many industry standards. Up-to-now, most promising multi-beam solutions can improve processing speed a hundred to a thousand times. However, productive and efficient utilization of a new generation of kW-class ultrashort pulsed lasers for precise nanostructuring requires a much higher number of beams. In this work, we introduce a unique combination of high-energy pulsed ultrashort laser system delivering up to 20 mJ at 1030 nm in 1.7 ps and novel Diffractive Laser-Induced Texturing element (DLITe) capable of producing 201 × 201 sub-beams of 5 µm in diameter on a square area of 1 mm2. Simultaneous nanostructuring with 40,401 sub-beams resulted in a matrix of microcraters covered by nanogratings and ripples with periodicity below 470 nm and 720 nm, respectively. The processed area demonstrated hydrophobic to superhydrophobic properties with a maximum contact angle of 153°.

Anti-Reflection Nanostructures on Tempered Glass by Dynamic Beam Shaping.

Reflectivity and surface topography of tempered glass were modified without any thermal damage to the surroundings by utilizing 1.7 ps ultrashort pulsed laser on its fundamental wavelength of 1030 nm. To speed up the fabrication, a dynamic beam shaping unit combined with a galvanometer scanning head was applied to divide the initial laser beam into a matrix of beamlets with adjustable beamlets number and separation distance. By tuning the laser and processing parameters, reflected intensity can be reduced up to 75% while maintaining 90% of transparency thus showing great potential for display functionalization of mobile phones or laptops.

Structure and Properties of Alloys Obtained by Aluminothermic Reduction of Deep-Sea Nodules.

This paper brings an innovative processing route of manganese deep-sea nodules, which results in completely new grades of alloys. Deep-sea nodules were processed by aluminothermic method without the extraction of individual elements, producing complexly alloyed manganese-based "natural alloys". Three levels of the amount of aluminum were used for the aluminothermic reduction, and hence the alloys differ strongly in the amount of aluminum, which has a significant effect on their phase composition. The alloys have very high wear resistance, comparable with tool steel. The disadvantage of low-aluminum alloy is the susceptibility to local thermal cracking during friction, which occurs especially in the case of a dry sliding wear against the static partner with low thermal conductivity.

Comparison of electrochemical performance of various boron-doped diamond electrodes: Dopamine sensing in biomimicking media used for cell cultivation.

Chemically inert and biocompatible boron-doped diamond (BDD) has been successfully used in neuroscience for sensitive neurochemicals sensing and/or as a growth substrate for neurons. In this study, several types of BDD differing in (i) fabrication route, i.e. conventional microwave plasma enhanced chemical vapour deposition (MW-PECVD) reactor vs. MW-PECVD with linear antenna delivery system, (ii) morphology, i.e. planar vs. porous BDD, and (iii) surface treatment, i.e. H-terminated (H-BDDs) vs. O-terminated (O-BDDs), were characterized from a morphological, structural, and electrochemical point of view. Further, planar and porous BDD-based electrodes were tested for sensing of dopamine in common biomimicking environments of pH 7.4, namely phosphate buffer (PB) and HEPES buffered saline (HBS). In HBS, potential windows are narrowed due to electrooxidation of its buffering component (i.e. HEPES), however, dopamine sensing in HBS is possible. H-BDDs (both planar and porous) outperformed O-BDDs as they provided clearer dopamine signals with higher peak currents. As expected, due to its enlarged surface area and increased sp2 content, the highest sensitivity and lowest detection limits of 8 × 10-8 mol L-1 and 6 × 10-8 mol L-1 in PB and HBS media, respectively, were achieved by square-wave voltammetry on porous H-BDD.

Large-Beam Picosecond Interference Patterning of Metallic Substrates.

In this paper, we introduce a method to efficiently use a high-energy pulsed 1.7 ps HiLASE Perla laser system for two beam interference patterning. The newly developed method of large-beam interference patterning permits the production of micro and sub-micron sized features on a treated surface with increased processing throughputs by enlarging the interference area. The limits for beam enlarging are explained and calculated for the used laser source. The formation of a variety of surface micro and nanostructures and their combinations are reported on stainless steel, invar, and tungsten with the maximum fabrication speed of 206 cm2/min. The wettability of selected hierarchical structures combining interference patterns with 2.6 µm periodicity and the nanoscale surface structures on top were analyzed showing superhydrophobic behavior with contact angles of 164°, 156°, and 150° in the case of stainless steel, invar, and tungsten, respectively.

The Influence of Powder Milling on Properties of SPS Compacted FeAl.

The Fe-28 at.% Al alloy was studied in this article. The aim was to describe the influence of gas atomized powder pre-milling before SPS (Spark Plasma Sintering) sintering on the structure and properties of the bulk materials. The initial powder was milled for 0.5, 1, and 8 h. It was proven that 1 h milling leads to the change in size and morphology of the particles, B2→A2 phase transformation, and to the contamination with the material from a milling vessel. Powder materials were compacted by the SPS process at 900, 1000, and 1100 °C. The differences between the bulk materials were tested by LM, SEM, and TEM microscopy, XRD, and neutron diffraction methods. It was proven that, although the structures of initial powder (B2) and milled powder (A2) were different, both provide after-sintering material with the same structure (D03) with similar structural parameters. Higher hardness and improved ductility of the material sintered from the milled powder are likely caused by the change in chemical composition during the milling process.

Grain morphology reconstruction of crystalline materials from Laue three-dimensional neutron diffraction tomography.

The macroscopic properties of advanced engineering and functional materials are highly dependent on their overall grain orientation distribution, size, and morphology. Here we present Laue 3D neutron diffraction tomography providing reconstructions of the grains constituting a coarse-grained polycrystalline material. Reconstructions of the grain morphology of a highly pure Fe cylinder and a Cu cube sample are presented. A total number of 23 and 9 grains from the Fe and Cu samples, respectively, were indexed and reconstructed. Validation of the grain morphological reconstruction is performed by post-mortem EBSD of the Cu specimen.

Cleaving silicene-terminated calcium disilicide in the transmission electron microscope.

Silicene, a monolayer of silicon atoms arranged in a honeycomb lattice, is excellently compatible with the materials used in today's semiconductor manufacturing. In this paper, silicene-terminated CaSi2 is cleaved inside a transmission electron microscope using an in situ manipulator. HRTEM studies on a standard lift-out lamella performed from several crystallographic orientations confirm the cell parameters of a = 3.7 Å and c = 30.60 Å, and allow to determine its exact orientation in the SEM/FIB system. A FIB procedure with corrected tilting and rotating angles has been developed to ensure that the tensile force applied by the manipulator is perpendicular to the (0 0 1) plane, and that the [1 0 0] pole axis could be used for HRTEM imaging. A sharp and flat cleavage interface with a length of more than 1 µm was observed in one in situ experiment. HRTEM images from multiple regions confirm that the flat cleavage follows the (0 0 3) plane of the CaSi2 crystal. The current in situ study demonstrates that a surface sheet with silicene-like atomic arrangement can be mechanically exfoliated from silicide compounds.

Properties Comparison of Ti-Al-Si Alloys Produced by Various Metallurgy Methods.

Melting metallurgy is still the most frequently used and simplest method for the processing of metallic materials. Some of the materials (especially intermetallics) are very difficult to prepare by this method due to the high melting points, poor fluidity, or formation of cracks and pores after casting. This article describes the processing of Ti-Al-Si alloys by arc melting, and shows the microstructure, phase composition, hardness, fracture toughness, and compression tests of these alloys. These results are compared with the same alloys prepared by powder metallurgy by the means of a combination of mechanical alloying and spark plasma sintering. Ti-Al-Si alloys processed by melting metallurgy are characterized by a very coarse structure with central porosity. The phase composition is formed by titanium aluminides and titanium silicides, which are full of cracks. Ti-Al-Si alloys processed by the powder metallurgy route have a relatively homogeneous fine-grained structure with higher hardness. However, these alloys are very brittle. On the other hand, the fracture toughness of arc-melted samples is immeasurable using Palmqvist's method because the crack is stopped by a large area of titanium aluminide matrix.

Effect of Initial Powders on Properties of FeAlSi Intermetallics.

FeAlSi intermetallics are materials with promising high-temperature mechanical properties and oxidation resistance. Nevertheless, their production by standard metallurgical processes is complicated. In this study, preparation of powders by mechanical alloying and properties of the samples compacted by spark plasma sintering was studied. Various initial feedstock materials were mixed to prepare the material with the same chemical composition. Time of mechanical alloying leading to complete homogenization of powders was estimated based on the microstructure observations, results of XRD and indentation tests. Microstructure, phase composition, hardness and fracture toughness of sintered samples was studied and compared with the properties of powders before the sintering process. It was found that independently of initial feedstock powder, the resulting phase composition was the same (Fe3Si + FeSi). The combination of hard initial powders required the longest milling time, but it led to the highest values of fracture toughness.

Structure and Properties of Fe-Al-Si Alloy Prepared by Mechanical Alloying.

Fe-Al-Si alloys have been previously reported as an interesting alternative to common high-temperature materials. This work aimed to improve the properties of FeAl20Si20 alloy (in wt.%) by the application of powder metallurgy process consisting of ultrahigh-energy mechanical alloying and spark plasma sintering. The material consisted of Fe3Si, FeSi, and Fe3Al2Si3 phases. It was found that the alloy exhibits an anomalous behaviour of yield strength and ultimate compressive strength around 500 °C, reaching approximately 1100 and 1500 MPa, respectively. The results also demonstrated exceptional wear resistance, oxidation resistance, and corrosion resistance in water-based electrolytes. The tested manufacturing process enabled the fracture toughness to be increased ca. 10 times compared to the cast alloy of the same composition. Due to its unique properties, the material could be applicable in the automotive industry for the manufacture of exhaust valves, for wear parts, and probably as a material for selected aggressive chemical environments.

Nitrous oxide as an effective AFM tip functionalization: a comparative study.

We investigate the possibility of functionalizing Au tips by N2O molecules deposited on a Au(111) surface and their further use for imaging with submolecular resolution. First, we characterize the adsorption of the N2O species on Au(111) by means of atomic force microscopy with CO-functionalized tips and density functional theory (DFT) simulations. Subsequently we devise a method of attaching a single N2O to a metal tip apex and benchmark its high-resolution imaging and spectroscopic capabilities using FePc molecules. Our results demonstrate the feasibility of high-resolution imaging. However, we find an inherent asymmetry of the N2O probe-particle adsorption on the tip apex, in contrast to a CO tip reference. These findings are consistent with DFT calculations of the N2O- and CO tip apexes.