| 1. |
- Edström, Daniel, 1986-, et al.
(författare)
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Mechanical properties of VMoNO as a function of oxygen concentration : Toward development of hard and tough refractory oxynitrides
- 2019
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Ingår i: Journal of Vacuum Science & Technology. A. Vacuum, Surfaces, and Films. - : American Institute of Physics (AIP). - 0734-2101 .- 1520-8559. ; 37:6
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Tidskriftsartikel (refereegranskat)abstract
- Improved toughness is a central goal in the development of wear-resistant refractory ceramic coatings. Extensive theoretical and experimental research has revealed that NaCl-structure VMoN alloys exhibit surprisingly high ductility combined with high hardness and toughness. However, during operation, protective coatings inevitably oxidize, a problem that may compromise material properties and performance. Here, the authors explore the role of oxidation in altering VMoN properties. Density functional theory and theoretical intrinsic hardness models are used to investigate the mechanical behavior of cubic V0.5Mo0.5N1-xOx solid solutions as a function of the oxygen concentration x. Elastic constant and intrinsic hardness calculations show that oxidation does not degrade the mechanical properties of V0.5Mo0.5N. Electronic structure analyses indicate that the presence of oxygen reduces the covalent bond character, which slightly lowers the alloy strength and intrinsic hardness. Nevertheless, the character of metallic d-d states, which are crucial for allowing plastic deformation and enhancing toughness, remains unaffected. Overall, the authors' results suggest that VMoNO oxynitrides, with oxygen concentrations as high as 50%, possess high intrinsic hardness, while still being ductile. Published by the AVS.
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| 2. |
- Landälv, Ludvig, 1982-, et al.
(författare)
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Influence of Si doping and O-2 flow on arc-deposited (Al,Cr)(2)O-3 coatings
- 2019
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Ingår i: Journal of Vacuum Science & Technology. A. Vacuum, Surfaces, and Films. - : A V S AMER INST PHYSICS. - 0734-2101 .- 1520-8559. ; 37:6
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Tidskriftsartikel (refereegranskat)abstract
- (Al,Cr)(2)O-3 coatings with Al/( Al + Cr) = 0.5 or Al = 70 at. %, doped with 0, 5, or 10 at. % Si, were deposited on hard metal and Si(100) substrates to elucidate the influence of Si on the resulting coatings. The chemical analysis of the coatings showed between 3.3 and 7.4 at. % metal fraction Si incorporated into all studied coatings depending on cathode Si composition. The incorporated Si content does not change significantly with different oxygen flows covering a wide range of deposition conditions from low to high O-2 flow during growth. The addition of Si promotes the metastable B1-like cubic structure over the thermodynamically stable corundum structure. The hardness determined by nanoindentation of the as-deposited coatings is slightly reduced upon Si incorporation as well as upon increased Al content. Si is found enriched in droplets but can also be found at a lower content, evenly spread, without visible segregation at the similar to 5 nm scale, in the actual oxide coating. The positive effect of improved cathode erosion upon Si incorporation has to be balanced against the promotion of the metastable B1-like structure, having lower room temperature hardness and inferior thermal stability compared to the corundum structure. Published by the AVS.
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| 3. |
- Landälv, Ludvig, 1982-, et al.
(författare)
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Phase composition and transformations in magnetron-sputtered (Al,V)2O3 coatings
- 2019
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Ingår i: Thin Solid Films. - : Elsevier BV. - 0040-6090 .- 1879-2731. ; 688
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Tidskriftsartikel (refereegranskat)abstract
- Coatings of (Al1-xVx)2O3, with x ranging from 0 to 1, were deposited by pulsed DC reactive sputter deposition on Si(100) at a temperature of 550 °C. XRD showed three different crystal structures depending on V-metal fraction in the coating: α-V2O3 rhombohedral structure for 100 at.% V, a defect spinel structure for the intermediate region, 63–42 at.% V. At lower V-content, 18 and 7 at.%, a gamma-alumina-like solid solution was observed, shifted to larger d-spacing compared to pure γ-Al2O3. The microstructure changes from large columnar faceted grains for α-V2O3 to smaller equiaxed grains when lowering the vanadium content towards pure γ-Al2O3. Annealing in air resulted in formation of V2O5 crystals on the surface of the coating after annealing to 500 °C for 42 at.% V and 700 °C for 18 at.% V metal fraction respectively. The highest thermal stability was shown for pure γ-Al2O3-coating, which transformed to α-Al2O3 after annealing to 1100 °C. Highest hardness was observed for the Al-rich oxides, ~24 GPa. The latter decreased with increasing V-content, larger than 7 at.% V metal fraction. The measured hardness after annealing in air decreased in conjunction with the onset of further oxidation of the coatings.
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| 4. |
- Landälv, Ludvig, 1982-, et al.
(författare)
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Phase evolution of radio frequency magnetron sputtered Cr-rich (Cr,Zr)(2)O-3 coatings studied by in situ synchrotron X-ray diffraction during annealing in air or vacuum
- 2019
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Ingår i: Journal of Materials Research. - : CAMBRIDGE UNIV PRESS. - 0884-2914 .- 2044-5326. ; 34:22, s. 3735-3746
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Tidskriftsartikel (refereegranskat)abstract
- The phase evolution of reactive radio frequency (RF) magnetron sputtered Cr0.28Zr0.10O0.61 coatings has been studied by in situ synchrotron X-ray diffraction during annealing under air atmosphere and vacuum. The annealing in vacuum shows t-ZrO2 formation starting at similar to 750-800 degrees C, followed by decomposition of the alpha-Cr2O3 structure in conjunction with bcc-Cr formation, starting at similar to 950 degrees C. The resulting coating after annealing to 1140 degrees C is a mixture of t-ZrO2, m-ZrO2, and bcc-Cr. The air-annealed sample shows t-ZrO2 formation starting at similar to 750 degrees C. The resulting coating after annealing to 975 degrees C is a mixture of t-ZrO2 and alpha-Cr2O3 (with dissolved Zr). The microstructure coarsened slightly during annealing, but the mechanical properties are maintained, with no detectable bcc-Cr formation. A larger t-ZrO2 fraction compared with alpha-Cr2O3 is observed in the vacuum-annealed coating compared with the air-annealed coating at 975 degrees C. The results indicate that the studied pseudo-binary oxide is more stable in air atmosphere than in vacuum.
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| 5. |
- Landälv, Ludvig, 1982-
(författare)
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Physical vapor deposition and thermal stability of hard oxide coatings
- 2019
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- The state-of-the-art tools for machining metals are primarily based on a metal-ceramic composite (WC-Co) coated with different combinations of carbide, nitride, and oxide coatings. Combinations of these coating materials are optimized to withstand specific wear conditions. Oxide coatings, mainly α-Al2O3, are especially desired because of their high hot-hardness, chemical inertness with respect to the workpiece, and their low friction. The search for possible alloy elements, which may facilitate the deposition of such oxides by means of physical vapor deposition (PVD) techniques, has been the goal of this thesis. The sought alloy should form thermodynamically stable or metastable compounds, compatible with the temperature of use in metal cutting application. This thesis deals with process development and coating characterization of such new oxide alloy thin films, focusing on the Al-V-O, Al-Cr-Si-O, and Cr-Zr-O systems.Alloying aluminum oxide with iso-valent vanadium is a candidate for forming the desired alloys. Therefore, coatings of (Al1-xVx)2O3, with x ranging from 0 to 1, were deposited with reactive sputter deposition. X-ray diffraction showed three different crystal structures depending on V-metal fraction in the coating: α-V2O3 rhombohedral structure for 100 at.% V, a defect spinel structure for the intermediate region, (63 - 42 at.% V), and a gamma-alumina-like solid solution at lower V-content, (18 and 7 at.%), were observed, the later was shifted to larger d-spacing compared to the pure γ-Al2O3 sample obtained if deposited with only Al-target. Annealing the Al-rich coatings in air resulted in formation of V2O5 crystals on the surface of the coating after annealing to 500 °C for 42 at.% V and 700 °C for 18 at.% V metal fraction respectively. The highest thermal stability was shown for pure γ-Al2O3-coating which transformed to α-Al2O3 after annealing to 1100° C. Highest hardness was observed for the Al-rich oxides, ~24 GPa. The hardness then decreases with increasing V-content, larger than 7 at.% V metal fraction. Doping the Al2O3 coating with 7 at.% V resulted in a significant surface smoothening compared to the binary oxide. The measured hardness after annealing in air decreased in conjunction with the onset of further oxidation of the coatings. This work increases the understanding of this complicated material system with respect to possible phases formed with pulsed DC magnetron sputtering deposition as well as their response to annealing in air.The inherent difficulties of depositing insulating oxide films with PVD, requiring a closed electrical circuit, makes the investigation of process stability an important part of this research. In this context, I investigated the influence of adding small amount of Si in Al-Cr cathode on the coating properties in a pulsed DC industrial cathodic arc system and the plasma characteristics, process parameters, and coating properties in a lab DC cathodic arc system. Si was chosen here due to a previous study showing improved erosion behavior of Al-Cr-Si over pure Al-Cr cathode without Si incorporation in the coating. The effect of Si in the Al-Cr cathode in the industrial cathodic arc system showed slight improvements on the cathode erosion but Si was found in all coatings where Si was added in the cathode. The Si addition promoted the formation of the B1-like metastable cubic oxide phase and the incorporation led to reduced or equal hardness values compared to the corresponding Si-free processes. The DC-arc plasma study on the same material system showed only small improvements in the cathode erosion and process stability (lower pressure and cathode voltage) when introducing 5 at.% Si in the Al70Cr30-cathode. The presence of volatile SiO species could be confirmed through plasma analysis, but the loss of Si through these species was negligible, since the coating composition matched the cathode composition also under these conditions. The positive effect of added Si on the process stability at the cathode surface, should be weighed against Si incorporation in the coating. This incorporation seems to lead to a reduction in mechanical properties in the as-deposited coatings and promote the formation of a B1-like cubic metastable oxide structure for the (Al,Cr)2O3 oxide. This formation may or may not be beneficial for the final application since literature indicates a slight stabilization of the metastable phase upon Si-incorporation, contrary to the effect of Cr, which stabilizes the α-phase.The thermal stability of alloys for metal cutting application is crucial for their use. Previous studies on another alloy system, Cr-Zr-O, had shown solid solution, for Cr-rich compositions in that material system, in the sought corundum structure. The thermal stability of α-Cr0.28Zr0.10O0.61 coating deposited by reactive radio frequency (RF)-magnetron sputtering at 500 °C was therefore investigated here after annealing in vacuum up to 870 °C. The annealed samples showed transformation of α-(Cr,Zr)2O3 and amorphous ZrOx-rich areas into tetragonal ZrO2 and bcc-Cr. The instability of the α-(Cr,Zr)2O3 is surprising and possibly related to the annealing being done under vacuum, facilitating the loss of oxygen. Further in situ synchrotron XRD annealing studies on the α-Cr0.28Zr0.10O0.61 coating in air and in vacuum showed increased stability for the air annealed sample up to at least 975 °C, accompanied with a slight increase in ex-situ measured nanohardness. The onset temperature for formation of tetragonal ZrO2 was similar to that for isothermally vacuum annealing. The synchrotron-vacuum annealed coating again decomposed into bcc-Cr and t-ZrO2, with an addition of monoclinic–ZrO2 due to grain growth. The stabilization of the room temperature metastable tetragonal ZrO2 phase, due to surface energy effects present with small grains sizes, may prove to be useful for metal cutting applications. The observed phase segregation of α-(Cr,Zr)2O3 and formation of tetragonal ZrO2 with corresponding increase in hardness for this pseudobinary oxide system also opens up design routes for pseudobinary oxides with tunable microstructural and mechanical properties.
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| 6. |
- Landälv, Ludvig, 1982-, et al.
(författare)
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Structural evolution in reactive RF magnetron sputtered (Cr,Zr)2O3 coatings during annealing
- 2017
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Ingår i: Acta Materialia. - : PERGAMON-ELSEVIER SCIENCE LTD. - 1359-6454 .- 1873-2453. ; 131, s. 543-552
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Tidskriftsartikel (refereegranskat)abstract
- Reactive RF-magnetron sputtering is used to grow Cr0.28Zr0.10O0.61 coatings at 500 degrees C. Coatings are annealed at 750 degrees C, 810 degrees C, and 870 degrees C. The microstructure evolution of the pseudobinary oxide compound is characterized through high resolution state of the art HRSTEM and HREDX-maps, revealing the segregation of Cr and Zr on the nm scale. The as-deposited coating comprises cc-(Cr,Zr)(2)O-3 solid solution with a Zr-rich (Zr,Cr)O-x. amorphous phase. After annealing to 750 degrees C tetragonal ZrO2 nucleates and grows from the amorphous phase. The ZrO2 phase is stabilized in its tetragonal structure at these fairly low annealing temperatures, possibly due to the small grain size (below 30 nm). Correlated with the nucleation and growth of the tetragonal-ZrO2 phase is an increase in hardness, with a maximum hardness after annealing to 750 degrees C, followed by a decrease in hardness upon coarsening, bcc metallic Cr phase formation and loss of oxygen, during annealing to 870 degrees C. The observed phase segregation opens up future design routes for pseudobinary oxides with tunable microstructural and mechanical properties. (C) 2017 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.
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| 7. |
- Landälv, Ludvig, 1982-
(författare)
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Thin Film and Plasma Characterization of PVD Oxides
- 2017
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Licentiatavhandling (övrigt vetenskapligt/konstnärligt)abstract
- The state-of-the-art tools for machining metals are primarily based on a metal-ceramic composite(WC-Co) coated with different combinations of carbide, nitride and oxide coatings. Combinations of these coating materials are optimized to withstand specific wear conditions. Oxide coatings are especially desired because of their possible high hot hardness, chemical inertness with respect to the workpiece, and their low friction.This thesis deals with process and coating characterization of new oxide coatings deposited by physical vapor deposition (PVD) techniques, focusing on the Cr-Zr-O and Al-Cr-Si-O systems.The thermal stability of α-Cr0.28Zr0.10O0.61 deposited by reactive radio frequency (RF)-magnetron sputtering at 500 °C was investigated after annealing up to 870 °C. The annealed samples showed transformation of α-(Cr,Zr)2O3 and amorphous ZrOx-rich areas into tetragonal ZrO2 and bcc Cr. The instability of the α-(Cr,Zr)2O3 is surprising and possibly related to the annealing being done under vacuum, facilitating the loss of oxygen. The stabilization of the room temperature metastable tetragonal ZrO2 phase, due to surface energy effects, may prove to be useful for metal cutting applications. The observed phase segregation of α-(Cr,Zr)2O3 and formation of tetragonal ZrO2 with corresponding increase in hardness for this pseudo-binary oxide system also opens up design routes for pseudo-binary oxides with tunable microstructural and mechanical properties.The inherent difficulties of depositing insulating oxide films with PVD, demanding a closed circuit, makes the investigation of process stability an important part of this research. In this context, we investigated the influence of adding small amount of Si in Al-Cr cathode on plasma characteristics ,process parameters, and coating properties. Si was chosen here due to a previous study showing improved erosion behavior of Al-Cr-Si over pure Al-Cr cathode without Si incorporation in the coating.This work shows small improvements in cathode erosion and process stability (lower pressure and cathode voltage) when introducing 5 at % Si in the Al70Cr30-cathode. This also led to fewer droplets at low cathode current and intermediate O2 flow. A larger positive effect on cathode erosion was observed with respect to cleaning the cathode from oxide contamination by increasing cathode current with 50%. However, higher cathode current also resulted in increased amount of droplets in the coating which is undesirable. Through plasma analysis the presence of volatile SiO species could be confirmed but the loss of Si through volatile SiO species was negligible, since the coating composition matched the cathode composition. The positive effect of added Si on the process stability at the cathode surface should be weighed against Si incorporation in the coating. This incorporation may or may not be beneficial for the final application since literature states that Si promotes the metastable γ-phase over the thermodynamically stable α-phase of pure Al2O3, contrary to the effect of Cr, which stabilizes the α-phase.
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| 8. |
- Zhirkov, Igor, 1980-, et al.
(författare)
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Effect of Si on DC arc plasma generation from Al-Cr and Al-Cr-Si cathodes used in oxygen
- 2017
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Ingår i: Journal of Applied Physics. - : AMER INST PHYSICS. - 0021-8979 .- 1089-7550. ; 121:8
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Tidskriftsartikel (refereegranskat)abstract
- Al2O3 alloyed with Cr is an important material for the tooling industry. It can be synthesized from an arc discharge using Al-Cr cathodes in an oxygen atmosphere. Due to formation of Al-rich oxide islands on the cathode surface, the arc process stability is highly sensitive to oxygen pressure. For improved stability, the use of Al0.70Cr0.25Si0.05 cathodes has previously been suggested, where Si may reduce island formation. Here, we have investigated the effect of Si by comparing plasma generation and thin film deposition from Al0.7Cr0.3 and Al0.7Cr0.25Si0.05 cathodes. Plasma ion composition, ion energies, ion charge states, neutral species, droplet formation, and film composition have been characterized at different O-2 flow rates for arc currents of 60 and 90 A. Si and related compounds are detected in plasma ions and in plasma neutrals. Scanning electron microscopy and energy dispersive X-ray analysis show that the cathode composition and the film composition are the same, with Si present in droplets as well. The effect of Si on the process stability, ion energies, and ion charge states is found to be negligible compared to that of the arc current. The latter is identified as the most relevant parameter for tuning the properties of the reactive discharge. The present work increases the fundamental understanding of plasma generation in a reactive atmosphere, and provides input for the choice of cathode composition and process parameters in reactive DC arc synthesis.
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