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Superlattice structures enable the simultaneous enhancement in hardness (H) and fracture toughness (KIC) of ceramic-like coatings. While a deeper understanding of this effect has been gained for fcc-structured transition metal nitrides (TMN), hardly any knowledge is available for hexagonal diborides (TMB2). Here we show that superlattices can-similarly to nitrides-increase the hardness and toughness of diboride films. For this purpose, we deposited TiB2/WB2 and TiB2/ZrB2 superlattices with different bilayer periods (?) by non-reactive sputtering. Nanoindentation and in-situ microcantilever bending tests yield a distinct H peak for the TiB2/WB2 system (45.5 & PLUSMN; 1.3 GPa for ? = 6 nm) but no increase in KIC related to a difference in shear moduli (112 GPa). Contrary, the TiB2/ZrB2 system shows no peak in H, but for KIC with 3.70 & PLUSMN; 0.26 MPa & BULL;m1/2 at ? = 4 nm originating from differences in lattice spacing (0.14 & ANGS;), hence causing coherent stresses retarding crack growth.

Ternary W1-x TaxB2-z is a promising protective coating material possessing enhanced ductile character and phase stability compared to closely related binaries. Here, the oxidation resistance of W1-xTaxB2-z thin films was experimentally investigated at temperatures up to 700 degrees C. Ta alloying in sputter deposited WB2-z coatings led to decelerated oxide scale growth and a changed growth mode from paralinear to a more linear (but retarded) behavior with increasing Ta content. The corresponding rate constants decrease from k(p)* = 6.3.10(-4) mu m(2)/s for WB2-z to k(p)* = 1.1.10(-4) mu m(2)/s for W0.66Ta0.34B2-z as well as k(1) = 2.6.10(-5) mu m/s for TaB2-z, underlined by decreasing scale thicknesses ranging from 1170 nm (WB2-z), over 610 nm (W0.66Ta0.34B2-z) to 320 nm (TaB2-z) after 10 min at 700 degrees C. Dense and adherent scales exhibit an increased tantalum content (columnar oxides), which suppresses the volatile character of tungsten-rich as well as boron oxides, hence being a key-factor for enhanced oxidation resistance. Thus, adding Ta (in the range of x = 0.2-0.3) to a-structured WB2-z does not only positively influence the ductile character and thermal stability but also drastically increases the oxidation resistance.

The outstanding thermo-mechanical and chemical stability of Al2O3 thin films attracts particular attention in academia and industry. Here we show that alloying of the powder metallurgically prepared Al targets with 2 as well as 5 at.% of Cr, Mo, or W significantly improves the process stability (e.g., reducing arcing events) for Al2O3, allowing their reactive magnetron sputtering in DC mode (substrate temperature was always 360 degrees C). Contrary to these microalloying elements, Nb did not change or improve the process characteristics of the Al target due to the relatively coarse Nb particles (< 125 mu m). Particularly the small (< 10 mu m) and fine-dispersed W particles are very effective in stopping the collision cascades to concentrate them to the near subsurface target-regions. This leads to a shift of the target-poisoning onset from O-2/(Ar + O-2) flow-rate-ratios of about 32 to 52%, specifically when adding 5 at.% to the Al target. Thereby also improved deposition rates are possible. However, detailed X-ray diffraction (XRD) and transmission electron microscopy studies show that only thin films developed from the 2 at.% W alloyed Al target have a nanocrystalline gamma-Al2O3-based structure comparable to those prepared from Al or Cr alloyed Al targets. The films are with 28.3 GPa instead of 26.8 GPa slightly harder when sputtered from Al0.98W0.02 instead of Al targets. Higher W contents (and also Nb) in the target lead to the formation of Al2O3-based films with considerably lower crystalline phase fractions and hardness (similar to 13 GPa). Hardest films, with 30.0 and 29.6 GPa, are obtained when using Al0.98Cr0.02 and Al0.98Cr0.05 targets, respectively. The formation of volatile Mo-oxides during film growth interferes the structure development, leading to rather soft films with 8.0 GPa especially when using the higher Mo alloyed Al0.98Cr0.05 target. Based on our results we can conclude that microalloying the Al targets with small and fine-dispersed Cr

Crystalline (Hf,Ta,Ti,V,Zr)N nitride thin films, with a high-entropy metal-sublattice, were synthesized at 440 degrees C by reactive magnetron sputtering using an equimolar Hf-Ta-Ti-V-Zr-compound target. The coatings are single-phase fcc structured mono-nitrides for N-2/(Ar + N-2) flow-rate-ratios (f(N2)) between 30 and 45%. For higher f(N2) a small fraction of a second phase (next to the fcc matrix) can be detected by X-ray diffraction (XRD) and selected area electron diffraction (SAED). All coatings studied (prepared with f(N2) between 30 and 60%) show similar chemical compositions and hardness (H) values between 30.0 and 34.0 GPa with indentation moduli of similar to 460 GPa. Atom probe tomography (APT) indicates a homogenous distribution of all elements within our fcc-(Hf,Ta,Ti,V,Zr)N even after vacuum-annealing at 1300 degrees C. While H decreased from 32.5 to 28.1 GPa by this annealing treatment, the coating is still single-phase fcc structured with a defect density (expressed by XRD and SAED features, transmission electron microscopy contrast, and grain sizes) comparable to the as-deposited state. Only after vacuum-annealing at 1500 degrees C, XRD and APT reveal the formation of hexagonal structured (Ta,V)(2)N. The onset of nitrogen-loss - detected by thermogravimetric analysis - is similar to 1350 degrees C. Based on our results we can conclude that the sluggish diffusion within our fcc-(Hf,Ta,Ti,V,Zr)N warrants the single-phase fcc structure up to 1300 degrees C, although ab initio based calculations would suggest the lower-entropy products [fcc-(Hf,Zr)N, fcc-(Ta,V)N, and fcc-TiN] and [fcc-(Hf,Zr)N and fcc-(Ta,Ti,V)N] to be energetically more stable up to 1302 K.

Tailoring mechanical properties of transition metal carbides by substituting carbon with nitrogen atoms is a highly interesting approach, as thereby the bonding state changes towards a more metallic like character and thus ductility can be increased. Based on ab initio calculations we could prove experimentally, that up to a nitrogen content of about 68% on the non-metallic sublattice, Ta-C-N crystals prevail a face centered cubic structure for sputter deposited thin films. The cubic structure is partly stabilized by non-metallic as well as Ta vacancies-the latter are decisive for nitrogen rich compositions. With increasing nitrogen content, the originally super-hard fcc-TaC0.71 thin films soften from 40 GPa to 26 GPa for TaC0.33N0.67, accompanied by a decrease of the indentation modulus. With increasing nitrogen on the non-metallic sublattice (hence, decreasing C) the damage tolerance of Ta-C based coatings increases, when characterized after the Pugh and Pettifor criteria. Consequently, varying the non-metallic sublattice population allows for an effective tuning and designing of intrinsic coating properties.

The phase evolution of Al1-xCrx-based intermetallic coatings and corresponding substoichiometric oxides grown by cathodic arc evaporation was investigated in order to obtain a better understanding of the relation between oxygen flow rate, Al and Cr content, and structural evolution of the coatings deposited. When using 20 sccm Ar, or 50 sccm O-2, or 100 sccm O-2 per active source (p.a.s.) the cathode reaction zone consists of various intermetallic Al-Cr-compounds, which are in good agreement with the binary Al-Cr phase diagram. This is generally also reflected in the phase composition of the metallic and substoichiometric oxide coatings. The Al-rich compositions, Al0.75Cr0.25 and Al0.70Cr0.30, show a strong tendency for the formation of gamma(1)-Al8Cr5 phases. Mostly, the coating compositions of the metallic constituents of the synthesised intermetallic and substoichiometric oxide coatings deviate from the elemental compositions of the cathode, show enrichment in Cr. This deviation is more pronounced for Cr-rich cathodes using low O-2 flow rates during deposition. The dense columnar structure of the intermetallic coatings (hardness values between 2.5 and 10.2 GPa) turns into a nano-composite-like morphology for depositions with 50 and 100 sccm O-2 p.a.s., which in turn leads to a significant hardness increase up to similar to 24 GPa. Among all coatings investigated, the Cr-rich compositions have higher hardness and denser morphology than the Al-rich layers.

Physical vapor deposited (PVD) WB2 thin films crystallize in the alpha-AIB(2)-prototype structure rather than in their thermodynamically stable (omega-W2B5-z-prototype structure. Contrary to the majority of alpha-AlB2-type transition metal diborides (TMB2), alpha-WB2 exhibits a more ductile character. Combining density functional theory and sophisticated experiments, we show that the stability of alpha-WB2 thin films is basically influenced by point defects such as vacancies present in PVD materials. With the help of alpha-TaB2 (one of the most ductile TMB2 with high preference for alpha-AlB2-type), the thermally driven decomposition and phase transformation of alpha-W1-xTaxB2-z to the omega-W2B5-z-type can be shifted to temperatures above 1200 degrees C.

Using nonreactive sputter deposition allows the preparation of single-phase fcc structured TaCy thin films over a wide compositional range with y between 0.63 and 1.04. Among this composition range, the C-deficient TaC0.78 exhibits the highest as deposited hardness of 43.4 +/- 0.65 GPa combined with the highest thermal stability. Even after vacuum annealing to 2400 degrees C, no vacancy-ordered or faulted Ta-C based phases can be detected. The stabilization of carbon deficient fcc structured TaCy near y of about 0.75, revealed the decisive character of vacancy engineered thin films materials for ultra-high temperature applications. (C) 2018 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Transition metal carbides are known for their exceptional thermal stability and mechanical properties, notably governed by the carbon content and the prevalent vacancies on the non-metallic sublattice. However, when using reactive deposition techniques, the formation of amorphous C-containing phases is often observed. Here, we show that non-reactive magnetron sputtering of HfC0.89 or TaC0.92 targets lead to fully crystalline coatings. Their C content depends on the target-to-substrate alignment and globally increases from HfC0.66 to HfC0.76 and from TaC0.69 to TaC0.75 with increasing bias potential from floating to - 100 V, respectively, when using a substrate temperature T-sub of 500 degrees C. Increasing T-sub to 700 degrees C leads to variations from TaC0.71 to TaC0.81. All HfCy films are single-phase face-centered cubic, whereas the TaCy films also contain small fractions of the hexagonal Ta2C phase. The highest hardness and indentation modulus among all coatings studied is obtained for TaC0.75 with H = 41.9 +/- 03 GPa and E = 466.8 +/- 15 GPa. Ab initio calculations predict an easy formation of vacancies on the C-sublattice, especially in the Ta-C system, and a temperature driven stabilization of defected structures at high temperatures, with fewer vacancies on the C sublattice for Hf-C than for Ta-C The predicted phase stability is proven up to 2400 C for both systems by annealing experiments in vacuum.