Nanocrystalline hard coatings within the quasi-binary system TiN–TiB2

Ti–B–N films with a gradient in the chemical composition were deposited onto austenitic stainless steel sheets by means of unbalanced DC magnetron co-sputtering using a segmented TiN\Tib₂ target. Film microstructure was characterized by means of electron-probe microanalysis (EPMA), transmission electron microscopy (TEM), electron energy-loss spectroscopy (EELS), and X-ray diffraction (XRD) as well as glancing angle X-ray diffraction (GAXRD). The mechanical properties of the coatings were measured using a depth-sensing nanoindenter. The composition of the films was found to lie close to the quasi-binary section TiN–TiB₂ within the ternary system Ti–B–N. The grain size determined from TEM investigations range between 3 and 5 nm. Coatings consisted of a nanocrystalline fcc TiN phase (with boron atoms and oxygen impurities dissolved), and TiB₂, TiB and B₂O₃. Microstructure as well as chemical composition of the films were not influenced significantly by the deposition parameters used in this investigation. Contrary, the mechanical properties were strongly influenced varying the ion bombardment. Hardness values exceeding 50 GPa and elastic moduli close to 500 GPa were obtained.     

Optical properties and corrosion behaviour of sputtered Zr-B and Zr-B-N coatings

In this paper, we present results on the structure, optical properties and corrosion behaviour of Zr-B and Zr-B-N coatings employing non-reactive and reactive d.c. magnetron sputter deposition. The addition of nitrogen reduced the grain size—coatings deposited at nitrogen flow rates f(N₂) of less than approximately 14 sccm (standard cm³ min^-1) were extremely fine grained, while nitrogen flow rates of more than 14sccm led to fracture-amorphous coatings with a very smooth surface. The hardness and abrasion resistance decreased with the increase in nitrogen content. Pure Zr-B coatings are silver-greyish with metallic brilliance but nitrogen changes the colour from dark grey or black at low contents to interference colours in the amorphous state. Ellipsometric measurements of the refractive index n and adsorption coefficient k supported the results derived from electron microscopy, colour measurements and mechanical testing. The transition point between the fine-grained and fracture-amorphous structure lies in the range of f(N₂) around 10 sccm. The black coatings deposited with such nitrogen levels showed good corrosion and abrasion resistance combined with a satisfying hardness. In some cases, increasing the nitrogencontent improved the corrosion resistance. In potentio- dynamic experiments, more positive free corrosion and pitting potentials were demonstrated. However, in salt spray testing and immersion testing using an artificial sweat solution, no beneficial effect of high nitrogen additions was noticed. Zr-B-N coatings deposited with nitrogen flow values in the range 10–20 sccm offer an excellent choice for decorative purposes, owing to their dark grey or intense black colour and good corrosion resistance.     

Characterization of tribo-layers on self-lubricating plasma-assisted chemical-vapor-deposited TiN coatings

Recently, several new solid lubricants and modern lubrication concepts have been developed to achieve lower friction and wear and thus longer lifetime in severe tribological applications. The aim of this study is to characterize tribo-layers formed during ball-on-disc testing on low-friction, Cl-containing TiN coatings deposited by plasma assisted chemical vapor deposition and to clarify their formation mechanism. Characterization of the transfer layers was done by optical microscopy, optical profilometry, Raman spectroscopy, Auger electron spectroscopy and X-ray photoelectron spectroscopy. Differential scanning calorimetry was used to provide information on the chlorine-influenced chemical reactions of the coatings in ambient air. Iron oxide layers of a thickness in the nm-range have been found on low-chlorine containing TiN coatings (<3 at.% Cl) showing friction coefficients of approximately 0.8, whereas on TiN coatings with higher chlorine contents (>3 at.% Cl) rutile layers were preferably formed, resulting in friction coefficients below 0.2. This self-lubrication mechanism can be explained by the in-situ formation of easy-shearable titanium oxides in the contact zone in the presence of humidity and oxygen.     

On forecasting large and infrequent snow avalanches

Snow avalanches that threaten a highway or a residential area are often large avalanches that have a return period > 1 year. Danger assessment strongly relies on precipitation data since these avalanches are typically triggered by major snow storms. Given the extensive protection work that is in place in the European Alps, the avalanche control service (also called avalanche commission) responsible for danger assessment will usually monitor the avalanche situation throughout the winter, but only become active in case of a major snow fall. Related safety concepts describing the procedures and measures to be taken in a given danger situation are therefore often based on threshold values for new snow. By analysing the avalanche occurrence of a major avalanche path, we show that forecasting based on new snow amounts involves high uncertainty. Whereas the return period of an avalanche to, for example, the road was about 5 years, the return period for the corresponding new snow depth was substantially smaller, in our case slightly less than 2 years. Similar proportions were found for a number of other avalanche paths with different snow climate. The return period of the critical new snow depth was about 2–5 times smaller than the return period of the avalanche. This proportion is expected to increase with increasing return period. Hence, based on the return period of an avalanche path a first estimate for the critical new snow depth can be made. With a return period of the critical new snow depth of 1–2 years, avalanche prediction for individual avalanche path becomes very challenging since the false alarm ratio is expected to be high.     

Solvothermal synthesis,nanostructural characterization and gas cryo-adsorption studies in a metal–organic framework (IRMOF-1) material

A nanoporous metal–organic framework material, exhibiting an IRMOF-1 type crystalline structure, was prepared by following a direct solvothermal synthesis approach, using zinc nitrate and terephthalic acid as precursors and dimethylformamide as solvent, combined with supercritical CO₂ activation and vacuum outgassing procedures. A series of advanced characterization methods were employed, including scanning electron microscopy, Fourier-transform infrared radiation spectroscopy and X-ray diffraction, in order to study the morphology, surface chemistry and structure of the IRMOF-1 material directly upon its synthesis. Porosity properties, such as Brunauer–Emmet–Teller (BET) specific area (～520 m²/g) and micropore volume (～0.2 cm³/g), were calculated for the activated sample based on N₂ gas sorption data collected at 77 K. The H₂ storage performance was preliminary assessed by low-pressure (0–1 bar) H₂ gas adsorption and desorption measurements at 77 K. The activated IRMOF-1 material of this study demonstrated a fully reversible H₂ sorption behavior combined with an adequate gravimetric H₂ uptake relative to its BET specific area, thus achieving a value of ～1 wt.% under close-to-atmospheric pressure conditions.     

The mental lexicon is fully specified: Evidence from eye-tracking.

Four visual-world experiments, in which listeners heard spoken words and saw printed words, compared an optimal-perception account with the theory of phonological underspecification. This theory argues that default phonological features are not specified in the mental lexicon, leading to asymmetric lexical matching: Mismatching input (pin) activates lexical entries with underspecified coronal stops (tin), but lexical entries with specified labial stops (pin) are not activated by mismatching input (tin). The eye-tracking data failed to show such a pattern. Although words that were phonologically similar to the spoken target attracted more looks than did unrelated distractors, this effect was symmetric in Experiment 1 with minimal pairs (tin–pin) and in Experiments 2 and 3 with words with an onset overlap (peacock–teacake). Experiment 4 revealed that /t/-initial words were looked at more frequently if the spoken input mismatched only in terms of place than if it mismatched in place and voice, contrary to the assumption that /t/ is unspecified for place and voice. These results show that speech perception uses signal-driven information to the fullest, as was predicted by an optimal perception account. (PsycINFO Database Record (c) 2011 APA, all rights reserved)     

Oxidation and diffusion study on AlCrVN hard coatings using oxygen isotopes O and O

The present work aims to investigate the oxidation behaviour of AlCrVN hard coatings of equal composition but of different crystal structure. In order to gain more information about the mechanisms that are active during oxidation, a two-stage oxidation procedure has been applied where different isotopes, ¹⁶O and ¹⁸O, were introduced in each step. The analysis by means of secondary ion mass spectrometry depth profiling with its inherent isotope selectivity provided information on the general oxidation behaviour as well as the oxygen diffusion during the oxidation process. The single-phase coating with its face-centred cubic (fcc) structure presents a higher oxidation resistance as compared to the dual-phase coating containing a wurtzite and an fcc phase. After the annealing treatment the surface of the latter is entirely covered by VO₂ and V₂O₅ as evidenced by Raman spectroscopy. The single-phase coating, on the other hand, reveals unoxidised coating material and AlVO₄ crystals. However, even though exhibiting a significantly different oxidation resistance, the oxygen diffusion is similar. In both cases the peak values of ¹⁸O, which was introduced in the second stage, were found near the oxide-nitride interface indicating that O atoms diffused through the already formed oxides. Additional experiments using a gas mixture comprising natural water vapour H₂¹⁶O and ¹⁸O₂ revealed that mainly the presence of molecular oxygen causes oxidation as with increasing water vapour partial pressure the oxide layer thickness was significantly reduced.     

Recrystallization and grain growth of nanocomposite Ti–B–N coatings

Nanocomposite Ti–B–N coatings with different chemical composition were prepared by non-reactive co-sputtering of a segmented TiN–TiB₂ target. The coatings investigated are primarily composed of nanocrystalline TiN and TiB₂ phases. Increasing boron content results in a decreasing grain size from approximately 6 to 2 nm. During a thermal treatment of such coatings solely recovery and recrystallization with subsequent grain growth would appear, since the two phases are in thermodynamic equilibrium. Differential scanning calorimetry (DSC) and X-ray diffraction analysis were used to investigate the recrystallization behavior and subsequent grain growth of the nanocomposite Ti–B–N coatings. On heating the coating samples, which were removed chemically from their low alloyed steel substrates, an exothermal peak appeared during the DSC measurements indicating grain growth. From the onset temperature of this peak the recrystallization temperature was found which increases with increasing boron content from 1032 to 1070 °C. Activation energies for grain growth are obtained from Kissinger plots and yield values decreasing from 7.9 to 4.4 eV with increasing boron content. After heat treatment up to 1400 °C during the DSC measurements the coatings showed grain sizes within the range of 15–30 nm. It was found that the highest recrystallization temperature does not imply the highest activation energy for grain growth.     

A comparative study on the evaluation of the tribological behaviour of polymer/zinc coated steel sheets

A major factor affecting the formability of coated automative steel sheets is the interfacial frictional behaviour between the sheet and the forming die. Within this study, the suitability of standard laboratory-type tribological tests (pin-on-disc and block-on-cylinder test) to evaluate the tribological behaviour of uncoated and zinc and zinc/polymer coated steel sheets in dry sliding contact with cold working steel is investigated. The results obtained are compared to those obtained by a deep drawing experiment. Friction coefficients measured during the running-in stage of the pin-on-disc test seem to be well suited to distinguish between the different frictional behaviour of coated steel sheets.     

Carbon doped α-Al2O3 coatings grown by chemical vapor deposition

Alumina (Al₂O₃) coatings deposited by chemical vapor deposition (CVD) with different modifications and dopants are widely applied as wear resistant coatings on cemented carbide cutting tools. The aim of this work was to investigate the influence of CH₄ addition on the deposition of α-Al₂O₃ by low-pressure chemical vapor deposition (LPCVD). The coatings were deposited at 1005 °C on a TiN–TiCN base layer using a precursor gas mixture of AlCl₃, CH₄, CO₂, HCl, H₂S, and H₂. Coating characterization was conducted by scanning electron microscopy (SEM), glow discharge optical emission spectroscopy (GDOES), X-ray photoelectron spectroscopy (XPS), time-of-flight secondary ion mass spectroscopy (ToF-SIMS), glancing angle X-ray diffraction (GAXRD), nanoindentation and tribological ball-on-disk tests against Al₂O₃ balls. Additionally, the ball-on-disk wear tracks were investigated by Raman spectroscopy.