| 1. |
- Pöllmann, P. J., et al.
(author)
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Metastable phase formation of (Mo,Cr)2AlB2 MAB phase thin films revealed by theory and experiments
- 2024
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In: Materials Research Letters. - : Taylor & Francis. - 2166-3831. ; 12:1, s. 58-66
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Journal article (peer-reviewed)abstract
- A (Mo0.24Cr0.76)0.40Al0.32B0.28 thin film was deposited by direct current magnetron sputtering at 600 °C substrate temperature. Analysis by X-ray diffraction, energy-dispersive X-ray spectroscopy, elastic recoil detection analysis, and high-resolution scanning transmission electron microscopy revealed the formation of the previously unreported (Mo,Cr)2AlB2 MAB phase, along with Cr3AlB4, CrB4, and Mo, in good agreement with density functional theory (DFT) calculations. Hence, the MAB phase family in the Mo-Cr-Al-B system is extended by a novel, quaternary member.
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| 2. |
- Glechner, T., et al.
(author)
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Correlation between fracture characteristics and valence electron concentration of sputtered Hf-C-N based thin films
- 2020
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In: Surface & Coatings Technology. - : Elsevier BV. - 0257-8972 .- 1879-3347. ; 399
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Journal article (peer-reviewed)abstract
- Hard protective coating materials based on transition metal nitrides and carbides typically suffer from limited fracture tolerance. To further tune these properties non-metal alloying - substituting C with N - has been proven favorable for magnetron sputtered Hf-C-N based thin films. A theoretically predicted increase in valence electron concentration (from 8.0 to 9.0 e/f.u. from Hf-C to Hf-N) through nitrogen alloying lead to an increase in fracture toughness (K-IC obtained during in-situ SEM cantilever bending) from 1.89 +/- 0.15 to 2.33 +/- 0.18 MPa.m(1/2) for Hf0.43C0.57 to Hf0.35C0.30N0.35, respectively. The hardness remains close to the super-hard regime with values of 37.8 +/- 2.1 to 39.9 +/- 2.7 GPa for these specific compositions. Already the addition of small amounts of nitrogen, while sputtering a ceramic Hf-C target, leads to a drastic increase of nitrogen on the non-metallic sublattice for fcc single phased structured HfC1-xNx films, where x = N/(C + N). The here obtained results also provide experimental proof for the correlation between fracture characteristics and valence electron concentration.
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| 3. |
- Ruess, H., et al.
(author)
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HPPMS deposition from composite targets : Effect of two orders of magnitude target power density changes on the composition of sputtered Cr-Al-C thin films
- 2017
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In: Vacuum. - : PERGAMON-ELSEVIER SCIENCE LTD. - 0042-207X .- 1879-2715. ; 145, s. 285-289
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Journal article (peer-reviewed)abstract
- The effect of target power density, substrate bias potential and substrate temperature on the thin film composition was studied. A Cr-Al-C composite target was sputtered utilizing direct current (DCMS: 2.3 W/cm(2)) and high power pulsed magnetron sputtering (HPPMS: 373 W/cm(2)) generators. At floating potential, all Cr-Al-C thin films showed similar compositions, independently of the applied target power density. However, as substrate bias potential was increased to -400 V, aluminum deficiencies by a factor of up to 1.6 for DCMS and 4.1 for HPPMS were obtained. Based on the measured ion currents at the substrate, preferential re-sputtering of Al is suggested to cause the dramatic Al depletion. As the substrate temperature was increased to 560 degrees C, the Al concentration was reduced by a factor of up to 1.9 compared to the room temperature deposition. This additional reduction may be rationalized by thermally induced desorption being active in addition to re-sputtering.
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| 4. |
- Bahr, A., et al.
(author)
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High-temperature oxidation resistance of ternary and quaternary Cr-(Mo)-Si-B2-z coatings-Influence of Mo addition
- 2023
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In: Surface & Coatings Technology. - : Elsevier. - 0257-8972 .- 1879-3347. ; 468
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Journal article (peer-reviewed)abstract
- The Si-based alloying of transition metal diborides is a promising strategy to improve their limited oxidation resistance in high-temperature environments. In this study, we investigate the oxidation resistance of ternary and quaternary Cr-(Mo)-Si-B2-z coatings sputter-deposited from alloyed CrB2/TMSi2 targets (TM = Cr, Mo). The asdeposited Cr-(Mo)-Si-B2-z coatings are stabilized in the single-phased hexagonal AlB2-structure, except the high-Si containing Cr0.26Mo0.11Si0.24B0.39 presenting amorphous character. The Mo-containing Cr-Mo-Si-B2-z films exhibit relatively high hardness compared to their ternary Cr-Si-B2-z counterparts, obtaining up to 26 GPa due to the formation of (Cr,Mo)B-2 solid solutions. The Si-alloying in ternary and quaternary coatings provides oxidation resistance up to 1200 degrees C, owing to the formation of highly protective double-layered scales consisting of SiO2 with a Cr2O3 layer on top, inhibiting oxygen inward diffusion. The quaternary Cr0.31Mo0.07Si0.15B0.47 coating is distinguished by superior oxidation resistance with lower porosity and void formation compared to the ternary Cr0.37Si0.16B0.47. Mo proved to be the key element for the higher stability and enhanced oxidation resistance due to the evolution of the MoSi2 phase at similar to 600 degrees C. This phase formation controls the Si diffusion and mobility within the microstructure, thus reducing the porosity and governing the Si supply to form SiO2 scale. The quaternary Cr0.31Mo0.07Si0.15B0.47 coating maintained an oxidation resistance up to 30 h at 1200 degrees C by forming a 2.5 mu m dense amorphous Si-based oxide scale with a thin Cr2O3 on top.
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| 5. |
- Bahr, A., et al.
(author)
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Non-reactive HiPIMS deposition of NbCx thin films : Effect of the target power density on structure-mechanical properties
- 2022
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In: Surface & Coatings Technology. - : Elsevier. - 0257-8972 .- 1879-3347. ; 444
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Journal article (peer-reviewed)abstract
- The exceptional mechanical properties of transition metal carbide coatings are known to be governed by the carbon content and its morphological distribution. Here, we verify the influence of the target peak power density on the chemical composition, microstructure, and mechanical properties of NbCx coatings grown by non-reactive high-power impulse magnetron sputtering (HiPIMS). By tuning the pulse parameters, the power density can be increased from 0.11 to 1.48 kW/cm2 leading to a decrease in the C/Nb ratio from 1.52 to 0.99 within the films - proven by combined elastic backscattering and time-of-flight elastic recoil detection analysis. This decrease in the C/Nb ratio is accompanied by microstructural changes from nanocomposite morphologies with an average grain size of 6.6 +/- 2.5 nm at 0.13 kW/cm2 into more columnar structures with an average column width of 65.2 +/- 18.7 nm at 1.48 kW/cm2. Independent from the C/Nb ratio, all films exhibit a single face-centered cubic structure. The mechanical properties correlate with the enhanced growth behavior dominated by ions at higher peak power densities and the varied C/Nb ratios. A maximum in hardness and fracture toughness of H = 38.7 +/- 3.6 GPa and KIc = 2.78 +/- 0.13 MPa center dot m1/2 (at 3.2 GPa residual compressive stress), is obtained for the nearly stoichiometric NbC coating exhibiting C/Nb ratio of 1.06.
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| 6. |
- Dalbauer, V, et al.
(author)
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On the phase formation of cathodic arc evaporated Al1-xCrx-based intermetallic coatings and substoichiometric oxides
- 2018
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In: Surface & Coatings Technology. - : ELSEVIER SCIENCE SA. - 0257-8972 .- 1879-3347. ; 352, s. 392-398
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Journal article (peer-reviewed)abstract
- 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.
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| 7. |
- Glechner, T., et al.
(author)
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Influence of the non-metal species on the oxidation kinetics of Hf, HfN, HfC, and HfB2 coatings
- 2021
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In: Materials & design. - : Elsevier. - 0264-1275 .- 1873-4197. ; 211
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Journal article (peer-reviewed)abstract
- The influence of the non-metal species on the oxidation resistance of transition metal ceramic based thin films is still unclear. For this purpose, we thoroughly investigated the oxide scale formation of a metal (Hf), carbide (HFC0.96), nitride (HfB1.5), and boride (HfB2.3) coating grown by physical vapor deposition. The non-metal species decisively affect the onset temperature of oxidation, ranging between 550 degrees C for HfC0.96 to 840 degrees C for HfN1.5. HfB2.3 and HfN1.5 obtain the slowest oxide scale kinetic following a parabolic law with k(p) values of 4.97.10(-10) and 5.66.10(-11) kg(2) m(-4) s(-1) at 840 degrees C, respectively. A characteristic feature for the oxide scale on Hf coatings, is a columnar morphology and a substantial oxygen inward diffusion. HfC0.96 reveals an ineffective oxycarbide based scale, whereas HfN(1.5 )features a scale with globular HfO2 grains. HfB(2.3 )exhibits a layered scale with a porous boron rich region on top, followed by a highly dense and crystalline HfO2 beneath. Furthermore, HfB(2.3 )presents a hardness of 47.7 +/- 2.7 GPa next to an exceptional low inward diffusion of oxygen during oxidation. This study showcases the strong influence of the non-metallic bonding partner despite the same metallic basis, as well as the huge potential for HfB2 based coatings also for oxidative environments.
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| 8. |
- Glechner, T., et al.
(author)
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Tuning structure and mechanical properties of Ta-C coatings by N-alloying and vacancy population
- 2018
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In: Scientific Reports. - : Springer Science and Business Media LLC. - 2045-2322. ; 8
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Journal article (peer-reviewed)abstract
- 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.
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| 9. |
- Hahn, R., et al.
(author)
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Unraveling the superlattice effect for hexagonal transition metal diboride coatings
- 2023
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In: Scripta Materialia. - : Elsevier. - 1359-6462 .- 1872-8456. ; 235
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Journal article (peer-reviewed)abstract
- 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.
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| 10. |
- Hudak, O. E., et al.
(author)
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Improved corrosion resistance of cathodic arc evaporated Al0.7Cr0.3_xVxN coatings in NaCl-rich media
- 2023
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In: Corrosion Science. - : Elsevier BV. - 0010-938X .- 1879-0496. ; 221
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Journal article (peer-reviewed)abstract
- The corrosion resistance of cathodic arc evaporated Al0.7Cr0.3_xVxN coatings with a vanadium content up to 22.3 at% has been electrochemically tested in a 0.1 M NaCl-solution. Significant improvement in the open porosity and corrosion rate was observed for coatings with higher V-contents, due to a denser and more refined coating morphology. Further reduction in the open porosity rate was achieved through an annealing step in air at 700 degrees C. Here, the formation of an AlVO4 top-oxide and underlying oxygen-rich V-depletion zone provides additional sealing of the coating surface, whilst reducing the corrosion current density to a final 1.59 x 10_9 A/cm2.
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