Strong compositional-dependent elastic properties have been observed theoretically and experimentally in Ti1−xAlxN alloys. The elastic constant, C11, changes by more than 50% depending on the Al-content. Increasing the Al-content weakens the average bond strength in the local octahedral arrangements resulting in a more compliant material. On the other hand, it enhances the directional (covalent) nature of the nearest neighbor bonds that results in greater elastic anisotropy and higher sound velocities. The strong dependence of the elastic properties on the Al-content offers new insight into the detailed understanding of the spinodal decomposition and age hardening in Ti1−xAlxN alloys.

We use a combination of in-situ x-ray scattering experiments during annealing and phasefield simulations to study the strain and microstructure evolution during decomposition of

Ti1−xAlxN is a technologically important alloy that undergoes a process of high temperature age-hardening that is strongly influenced by its elastic properties. We have performed first principles calculations of the elastic constants and anisotropy using the newly developed symmetry imposed force constant temperature dependent effective potential method, that include lattice vibrations and therefore the effects of temperature, including thermal expansion and intrinsic anharmonicity. These are compared with in situ high temperature x-ray diffraction measurements of the lattice parameter. We show that anharmonic effects are crucial to the recovery of finite temperature elasticity. The effects of thermal expansion and intrinsic anharmonicity on the elastic constants are of the same order, and cannot be considered separately. Furthermore, the effect of thermal expansion on elastic constants is such that the volume change induced by zero point motion has a significant effect. For TiAlN, the elastic constants soften non-uniformly with temperature: C11 decreases substantially when the temperature increases for all compositions, resulting in an increased anisotropy. These findings suggest that an increased Al content and annealing at higher temperatures will result in a harder alloy.

Funding agencies: Swedish Research Council (VR) [621-2011-4426, 621-2012-4401, 637-2013-7296]; Swedish Foundation for Strategic Research (SSF) [RMA08-0069, SRL10-0026]; VINNOVA [2013-02355(MC2)]; Erasmus Mundus Joint European Doctoral Program DocMASE; Ministry of Education

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This paper describes details of the spinodal decomposition and coarsening in metastable cubic Ti0.33Al0.67N and Ti0.50Al0.50N coatings during isothermal annealing, studied by in-situ small angle x-ray scattering, in combination with phase field simulations. We show that the isostructural decomposition occurs in two stages. During the initial stage, spinodal decomposition, of the Ti0.50Al0.50N alloy, the phase separation proceeds with a constant compositional wavelength of ∼2.8 nm of the AlN- and TiN-rich domains. The time for spinodal decomposition depends on annealing temperature as well as alloy composition. After the spinodal decomposition, the coherent cubic AlN- and TiN-rich domains coarsen. The coarsening rate is kinetically limited by diffusion, which allowed us to estimate the diffusivity and activation energy of the metals to 1.4 × 10−6 m2 s−1 and 3.14 eV at−1, respectively.

In the present work, we have studied the decomposition of arc-evaporated Ti 0.55 Al 0.45 N and Ti 0.36 Al 0.64 N during heat treatments in vacuum by in situ synchrotron wide-angle X-ray scattering primarily to characterize the kinetics of the phase transformation of AlN from the cubic (c) NaCl structure to the hexagonal (h) wurtzite structure. In addition, in situ small-angle X-ray scattering measurements were conducted to explore details of the wavelength evolution of the spinodal decomposition, thus providing information about the critical size of the c-AlN-rich domains prior to the onset of the transformation to h-AlN. We report the fractional cubic to hexagonal transformation of AlN in Ti 1Àx Al x N as a function of time and extract activation energies between 320 and 350 kJ mol À1 depending on the alloy composition. The onset of the hexagonal transformation occurs $50 K lower in Ti 0.36 Al 0.64 N compared to Ti 0.55 Al 0.45 N where the high Al content alloy also has a significantly higher transformation rate. A critical wavelength for the cubic domains of $13 nm was observed for both alloys. Scanning transmission electron microscopy shows a c-TiN/h-AlN microstructure with a striking morphology resemblance to the c-TiN/c-AlN microstructure present prior to the hexagonal transformation.

Small-angle x-ray scattering was used to study in situ decomposition of an arc evaporated TiAlN coating into cubic-TiN and cubic-AlN particles at elevated temperature. At the early stages of decomposition particles with ellipsoidal shape form, which grow and change shape to spherical particles at higher temperatures. The spherical particles grow at a rate of 0.18 Å/°C while coalescing.

Effects of thermal annealing on the structural, mechanical, and tribological properties of hard fluorinated carbon films deposited by plasma enhanced chemical vapor deposition Evolution of the growth stress, stiffness, and microstructure of alumina thin films during vapor depositionThe influence of substrate bias and chemical composition on the formed microstructure and resulting hardness of arc evaporated Zr 1Àx Al x N films in the compositional span 0.12 x 0.74 is investigated. A cubic ZrAlN phase is formed at low aluminum contents (x 0.38) whereas for a high Al-content, above x ¼ 0.70, a single-phase hexagonal structure is obtained. For intermediate Al-contents, a two-phase structure is formed. The cubic structured films exhibit higher hardness than the hexagonal structured ones. A low bias results in N-rich films with a partly defect-rich microstructure while a higher substrate bias decreases the grain size and increases the residual stress in the cubic ZrAlN films. Recrystallization and out-diffusion of nitrogen from the lattice in the cubic ZrAlN films takes place during annealing at 800 C, which results in an increased hardness. The cubic ZrAlN phase is stable to annealing temperatures of 1000 C while annealing at higher temperature results in nucleation and growth of hexagonal AlN. In the high Al-content ZrAlN films, formation of ZrN-and AlN-rich domains within the hexagonal lattice during annealing at 1000 C improves the mechanical properties.

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