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. |
- 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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3. |
- Fuger, C., et al.
(author)
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Influence of Ta on the oxidation resistance of WB2-z coatings
- 2021
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In: Journal of Alloys and Compounds. - : Elsevier. - 0925-8388 .- 1873-4669. ; 864
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Journal article (peer-reviewed)abstract
- 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.
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4. |
- 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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5. |
- 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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6. |
- Kirnbauer, A., et al.
(author)
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Mechanical properties and thermal stability of reactively sputtered multi-principal-metal Hf-Ta-Ti-V-Zr nitrides
- 2020
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In: Surface & Coatings Technology. - : ELSEVIER SCIENCE SA. - 0257-8972 .- 1879-3347. ; 389
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Journal article (peer-reviewed)abstract
- 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.
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7. |
- Kirnbauer, A., et al.
(author)
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Thermal stability and mechanical properties of sputtered (Hf,Ta,V,W,Zr)-diborides
- 2020
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In: Acta Materialia. - : PERGAMON-ELSEVIER SCIENCE LTD. - 1359-6454 .- 1873-2453. ; 200, s. 559-569
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Journal article (peer-reviewed)abstract
- Non-reactive magnetron sputtering of a diboride target composed of HfB2, TaB2, VB2, W2B5, and ZrB2 with equimolar composition leads to the formation of crystalline single-phase solid solution diboride thin films, (Hf,Ta,V,W,Zr)B2, with a high-entropy metal-sublattice. Their growth morphology (dense and fine- fibrous), crystal structure (AlB2-type), as well as mechanical properties (indentation modulus E of ~580 GPa and hardness H of ~45 GPa), and chemical compositions are basically independent of the substrate bias potential applied (varied between -40 and -100 V) during the deposition at 450 °C. Detailed X-ray diffraction (XRD) and atom probe tomography (APT) studies indicate that the (Hf,Ta,V,W,Zr)B2 thin films remain single-phase AlB2-structured (with randomly distributed elements at the metal-sublattice) during vacuum-annealing at temperatures up to 1200 °C. Only when increasing the annealing temperature to 1400 °C, the formation of small orthorhombic structured (V,W)B-based regions can be detected, indicating the onset of decomposition of (Hf,Ta,V,W,Zr)B2 thin films into (Hf,Ta,Zr)B2 and (V,W)B, accompanied by the formation of confined B-rich boundary regions between these phases. After annealing at 1400 °C the hardness is still very high with ~44 GPa, as the volume fraction of the newly formed (V,W)B-rich domains is small and the majority of the coating is still solid-solution (Hf,Ta,V,W,Zr)B2 with severe lattice distortions. Only at even higher Ta of 1500 and 1600 °C, H decreased to ~39 GPa.
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8. |
- Moraes, V., et al.
(author)
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Substoichiometry and tantalum dependent thermal stability of alpha-structured W-Ta-B thin films
- 2018
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In: Scripta Materialia. - : Elsevier BV. - 1359-6462 .- 1872-8456. ; 155, s. 5-10
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Journal article (peer-reviewed)abstract
- 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.
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9. |
- 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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10. |
- Syed, Muhammad Bilal, et al.
(author)
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Effect of varying N(2)pressure on DC arc plasma properties and microstructure of TiAlN coatings
- 2020
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In: Plasma sources science & technology. - : IOP PUBLISHING LTD. - 0963-0252 .- 1361-6595. ; 29:9
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Journal article (peer-reviewed)abstract
- Detailed knowledge of correlations between direct current (DC) cathodic arc deposition process parameters, plasma properties, and the microstructure of deposited coatings are essential for a comprehensive understanding of the DC cathodic arc deposition process. In this study we have probed the plasma, generated by DC arc on a Ti-50 at.% Al cathode in a N(2)ambience, at the growth front of the TiAlN coating. Several consequences of an increasing N(2)pressure are observed, including a decreased electron temperature, an increased electron density, and a loss of energetic ions. As a result, the preferred growth texture switches from 220 to 111. It is also observed that neutrals in the plasma can significantly contribute to the growth of TiAlN coatings.
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11. |
- Zhu, Jianqiang, et al.
(author)
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Effects of cathode grain size and substrate fixturing on the microstructure evolution of arc evaporated Cr-cathodes and Cr-N coating synthesis
- 2014
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In: Journal of Vacuum Science & Technology. A. Vacuum, Surfaces, and Films. - : American Vacuum Society. - 0734-2101 .- 1520-8559. ; 32:2, s. 021515-
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Journal article (peer-reviewed)abstract
- The influence of the cathode grain size and the substrate fixturing on the microstructure evolution of the Cr cathodes and the resulting Cr-N coating synthesis is studied. Hot isostatic pressed Cr cathodes with three different grain sizes were arc evaporated in a nitrogen atmosphere and Cr-N coatings were deposited on cemented carbide substrate at 2 and 4 Pa nitrogen pressure, respectively. The Cr cathodes before and after arc discharging are composed of polycrystalline α-Cr regardless of the grain size. A converted layer forms on the Cr cathode surface and its microstructure differs with the cathode grain size. A stationary substrate fixturing results in ditches covering the cathode surface while a single rotating fixturing does not. The increased grain size of the virgin Cr cathodes enhances the quantities of the ditches. The possible causes are addressed. At 2 Pa nitrogen pressure, the Cr-N coatings deposited with the single rotating fixturing comprise only cubic CrN phase while the ones deposited with the stationary fixturing contain a mixture of hexagonal Cr2N and cubic CrN phases. By the increasing grain size of the Cr cathode, the droplet density of the Cr-N coatings increase somewhat while the hardness decreases for the Cr-N coatings deposited with stationary fixturing at 2 Pa nitrogen pressure.
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12. |
- Zhu, Jianqiang, et al.
(author)
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Influence of Ti-Si cathode grain size on the cathodic arc process and resulting Ti-Si-N coatings
- 2013
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In: Surface & Coatings Technology. - : Elsevier. - 0257-8972 .- 1879-3347. ; 235:25, s. 637-647
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Journal article (peer-reviewed)abstract
- The influence of the Ti-Si cathode grain size on cathodic arc processes and resulting Ti-Si-N coating synthesis has been studied. 63 mm Ti-Si cathodes containing 20-25 at % Si with four dedicated grain size of ~8 µm, ~20 µm, ~110 µm, and ~600 µm were fabricated via spark plasma sintering or hot isostatic pressing. They were evaporated in 2 Pa nitrogen atmosphere in an industrial-scale arc deposition system and the Ti-Si-N coatings were grown at 50 A, 70 A, and 90 A arc current. The composition and microstructure of the virgin and worn cathode surfaces as well as the resulting coatings were characterized using optical and electron microscopy, x-ray diffraction, elastic recoil detection analysis, x-ray photoelectron spectroscopy, and nanoindentation. The results show that the existence of multiple phases with different work function values directly influences the cathode spot ignition behavior and also the arc movement and appearance. Specifically, there is a preferential erosion of the Ti5Si3-phase grains. By increasing the grain size of the virgin cathode, the preferential erosion is enhanced, such that the cathode surface morphology roughens substantially after 600 Ah arc discharging. The deposition rate of the Ti-Si-N coating is increased with decreasing grain size of the evaporated Ti-Si cathodes. The composition, droplet density, and droplet shape of the coatings are influenced by the arc movement, which is also shown to depend on the cathode grain size.
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