The differences in work function (W.F.) and cohesive energy (C.E.) of the phases constituting the cathode, plays an important role in the formation of the converted layer at its near-surface region during cathodic arc deposition. As a consequence, this also affects the deposition conditions for the coatings. In this study, we explore the effect of W.F. and C.E. of the constituent phases during arc evaporation by utilizing two kinds of customized Ti-50 at.% Al cathodes with different phase compositions. Our results show that during reactive arc evaporation the disparity in W.F. and C.E. among the constituent phases of Ti-50 at.% Al cathodes leads to preferential erosion of the phases with lower W.F. and C.E. The aforementioned preferential erosion begets higher surface roughness on the Ti-50 at.% Al cathode with a wider range of W.F. and C.E. disparity. It is also observed that the thermal conductivity of the Ti-50 at.% Al cathode plays a dominant role in the deposition rate of Ti-Al-N coating. This article also presents how the surface geometry of the cathode in the presence of arc guiding magnetic field significantly influences the microstructure of the deposited coatings.

The effect of metal alloying on mechanical properties including hardness and fracture toughness were investigated in three alloys, Ti 0.33Al0.50(Me) 0.17N (Me = Cr, Nb and V), and compared to Ti0.50Al0.50N, in the as-deposited state and after annealing. All studied alloys display similar as-deposited hardness while the hardness evolution during annealing is found to be connected to phase transformations, related to the alloy’s thermal stability. The most pronounced hardening was observed in Ti0.50Al0.50N, while all the coatings with additional metal elements sustain their hardness better and they are harder than Ti0.50Al0.50N after annealing at 1100 °C. Fracture toughness properties were extracted from scratch tests. In all tested conditions, as-deposited and annealed at 900 and 1100 °C, Ti0.33Al0.50Nb0.17N show the least surface and sub-surface damage when scratched despite the differences in decomposition behavior and h-AlN formation. Theoretically estimated ductility of phases existing in the coatings correlates well with their crack resistance. In summary, Ti0.33Al0.50Nb0.17N is the toughest alloy in both as-deposited and post-annealed states.

Time evolution of catalytic CO2 hydrogenation to methanol and dimethyl ether (DME) has been investigated in a high-temperature high-pressure reaction chamber where products accumulate over time. The employed catalysts are based on a nano-assembly composed of Cu nanoparticles infiltrated into a Zr doped SiOx mesoporous framework (SBA-15): Cu-Zr-SBA-15. The CO2 conversion was recorded as a function of time by gas chromatography-mass spectrometry (GC-MS) and the molecular activity on the catalyst’s surface was examined by diffuse reflectance in-situ Fourier transform infrared spectroscopy (DRIFTS). The experimental results showed that after 14 days a CO2 conversion of 25% to methanol and DME was reached when a DME selective catalyst was used which was also illustrated by thermodynamic equilibrium calculations. With higher Zr content in the catalyst, greater selectivity for methanol and a total 9.5% conversion to methanol and DME was observed, yielding also CO as an additional product. The time evolution profiles indicated that DME is formed directly from methoxy groups in this reaction system. Both DME and methanol selective systems show the thermodynamically highest possible conversion.

Nitrogen sub-stoichiometric (Ti_0.52Al_0.48)Ny (0.92 ≥ y  ≥ 0.46) coatings were grown in a mixed Ar/N2 atmosphere by cathodic arc deposition on cemented carbide (WC/Co-based) substrates. The coatings present a columnar structure with decreasing column widths from 250 to 60nm, due to a corresponding reduced N content, accompanied by changes in preferred orientation from 200 to 111 to 220. Among these, coatings prepared with 0.92≥y≥0.75 exhibit spinodal decomposition and consequently age hardening at elevated temperatures. A reduced N content upshifts the hardness maximum by >300 °C. For these samples, the high temperature treatment resulted in interdiffusion of substrate elements, Co and C, mainly along column boundaries. Nevertheless, no detrimental effect in the hardness could be correlated. Conversely, a low N content sample (y=0.46) presents significant lattice diffusion of substrate elements Co, C, W, and Ta in the coating. In this case, the substrate elements are present throughout the coating, forming additional phases such as c-Ti(C,N), c-Co(Al,Ti,W), and c-(Ti,W,Ta)(C,N), with an observed increased hardness from 16 to 25GPa. We suggest that the substitution of nitrogen by carbon and the solution of W and Ta in c-TiN are responsible for the observed hardening. Our investigation shows the potential of sub-stoichiometric (Ti_1-xAl_x)Ny coatings for high temperature applications such as cutting tools and puts forth corresponding criteria for N content selection.

Today's research on the cathodic arc deposition technique and coatings therefrom primarily focuses on the effects of, e.g., nitrogen partial pressure, growth temperature, and substrate bias. Detailed studies on the morphology and structure of the starting material—the cathode—during film growth and its influence on coating properties at different process conditions are rare. This work aims to study the evolution of the converted layer, its morphology, and microstructure, as a function of the cathode material grain size during deposition of Ti-Al-N coatings. The coatings were reactively grown in pure N2discharges from powder metallurgically manufactured Ti-50 at.% Al cathodes with grain size distribution averages close to 1800, 100, 50, and 10 μm, respectively, and characterized with respect to microstructure, composition, and mechanical properties. The results indicate that for the cathode of 1800 μm grain size the disparity in the work function among parent phases plays a dominant role in the pronounced erosion of Al, which yields the coatings rich in macro-particles and of high Al content. We further observed that a reduction in the grain size of Ti-50 at.% Al cathodes to 10 μm provides favorable conditions for self-sustaining reactions between Ti and Al phases upon arcing to form γ phase. The combination of self-sustaining reaction and the arc process not only result in the formation of hole-like and sub-hole features on the converted layer but also generate coatings of high Al content and laden with macro-particles.

A catalytically active nanoassembly comprising Cu-nanoparticles grown on integrated and active supports (large pore Zr-doped mesoporous SBA-15 silica) has been synthesized and used to promote CO2 hydrogenation. The doped mesoporous material was synthesized using a sal-gel method, in which the pore size was tuned between 11 and 15 nm while maintaining a specific surface area of about 700 m(2) g (1). The subsequent Cu nanoparticle growth was achieved by an infiltration process involving attachment of different functional groups on the external and internal surfaces of the mesoporous structure such that 7-10 nm sized Cu nanoparticles grew preferentially inside the pores. Chemisorption showed improved absorption of both CO2 and H-2 for the assembly compared to pure SBA-15 and 15% of the total CO2 was converted to methanol and dimethyl ether at 250 degrees C and 33 bar.

Atom probe tomography was used to compare Na and Sr modified Al-Si hypoeutectic alloys. Both Na and Sr promote the formation of nanometre-sized clusters in the Si eutectic phase. Compositional analyses of the clusters show an Al:Sr ratio of 2.92 +/- 0.46 and an Al:Na ratio of 1.07 +/- 0.23. It is proposed that SrAl2Si2 and NaAlSi clusters are formed at the Si/liquid interface and take part in the modification process by altering the eutectic Si growth.

In this work, we discuss the mixing thermodynamics of cubic (B1) Ti1-xAlxN/TiN(001) multilayers. We show that interfacial effects suppress the mixing enthalpy compared to bulk Ti1-xAlxN. The strongest stabilization occurs for compositions in which the mixing enthalpy of bulk Ti1-xAlxN has its maximum. The effect is split into a strain and an interfacial (or chemical) contribution, and we show that both contributions are significant. An analysis of the local atomic structure reveals that the Ti atoms located in the interfacial layers relax significantly different from those in the other atomic layers of the multilayer. Considering the electronic structure of the studied system, we demonstrate that the lower Ti-site projected density of states at epsilon(F) in the Ti1-xAlxN/TiN multilayers compared to the corresponding monolithic bulk explains a decreased tendency toward decomposition.

Wurtzite aluminium nitride is a technologically important wide band gap semiconductor with an unusually high thermal conductivity, used in optical applications and as a heatsink substrate. Many of its properties depend on an accurate description of its lattice dynamics, which have thus far only been captured in the quasiharmonic approximation. In this work, we demonstrate that anharmonicity has a considerable impact on its phase stability and transport properties, since anharmonicity is much stronger in the rocksalt phase. We compute a pressure-temperature phase diagram of AlN, demonstrating that the rocksalt phase is stabilised by increasing temperature, with respect to the wurtzite phase. We demonstrate that including anharmonicity, we can recover the thermal conductivity of the wurtzite phase (320 Wm⁻¹K⁻¹ under ambient conditions), and compute the hitherto unknown thermal conductivity of the rocksalt phase (96 Wm⁻¹K⁻¹). We also show that the electronic band gap decreases with temperature. These findings provide further evidence that anharmonic effects cannot be ignored in high temperature applications.

The cracking and delamination of TiN-coated hardmetals (WC-Co cemented carbides) when subjected to Brale indentation were studied. Experimental variables were substrate microstructure related to low (6 wt% Co) and medium (13 wt% Co) binder content, and surface finishes associated with grinding and polishing stages before film deposition. Brale indentation tests were conducted on both coated and uncoated hardmetals. Emphasis has been placed on assessing substrate microstructure and subsurface finish effects on load levels at which cracking and delamination phenomena emerge, the type of cracking pattern developed, and how fracture mechanisms evolve with increasing load. It is found that polished and coated hardmetals are more brittle (radial cracking) and the adhesion strength (coating delamination) diminishes with decreasing binder content. Such a response is discussed on the basis of the influence of intrinsic hardness/brittleness of the hardmetal substrate on both cracking at the subsurface level and effective stress state, particularly regarding changes in shear stress component. Grinding promotes delamination compared to the polished condition, but strongly inhibits radial cracking. This is a result of the interaction between elastic-plastic deformation imposed during indentation and several grinding-induced effects: remnant compressive stress field, pronounced surface texture and micro cracking within a thin altered subsurface layer. As a consequence, coating spallation prevails over radial cracking as the main mechanism for energy dissipation in ground and coated hardmetals. (C) 2016 Elsevier B.V. All rights reserved.