| 1. |
- Baben, Moritz to, et al.
(author)
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Unprecedented thermal stability of inherently metastable titanium aluminum nitride by point defect engineering
- 2017
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In: Materials Research Letters. - : TAYLOR & FRANCIS INC. - 2166-3831. ; 5:3, s. 158-169
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Journal article (peer-reviewed)abstract
- Extreme cooling rates during physical vapor deposition (PVD) allow growth of metastable phases. However, we propose that reactive PVD processes can be described by a gas-solid paraequilibrium defining chemical composition and thus point defect concentration. Weshow that this notion allows for point defect engineering by controlling deposition conditions. As example we demonstrate that thermal stability of metastable (Ti, Al) Nx, the industrial benchmark coating for wear protection, can be increased from 800 degrees C to unprecedented 1200 degrees C by minimizing the vacancy concentration. The thermodynamic approach formulated here opens a pathway for thermal stability engineering by point defects in reactively deposited thin films.
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| 2. |
- Evertz, Simon, et al.
(author)
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Boron Concentration Induced Co-Ta-B Composite Formation Observed in the Transition from Metallic to Covalent Glasses
- 2020
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In: Condensed Matter. - : MDPI. - 2410-3896. ; 5:1
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Journal article (peer-reviewed)abstract
- Due to their unique property combination of high strength and toughness, metallic glasses are promising materials for structural applications. As the behaviour of metallic glasses depends on the electronic structure which in turn is defined by chemical composition, we systematically investigate the influence of B concentration on glass transition, topology, magnetism, and bonding for B concentrations x = 2 to 92 at.% in the (Co6.8 +/- 3.9Ta)(100-x)B-x system. From an electronic structure and coordination point of view, the B concentration range is divided into three regions: Below 39 +/- 5 at.% B, the material is a metallic glass due to the dominance of metallic bonds. Above 69 +/- 6 at.%, the presence of an icosahedra-like B network is observed. As the B concentration is increased above 39 +/- 5 at.%, the B network evolves while the metallic coordination of the material decreases until the B concentration of 67 +/- 5 at.% is reached. Hence, a composite is formed. It is evident that, based on the B concentration, the ratio of metallic bonding to icosahedral bonding in the composite can be controlled. It is proposed that, by tuning the coordination in the composite region, glassy materials with defined plasticity and processability can be designed.
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| 3. |
- Hans, Marcus, et al.
(author)
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Spinodal decomposition of reactively sputtered (V0.64Al0.36)(0.49)N-0.51 thin films
- 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
- We investigate the decomposition mechanisms of metastable cubic (c-)(V0.64Al0.36)(0.49)N-0.51 thin films, grown by reactive high power pulsed magnetron sputtering, by combination of structural and compositional characterization at the nanometer scale with density functional theory (DFT) calculations. Based on thermodynamic considerations of partial derivative(2)Delta G/partial derivative x(2) < 0, spinodal decomposition is expected for c-V1-xAlxN with x >= 0.35. While no indications for spinodal decomposition are observable from laboratory and synchroton diffraction data after annealing in Ar atmosphere at 1300 degrees C, the formation of wurtzite (w-)AlN is evident after annealing at 900 degrees C by utilizing high energy synchrotron X-ray diffraction. However, the complementary nature of elemental V and Al maps, obtained by energy dispersive X-ray spectroscopy in scanning transmission electron microscopy mode, imply spinodal decomposition of c-(V0.64Al0.36)(0.49)N-0.51 into V- and Al-rich cubic nitride phases after annealing at 900 degrees C. These chemical modulations are quantified by atom probe tomography and maximum variations of x in V1-xAlxN are in the range of 0.36 to 0.50. The magnitude of the compositional modulations is enhanced after annealing at 1100 degrees C as x varies on average between 0.30 and 0.61, while the modulation wavelength remains unchanged at approximately 8 nm. Based on DFT data, the local x variation from 0.30 to 0.61 would cause lattice parameter variations from 4.111 to 4.099 angstrom. This difference corresponds to a shift of the (200) peak from 44.0 to 44.1 degrees. As the maximum decomposition-induced peak separation magnitude of 0.1 degrees is significantly smaller than the measured full width at half maximum of 0.4 degrees, spinodal decomposition cannot be unravelled by diffraction data. However, consistent with DFT predictions, spinodal decomposition in c-(V0.64Al0.36)(0.49)N-0.51 is revealed by chemical composition characterization at the nanometer scale.
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| 4. |
- Hans, Marcus, et al.
(author)
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Stress-Dependent Elasticity of TiAlN Coatings
- 2019
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In: Coatings. - : MDPI. - 2079-6412. ; 9:1
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Journal article (peer-reviewed)abstract
- We investigate the effect of continuous vs. periodically interrupted plasma exposure during cathodic arc evaporation on the elastic modulus as well as the residual stress state of metastable cubic TiAlN coatings. Nanoindentation reveals that the elastic modulus of TiAlN grown at floating potential with continuous plasma exposure is 7%-11% larger than for coatings grown with periodically interrupted plasma exposure due to substrate rotation. In combination with X-ray stress analysis, it is evident that the elastic modulus is governed by the residual stress state. The experimental dependence of the elastic modulus on the stress state is in excellent agreement with ab initio predictions. The macroparticle surface coverage exhibits a strong angular dependence as both density and size of incorporated macroparticles are significantly lower during continuous plasma exposure. Scanning transmission electron microscopy in combination with energy dispersive X-ray spectroscopy reveals the formation of underdense boundary regions between the matrix and TiN-rich macroparticles. The estimated porosity is on the order of 1% and a porosity-induced elastic modulus reduction of 5%-9% may be expected based on effective medium theory. It appears reasonable to assume that these underdense boundary regions enable stress relaxation causing the experimentally determined reduction in elastic modulus as the population of macroparticles is increased.
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| 5. |
- Holzapfel, Damian M., et al.
(author)
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Influence of ion irradiation-induced defects on phase formation and thermal stability of Ti0.27Al0.21N0.52 coatings
- 2022
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In: Acta Materialia. - : Elsevier. - 1359-6454 .- 1873-2453. ; 237
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Journal article (peer-reviewed)abstract
- The influence of changes induced by ion irradiation on structure and thermal stability of metastable cubic (Ti,Al)N coatings deposited by cathodic arc evaporation is systematically investigated by correlating experiments and theory. Decreasing the nitrogen deposition pressure from 5.0 to 0.5 Pa results in an ion flux-enhancement by a factor of three and an increase of the average ion energy from 15 to 30 eV, causing the stress-free lattice parameter to expand from 4.170 to 4.206 Å, while the chemical composition of Ti0.27Al0.21N0.52 remains unchanged. The 0.9% lattice parameter increase is a consequence of formation of Frenkel pairs induced by ion bombardment, as revealed by density functional theory (DFT) simulations. The influence of the presence of Frenkel pairs on the thermal stability of metastable Ti0.27Al0.21N0.52 is investigated by scanning transmission electron microscopy, differential scanning calorimetry, atom probe tomography and in-situ synchrotron X-ray powder diffraction. It is demonstrated that the ion flux and ion energy induced formation of Frenkel pairs increases the thermal stability as the Al diffusion enabled crystallization of the wurtzite solid solution is retarded. This can be rationalized by DFT predictions since the presence of Frenkel pairs increases the activation energy for Al diffusion by up to 142%. Hence, the thermal stability enhancement is caused by a hitherto unreported mechanism - the Frenkel pair impeded Al mobility and thereby retarded formation of wurtzite solid solution.
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