Hard coatings like (Al,Cr)N are commonly used to protect cemented carbide cuttings tools from wear and corrosion. While such coatings increase the tool-lifetime, they also hinder the recycling effort of damaged tools. We report a new recycling strategy for coated cemented carbide tools by applying an interlayer between an arc evaporated Al0.7Cr0.3N coating and the WC-Co substrate. By selectively dissolving this interlayer in a concentrated basic solution, the coating spalls off the substrate, which is left intact. Four bases have been tested as saturated solutions: LiOH, NaOH, KOH, and CsOH, of which NaOH showed the highest reactivity. It was therefore used for subsequent investigations. Three different methods have been tested: (1) a metallic Al-doped interlayer region between substrate and coating can be removed in 3 h at 140 degrees C. Depositing an (2) Al0.7Cr0.3 or (3) Al0.9Cr0.1N interlayer leads to a significantly faster removal compared to the first method. Hereby a substrate could be fully de-coated in 4 h at only 110 degrees C. The reaction time was also decreased by pre-treating the samples in concentrated HCl, HNO3, or H2SO4 solutions at 90 degrees C for 10 min before subjecting the samples to the NaOH bath. Such treated substrates were fully de-coated in 3 h at only 90 degrees C. While HNO3 oxidized the substrates significantly, HCl and H2SO4 caused only negligible substrate damage.

The H2O and H2O2 molecules resemble each other in a multitude of ways as has been noted in the literature. Here, we present density functional theory (DFT) calculations for the H2O2(s) and H2O22H(2)O(s) crystals and make selected comparisons with ice polymorphs. The performance of a number of dispersion-corrected density functionals-both self-consistent and a posteriori ones-are assessed, and we give special attention to the D3 correction and its effects. The D3 correction to the lattice energies is large: for H2O2(s) the D3 correction constitutes about 25% of the lattice energy using PBE, much more for RPBE, much less for SCAN, and it primarily arises from non-H-bonded interactions out to about 5 & Aring;.The large D3 corrections to the lattice energies are likely a consequence of several effects: correction for missing dispersion interaction, the ability of D3 to capture and correct various other kinds of limitations built into the underlying DFT functionals, and finally some degree of cell-contraction-induced polarization enhancement. We find that the overall best-performing functionals of the twelve examined are optPBEvdW and RPBE-D3. Comparisons with DFT assessments for ices in the literature show that where the same methods have been used, the assessments largely agree.

The H2O and H2O2 molecules resemble each other in a multitude of ways as has been noted in the literature. Here, we present density functional theory (DFT) calculations for the H2O2(s) and H2O2·2H2O(s) crystals and make selected comparisons with ice polymorphs. The performance of a number of dispersion-corrected density functionals-both self-consistent and a posteriori ones-are assessed, and we give special attention to the D3 correction and its effects. The D3 correction to the lattice energies is large: for H2O2(s) the D3 correction constitutes about 25% of the lattice energy using PBE, much more for RPBE, much less for SCAN, and it primarily arises from non-H-bonded interactions out to about 5 Å.The large D3 corrections to the lattice energies are likely a consequence of several effects: correction for missing dispersion interaction, the ability of D3 to capture and correct various other kinds of limitations built into the underlying DFT functionals, and finally some degree of cell-contraction-induced polarization enhancement. We find that the overall best-performing functionals of the twelve examined are optPBEvdW and RPBE-D3. Comparisons with DFT assessments for ices in the literature show that where the same methods have been used, the assessments largely agree.

The influence of changes induced by ion irradiation on structure and thermal stability of metastable cu-bic (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, caus-ing the stress-free lattice parameter to expand from 4.170 to 4.206 A, 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. (C) 2022 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

AlCr-based hard nitride coatings with different chemical compositions and architectures have been successfully developed and applied over the last few decades. Coating properties are mainly influenced by deposition conditions and the Al/Cr content. The fcc structure is dominant for an Al-content up to Al0.7Cr0.3N and is preferred for most cutting applications. Different (AlCrX)N alloying concepts, including X = Si, W, B, V, have been investigated in order to enhance oxidation resistance and wear behaviour and to provide tribological properties. AlCr-based oxynitrides and even pure oxides (Al1−xCrx)2O3 with different crystalline structures have been explored. Multi- and nanolayered coatings within the AlCr materials system, as well as in combination with (TiSi)N, for example, have also been implemented industrially. The dominant deposition technology is the vacuum arc process. Recently, advanced high-power impulse magnetron sputtering (HiPIMS) processes have also been successfully applied on an industrial scale. This paper describes basic coating properties and briefly addresses the main aspects of the coating processes as well as selected industrial applications.

Thermal stability of protective coatings is one of the performance-defining properties for advanced cutting and forming applications as well as for energy conversion. To investigate the effect of oxygen incorporation on the high-temperature behavior of (Ti,Al)N, metastable cubic (Ti,Al)N and (Ti,Al)(OxN1-x) coatings are synthesized using reactive arc evaporation. X-ray diffraction of (Ti,Al)N and (Ti,Al)(OxN1-x) coatings reveals that spinodal decomposition is initiated at approximately 800°C, while the subsequent formation of wurtzite solid solution is clearly delayed from 1000°C to 1300°C for (Ti,Al)(OxN1-x) compared to (Ti,Al)N. This thermal stability enhancement can be rationalized based on calculated vacancy formation energies in combination with spatially-resolved composition analysis and calorimetric data: Energy dispersive X-ray spectroscopy and atom probe tomography data indicate a lower O solubility in wurtzite solid solution compared to cubic (Ti,Al)(O,N). Hence, it is evident that for the growth of the wurtzite, AlN-rich phase in (Ti,Al)N, only mobility of Ti and Al is required, while for (Ti,Al)(O,N), in addition to mobile metal atoms, also non-metal mobility is required. Prerequisite for mobility on the non-metal sublattice is the formation of non-metal vacancies which require larger temperatures than for the metal sublattice due to significantly larger magnitudes of formation energies for the non-metal vacancies compared to the metal vacancies. This notion is consistent with calorimetry data which indicate that the combined energy necessary to form and grow the wurtzite phase is larger by a factor of approximately two in (Ti,Al)(O,N) than in (Ti,Al)N, causing the here reported thermal stability increase.

The presence of macroparticles in cathodic arc evaporated coatings is considered to be one major drawback of this synthesis method. We demonstrate with transmission electron microscopy (TEM) and atom probe tomography (APT) that the thermal stability of a macroparticle in the industrial benchmark coating (Ti,Al)N does not limit the overall coating thermal stability up to 1000 ?C because metal-rich macroparticles exhibit a higher thermal stability than the c-(Ti,Al)N matrix. It is shown that the superior stability of the macroparticle is enabled by the self-organized formation of a c-TiN based diffusion barrier shell around the macroparticle.

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.

We propose that crystalline ionic hydrates constitute a valuable resource for benchmarking theoretical methods for aqueous ionic systems. Many such structures are known from the experimental literature, and they contain a large variety of water-water and ion-water structural motifs. Here we have collected a data set (CRYSTALWATER50) of 50 structurally unique "in-crystal" water molecules, involved in close to 100 nonequivalent O-H···O hydrogen bonds. A dozen well-known DFT functionals were benchmarked with respect to their ability to describe these experimental structures and their OH vibrational frequencies. We find that the PBE, RPBE-D3, and optPBE-vdW methods give the best H-bond distances and that anharmonic OH frequencies generated from B3LYP//optPBE-vdW energy scans outperform the other methods, i.e., here we performed B3LYP energy scans along the OH stretching coordinate while the rest of the structure was kept fixed at the optPBE-vdW-optimized positions.

It is well known that surface energy differences thermodynamically stabilize nanocrystalline γ-Al2O3 over α-Al2O3. Here, through correlative ab initio calculations and advanced material characterization at the nanometer scale, we demonstrate that the metastable phase formation of nanocrystalline TiAlN, an industrial benchmark coating material, is crystallite size-dependent. By relating calculated surface and volume energy contributions to the total energy, we predict the chemical composition-dependent phase boundary between the two metastable solid solution phases of cubic and wurzite Ti1−xAlxN. This phase boundary is characterized by the critical crystallite size d critical . Crystallite size-dependent phase stability predictions are in very good agreement with experimental phase formation data where x was varied by utilizing combinatorial vapor phase condensation. The wide range of critical Al solubilities for metastable cubic Ti1−xAlxN from x max = 0.4 to 0.9 reported in literature and the sobering disagreement thereof with DFT predictions can at least in part be rationalized based on the here identified crystallite size-dependent metastable phase formation. Furthermore, it is evident that predictions of critical Al solubilities in metastable cubic TiAlN are flawed, if the previously overlooked surface energy contribution to the total energy is not considered.

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We present periodic plane‐wave density functional theory (DFT) Perdew–Burke–Ernzerhof (PBE‐D2) calculations for four highly hydrated crystals, Na 2 CO 3 ·10H 2 O, MgSO 4 ·7H 2 O, MgSO 4 ·11H 2 O, and Al(NO 3 ) 3 ·9H 2 O, containing 37 structurally unique water molecules and 74 unique hydrogen bonds. The calculated R (H···O) distances lie in the range 1.60–2.05 Å, the anharmonic OH frequencies in the range 2570–3425 cm −1 , and the water dipole moments lie in the range 2.9–4.3 Debye, as calculated from the Wannier function centers and the nuclei. We present the following findings. (i) Our optimized intramolecular r (OH) distances are always larger than the gas‐phase value and thus more accurate than those derived from neutron diffraction experiments; (ii) The local in situ electric field over the molecule, calculated from the positions of the nuclei and the Wannier centers in the surrounding crystal, appears to be a good descriptor of the pertturbation from the water molecule's surroundings as the internal molecular properties ( r e , ν , μ ) are found to correlate well with the crystal‐generated electric field; (iii) We have added DFT‐calculated data points to the well‐known experimental ‘OH frequency versus R (H···O)' correlation curve in a region where the experimental data points are scarce; (iv) For all 37 water molecules, the Wannier centers located in the lone‐pair region, and those located in the OH bonds, displace about equally much due to the polarizing environment. Finally, we propose that our resulting 'OH frequency versus Wannier‐type electric field' correlation curve may constitute a useful tool for predicting OH vibrational frequencies from snapshots from PBE‐D2‐based ab initio molecular dynamics simulations of water‐containing systems. © 2015 Wiley Periodicals, Inc.

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We present experimental and calculated IR spectra of the water molecules in crystalline aluminium nitrate nonahydrate and a method to generate a realistic and well resolved isotope-isolated spectrum from periodic DFT calculations. Our sample crystal contains 18 structurally different OH groups and is a perfect benchmark compound to validate vibrational models and the structure-property relationship of bound water molecules. FTIR spectra (ATR technique) were recorded for the Al(NO3)3·9H2O crystal at 138 and 298 K, and due to a multitude of OH contributions and couplings, they are naturally poorly resolved and yield a broad OH band in the range 3500 to 2700 cm(-1) at both temperatures. Isotope-isolated IR spectra have the clear advantage over non-deuterated spectra that they are better resolved and easier to interpret - here we have extended the experimental study by simulating the isotope-isolated IR spectrum, using PBE-D2 and auxiliary B3LYP calculations and an anharmonic OH vibrational model. We find excellent agreement between the shapes and frequency ranges of the experimental and calculated OH spectral bands. We make use of four different vibrational models: (i) a harmonic lattice-dynamical model for the isotope-isolated crystal with 1 H among 71 D, (ii) a harmonic lattice-dynamical model for the normal undeuterated crystal involving all the vibrational couplings, (iii) a harmonic 1-dimensional uncoupled OH vibrational model, and (iv) the anharmonic variant of the previous model, which yields the final spectrum. We also use the individual frequencies, resolved by the calculations, to quantify new or extended relationships involving OH frequencies versus local electric fields and H-bond distances. We explore the correlation between OH frequency and molecular dipole moment for bound water molecules.

International Journal of Quantum ChemistryVolume 115, Issue 18 The Following Article will be Published in an Upcoming Issue of the International Journal of Quantum ChemistryFree Access H-bond and electric field correlations for water in highly hydrated crystals Anik Sen, Anik SenSearch for more papers by this authorPavlin D. Mitev, Pavlin D. MitevSearch for more papers by this authorAnders Eriksson, Anders ErikssonSearch for more papers by this authorKersti Hermansson, Kersti HermanssonSearch for more papers by this author Anik Sen, Anik SenSearch for more papers by this authorPavlin D. Mitev, Pavlin D. MitevSearch for more papers by this authorAnders Eriksson, Anders ErikssonSearch for more papers by this authorKersti Hermansson, Kersti HermanssonSearch for more papers by this author First published: 01 August 2015 https://doi.org/10.1002/qua.24990AboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinkedInRedditWechat No abstract is available for this article. Volume115, Issue18Special Issue: FemEx -Female Excellence in Theoretical and Computational ChemistrySeptember 15, 2015 RelatedInformation

Precise molecular-level information on the water molecule is precious, since it affects our interpretation of the role of water in a range of important applications of aqueous media. Here we propose that electronic structure calculations for highly hydrated crystals yield such information. Properties of nine structurally different water molecules (19 independent OO hydrogen bonds) in the Al(NO3)3·9H2O crystal have been calculated from DFT calculations. We combine the advantage of studying different water environments using one and the same compound and method (instead of comparing a set of independent experiments, each with its own set of errors) with the advantage of knowing the exact atomic positions, and the advantage of calculating properties that are difficult to extract from experiment. We find very large Wannier dipole moments for H2O molecules surrounding the cations: 4.0-4.3 D (compared to our calculated value of 1.83 D in the gas phase). These are induced by the ions and the H-bonds, while other water interactions and the relaxation of the internal water geometry in fact decrease the dipole moments. We find a good correlation between the water dipole moment and the OO distances, and an even better (non-linear) correlation with the average electric field over the molecule. Literature simulation data for ionic aqueous solutions fit quite well with our crystalline 'dipole moment vs. OO distance' curve. The progression of the water and cation charges from 'small clusters ⇒ large clusters ⇒ the crystal' helps explain why the net charges on all the water molecules are so small in the crystal.

DC arc plasma from Ti, Al, and Ti1-xAlx (x = 0.16, 0.25, 0.50, and 0.70) compound cathodes was characterized with respect to plasma chemistry and charge-state-resolved ion energy. Scanning electron microscopy, X-ray diffraction, and Energy-dispersive X-ray spectroscopy of the deposited films and the cathode surfaces were used for exploring the correlation between cathode-, plasma-, and film composition. Experimental work was performed at a base pressure of 10−6 Torr, to exclude plasma-gas interaction. The plasma ion composition showed a reduction of Al of approximately 5 at. % compared to the cathode composition, while deposited films were in accordance with the cathode stoichiometry. This may be explained by presence of neutrals in the plasma/vapour phase. The average ion charge states (Ti = 2.2, Al = 1.65) were consistent with reference data for elemental cathodes, and approximately independent on the cathode composition. On the contrary, the width of the ion energy distributions (IEDs) were drastically reduced when comparing the elemental Ti and Al cathodes with Ti0.5Al0.5, going from ∼150 and ∼175 eV to ∼100 and ∼75 eV for Ti and Al ions, respectively. This may be explained by a reduction in electron temperature, commonly associated with the high energy tail of the IED. The average Ti and Al ion energies ranged between ∼50 and ∼61 eV, and ∼30 and ∼50 eV, respectively, for different cathode compositions. The attained energy trends were explained by the velocity rule for compound cathodes, which states that the most likely velocities of ions of different mass are equal. Hence, compared to elemental cathodes, the faster Al ions will be decelerated, and the slower Ti ions will be accelerated when originating from compound cathodes. The intensity of the macroparticle generation and thickness of the deposited films were also found to be dependent on the cathode composition. The presented results may be of importance for choice of cathodes for thin film depositions involving compound cathodes.

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Thin films consisting of TiN nanocrystallites encapsulated in a fully percolated SiNy tissue phase are archetypes for hard and superhard nanocomposites. Here, we investigate metastable SiNy solid solubility in TiN and probe the effects of surface segregation during the growth of TiSiN films onto substrates that are either flat TiN(001)/MgO(001) epitaxial buffer layers or TiN(001) facets of length 1–5nm terminating epitaxial TiN(111) nanocolumns, separated by voids, deposited on epitaxial TiN(111)/MgO(111) buffer layers. Using reactive magnetron sputter deposition, the TiSiN layers were grown at 550°C and the TiN buffer layers at 900°C. On TiN(001), the films are NaCl-structure single-phase metastable Ti1−xSixN(001) with N/(Ti+Si)=1 and 0≤x≤0.19. These alloys remain single-crystalline to critical thicknesses hc ranging from 100±30nm with x=0.13 to 40±10nm with x=0.19. At thicknesses h>hc, the epitaxial growth front breaks down locally to form V-shaped polycrystalline columns with an underdense feather-like nanostructure. In contrast, the voided epitaxial TiN(111) columnar surfaces, as well as the TiN(001) facets, act as sinks for SiNy. For Ti1−xSixN layers with global average composition values 〈x〉=0.16, the local x value in the middle of Ti1−xSixN columns increases from 0.08 for columns with radius r⋍2nm to x=0.14 with r⋍4nm. The average out-of-plane lattice parameter of epitaxial nanocolumns encapsulated in SiNy decreases monotonically with increasing Si fraction 〈x〉, indicating the formation of metastable (Ti,Si)N solid solutions under growth conditions similar to those of superhard nanocomposites for which the faceted surfaces of nanograins also provide sinks for SiNy.