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We report the formation of mesoporous films consisting of SBA-15 particles grown directly onto substrates and their usage as catalysts in esterification of acetic acid and ethanol. The film thickness was altered between 80 nm and 750 nm by adding NH4F to the synthesis solution. The salt also affects the formation rate of the particles, and substrates must be added during the formation of the siliceous network in the solution. Various substrate functionalizations were tested and hydrophobic substrates are required for a successful film growth. We show that large surfaces (amp;gt; 75 cm(2)), as well as 3D substrates, can be homogenously coated. Further, the films were functionalized, either with acetic acid through co-condensation, or by coating the films with a thin carbon layer through exposure to furfuryl alcohol fumes followed by carbonization and sulfonation with H2SO4. The carbon-coated film was shown to be an efficient catalyst in the esterification reaction with acetic acid and ethanol. Due to the short, accessible mesopores, chemical variability, and possibility to homogenously cover large, rough surfaces. the films have a large potential for usage in various applications such as catalysis, sensing, and drug delivery. ; Funding Agencies|Swedish research council (VR) [2015-00624]; Swedish Energy Agency [P42022-1]; Vinnova (FunMat-II project) [2016-05156]; Swedish Government Strategic Research Area in Materials Science on Functional Materials at Linkoping University (Faculty Grant SFO-Mat-LiU) [2009-00971]; Knut and Alice Wallenberg Foundation [KAW 2012.0083]

The electronic structure, chemical bonding, and interface component in ZrN-AlN nanocomposites formed byphase separation during thin film deposition of metastable Zr1−xAlxN (x = 0.0, 0.12, 0.26, 0.40) are investigatedby resonant inelastic x-ray scattering, x-ray emission, and x-ray absorption spectroscopy and compared to firstprinciples calculations including transitions between orbital angular momentum final states. The experimentalspectra are compared with different interface-slab model systems using first principles all-electron full-potentialcalculations where the core states are treated fully relativistically. As shown in this work, the bulk sensitivity andelement selectivity of x-ray spectroscopy enables one to probe the symmetry and orbital directions at interfacesbetween cubic and hexagonal crystals. We show how the electronic structure develops from local octahedralbond symmetry of cubic ZrN that distorts for increasing Al content into more complex bonding. This results inthree different kinds of bonding originating from semicoherent interfaces with segregated ZrN and lamellar AlNnanocrystalline precipitates. An increasing chemical shift and charge transfer between the elements takes placewith increasing Al content and affects the bond strength and increases resistivity. ; Fulltext published under the terms of the Creative Commons Attribution 4.0 International license. https://creativecommons.org/licenses/by/4.0/ No changes have been made to the fulltext. Funded by Bibsam. Funding agencies: Swedish Research Council (VR) LiLi-NFM Linnaeus EnvironmentSwedish Research Council [621-2009-5258]; Swedish Government Strategic Research Area in Materials Science on Functional Materials at Linkoping University (Faculty Grant SFO-Mat-LiU) [2009 00971, 2

Time evolution of catalytic CO2 hydrogenation to methanol and dimethyl ether (DME) has been investigated in a high-temperature high-pressure reaction chamber where products accumulate over time. The employed catalysts are based on a nano-assembly composed of Cu nanoparticles infiltrated into a Zr doped SiOx mesoporous framework (SBA-15): Cu-Zr-SBA-15. The CO2 conversion was recorded as a function of time by gas chromatography-mass spectrometry (GC-MS) and the molecular activity on the catalyst's surface was examined by diffuse reflectance in-situ Fourier transform infrared spectroscopy (DRIFTS). The experimental results showed that after 14 days a CO2 conversion of 25% to methanol and DME was reached when a DME selective catalyst was used which was also illustrated by thermodynamic equilibrium calculations. With higher Zr content in the catalyst, greater selectivity for methanol and a total 9.5% conversion to methanol and DME was observed, yielding also CO as an additional product. The time evolution profiles indicated that DME is formed directly from methoxy groups in this reaction system. Both DME and methanol selective systems show the thermodynamically highest possible conversion. ; Funding agencies: EUs Erasmus-Mundus program (The European School of Materials Doctoral Programme - DocMASE); Knut och Alice Wallenbergs Foundation [KAW 2012.0083]; Swedish Government Strategic Research Area (SFO Mat LiU) [2009 00971]; Swedish Energy Agency [42022-1]

Ab initio-calculated ideal strength and toughness describe the upper limits for mechanical properties attainable in real systems and can, therefore, be used in selection criteria for materials design. We employ density-functional ab initio molecular dynamics (AIMD) to investigate the mechanical properties of defect-free rocksalt-structure (B1) TiN and B1 Ti1-xAlxN (x = 0.25, 0.5, 0.75) solid solutions subject to [001], [110], and [111] tensile deformation at room temperature. We determine the alloys ideal strength and toughness, elastic responses, and ability to plastically deform up to fracture as a function of the Al content. Overall, TiN exhibits greater ideal moduli of resilience and tensile strengths than (Ti,Al)N solid solutions. Nevertheless, AIMD modeling shows that, irrespective of the strain direction, the binary compound systematically fractures by brittle cleavage at its yield point. The simulations also indicate that Ti0.5Al0.5N and Ti0.25Al0.75N solid solutions are inherently more resistant to fracture and possess much greater toughness than TiN due to the activation of local structural transformations (primarily of B1 -amp;gt; wurtzite type) beyond the elastic-response regime. In sharp contrast, (Ti,Al)N alloys with 25% Al exhibit similar brittleness as TiN. The results of this work are examples of the limitations of elasticity-based criteria for prediction of strength, brittleness, ductility, and toughness in materials able to undergo phase transitions with loading. Comparing present and previous findings, we suggest a general principle for design of hard ceramic solid solutions that are thermodynamically inclined to dissipate extreme mechanical stresses via transformation toughening mechanisms. ; Funding Agencies|Competence Center Functional Nanoscale Materials (FunMat-II) (Vinnova Grant)Vinnova [2016-05156]; Swedish Research Council (VR)Swedish Research Council [2019-05600]; Swedish Government Strategic Research Area in Materials Science on Functional Materials at Linkoping University (Faculty Grant SFO-Mat-LiU) [2009-00971]; Knut and AliceWallenberg Foundation throughWallenberg Scholar project [2018.0194]; Olle Engkvist Foundation

In this work, we discuss the mixing thermodynamics of cubic (B1) Ti1-xAlxN/TiN(001) multilayers. We show that interfacial effects suppress the mixing enthalpy compared to bulk Ti1-xAlxN. The strongest stabilization occurs for compositions in which the mixing enthalpy of bulk Ti1-xAlxN has its maximum. The effect is split into a strain and an interfacial (or chemical) contribution, and we show that both contributions are significant. An analysis of the local atomic structure reveals that the Ti atoms located in the interfacial layers relax significantly different from those in the other atomic layers of the multilayer. Considering the electronic structure of the studied system, we demonstrate that the lower Ti-site projected density of states at epsilon(F) in the Ti1-xAlxN/TiN multilayers compared to the corresponding monolithic bulk explains a decreased tendency toward decomposition. ; Funding Agencies|Swedish Foundation for Strategic Research (SSF) project SRL [10-0026]; Erasmus Mundus Joint European Doctoral Programme DocMASE; Multiscale computational-design of novel hard nanostructure coatings; Swedish Research Council (VR) [2015-04391, 621-2012-4401, 2014-4750]; Grant of Ministry of Education and Science of the Russian Federation [14.Y26.31.0005]; Tomsk State University Academic D. I. Mendeleev Fund Program [8.1.18.2015]; LiLi-NFM; Swedish Government Strategic Research Area Grant in Materials Science

In this study we explore the cutting performance of ZrAlN coatings. WC:Co cutting inserts coated by cathodic arc evaporated Zr1-xAlxN coatings with x between 0 and 0.83 were testeciin a longitudinal turning operation. The progress of wear was studied by optical microscopy and the used inserts were studied by electron microscopy. The cutting performance was correlated to the coating composition and the best performance was found for the coating with highest Al-content consisting of a wurtzite ZrAlN phase which is assigned to its high thermal stability. Material from the work piece was observed to adhere to the inserts during turning and the amount of adhered material and its chemical composition is independent on the Al-content of the coating. (C) 2015 Elsevier B.V. All rights reserved. ; Funding Agencies|Vinnova (Swedish Governmental Agency for Innovation Systems) through the VINN Excellence Center on Functional Nanoscale Materials (Fun Mat)

Available information concerning the elastic moduli of refractory carbides at temperatures (T) of relevance for practical applications is sparse and/or inconsistent. Ab initio molecular dynamics (AIMD) simulations at T = 300, 600, 900, and 1200 K are carried out to determine the temperature-dependences of the elastic constants of rocksalt-structure (B1) TiC, ZrC, HfC, VC, TaC compounds, as well as high-entropy (Ti,Zr,Hf,Ta,W)C and (V,Nb, Ta,Mo,W)C. The second-order elastic constants are calculated by least-square fitting of the analytical expressions of stress/strain relationships to simulation results obtained from three tensile and three shear deformation modes. Sound-velocity measurements are employed to validate AIMD values of bulk, shear, and elastic moduli of single-phase B1 (Ti,Zr,Hf,Ta,W)C and (V,Nb,Ta,Mo,W)C at ambient conditions. In comparison with the predictions of previous ab initio calculations - where the extrapolation of finite-temperature elastic properties accounted for thermal expansion while neglecting intrinsic vibrational effects - AIMD simulations produce a softening of shear elastic moduli with T in closer agreement with experiments. The results show that TaC is the system which exhibits the highest elastic resistances to tensile and shear deformation up to 1200 K, and indicate the (V,Nb,Ta,Mo,W)C system as candidate for applications that require superior toughness at room as well as elevated temperatures. (C) 2021 The Author(s). Published by Elsevier Ltd. ; Funding Agencies|Swedish Research CouncilSwedish Research CouncilEuropean Commission [VR-2015-04630]; Center for High Performance Computing (PDC) in Stockholm; High Performance Computing Center North (HPC2N) in Umea, Sweden; Competence Center Functional NanoscaleMaterials (FunMat-II) (Vinnova Grant) [2016-05156]; Swedish Research Council (VR)Swedish Research Council [2019-05600]; Swedish Government Strategic Research Area in Materials Science on Functional Materials at Linkoping University (Faculty Grant SFO-Mat-LiU) [200900971]; Knut and Alice Wallenberg Foundation through Wallenberg Scholar Project [2018.0194]; Olle Engkvist Foundation; Office of Naval Research ONR-MURIMURIOffice of Naval Research [N00014-15-1-2863]; Ministry of Science and Higher Education of the Russian Federation of NUSTMISIS [K2-2020-026, 211]

Atom probe tomography was used to compare Na and Sr modified Al-Si hypoeutectic alloys. Both Na and Sr promote the formation of nanometre-sized clusters in the Si eutectic phase. Compositional analyses of the clusters show an Al:Sr ratio of 2.92 +/- 0.46 and an Al:Na ratio of 1.07 +/- 0.23. It is proposed that SrAl2Si2 and NaAlSi clusters are formed at the Si/liquid interface and take part in the modification process by altering the eutectic Si growth. ; Funding Agencies|German Federal Ministry of Economics and Technology [AiF 17204 N]; European Regional Development Fund (AME-Lab) [C/4-EFRE-13/2009/Br]; German Research Foundation (DFG); Federal State Government of Saarland [INST 256/298-1 FUGG]; Erasmus Mundus Doctoral Programme DocMASE of the European Commission [FPA 2011-0020]; VINNOVA Strategic Faculty Grant VINNMER Marie Curie Chair [2011-03464]; Major International (Regional) Joint Research Project from China [51420105005]

We develop a method to accurately and efficiently determine the vibrational free energy as a function of temperature and volume for substitutional alloys from first principles. Taking Ti1-xAlxN alloy as a model system, we calculate the isostructural phase diagram by finding the global minimum of the free energy corresponding to the true equilibrium state of the system. We demonstrate that the vibrational contribution including anharmonicity and temperature dependence of the mixing enthalpy have a decisive impact on the calculated phase diagram of a Ti1-xAlxN alloy, lowering the maximum temperature for the miscibility gap from 6560 to 2860 K. Our local chemical composition measurements on thermally aged Ti0.5Al0.5N alloys agree with the calculated phase diagram. ; Funding Agencies|Swedish Foundation for Strategic Research Programs (Stiftelsen for Strategisk Forskning) [SRL10-0026, RMA08-0069]; FUNCASE; Swedish Research Council (Vetenskapsradet) [2012-4401, 621-2011-4426, 2015-04391, 637-2013-7296, 621-2011-4417, 330-2014-6336]; Swedish Government Strategic Research Area in Materials Science on Functional Materials at Linkoping University (Faculty Grant SFO-Mat-LiU) [2009 00971]; Swedish Governmental Agency for Innovation Systems (Vinnova) through the M-ERA.net project MC2; SECO Tools AB; Marie Sklodowska Curie Actions, Cofund [INCA 600398]; Erasmus Mundus Joint European Doctoral Programme DocMASE; Ministry of Education and Science of the Russian Federation [K2-2016-013]; Deutsche Forschungsgemeinschaft; Federal State Government of Saarland [INST 256/298-1 FUGG]

Ti1-x(AlySi1-y)xN coatings covering a wide compositional range, 0.38 < x < 0.76 and 0.68 ≤ y ≤ 1.00, are deposited to investigate the influence of Al+/Si+ ion irradiation on microstructural and mechanical properties. The samples are grown in Ar/N2 atmosphere by the hybrid high-power impulse and dc magnetron co-sputtering (HiPIMS/DCMS) method with substrate bias synchronized to the Al+/Si+-rich portion of the HiPIMS pulses. Two Ti targets are operated in DCMS mode, while one AlSi target is operated in HiPIMS mode. Four different AlSi target compositions are used: Al1.0Si0.0, Al0.9Si0.1, Al0.8Si0.2, and Al0.6Si0.4. X-ray diffractometry reveals that films without Si (i.e., y = 1.0) have high Al solubility in NaCl-structure, c-TiAlN, up to x ≤ 0.67 no w-AlN is detected. Once Si (y < 1.0) is introduced the Al solubility limit decreases, but remains higher than other PVD techniques, along with grain refinement and the formation of a SiNz rich tissues phase, as shown by transmission electron microscopy. The nanoindentation hardness is high (~ 30 GPa) for all films that do not contain the w-AlN phase. All the coatings have compressive stresses lower than -3 GPa. Interestingly, a range of films with different compositions displayed both high hardness (~ 30 GPa) and low residual stress (σ < 0.5 GPa). Such an unique combination of properties highlights the benefits of using HiPIMS/DCMS configuration with metal-ion-synchronized substrate bias, which utilizes the Al+/Si+ supplantation effect and minimizes the Ar+ incorporation. ; Funding agencies: VINNOVA (FunMat-II project grant no. 2016-05156), the Swedish Research Council (grants no 2017-03813 and 2017-06701), the Swedish government strategic research area grant AFM – SFO MatLiU (2009-00971), the Swedish Research Council VR-RFI (#2017-00646_9) and the Swedish Foundation for Strategic Research (contract RIF14-0053)

The differences in work function (W.F.) and cohesive energy (C.E.) of the phases constituting the cathode, plays an important role in the formation of the converted layer at its near-surface region during cathodic arc deposition. As a consequence, this also affects the deposition conditions for the coatings. In this study, we explore the effect of W.F. and C.E. of the constituent phases during arc evaporation by utilizing two kinds of customized Ti-50 at.% Al cathodes with different phase compositions. Our results show that during reactive arc evaporation the disparity in W.F. and C.E. among the constituent phases of Ti-50 at.% Al cathodes leads to preferential erosion of the phases with lower W.F. and C.E. The aforementioned preferential erosion begets higher surface roughness on the Ti-50 at.% Al cathode with a wider range of W.F. and C.E. disparity. It is also observed that the thermal conductivity of the Ti-50 at.% Al cathode plays a dominant role in the deposition rate of Ti-Al-N coating. This article also presents how the surface geometry of the cathode in the presence of arc guiding magnetic field significantly influences the microstructure of the deposited coatings. ; Funding agencies: VINN Excelence Excellence Center in Research and Innovation on Functional Nanoscale Materials (FunMat-II) by the Swedish Governmental Agency for Innovation Systems [2016-05156] ; FunMat-II

Aspects on the phase stability and mechanical properties of nitrogen deficient (Ti0.54Al0.46)N-y alloys were investigated. Solid solution alloys of (Ti,Al)N were grown by cathodic arc deposition. The kinetic energy of the impinging ions was altered by varying the substrate bias voltage from -30V to -80 V. Films deposited with a high bias value of -80V showed larger lattice parameter, finer columnar structure, and higher compressive residual stress resulting in higher hardness than films biased at -30V when comparing their as-deposited states. At elevated temperatures, the presence of nitrogen vacancies and point defects (anti-sites and self-interstitials generated by the ion-bombardment during coating deposition) in (Ti0.54Al0.46)N-0.87 influence the driving force for phase separation. Highly biased nitrogen deficient films have point defects with higher stability during annealing, which cause a delay of the release of the stored lattice strain energy and then accelerates the decomposition tendencies to thermodynamically stable c-TiN and w-AlN. Low biased nitrogen deficient films have retarded phase transformation to w-AlN, which results in the prolongment of age hardening effect up to 1100 degrees C, i.e., the highest reported temperature for Ti-Al-N material system. Our study points out the role of vacancies and point defects in engineering thin films with enhanced thermal stability and mechanical properties for high temperature hard coating applications. Published by AIP Publishing. ; Funding Agencies|European Unions Erasmus Mundus doctoral program in Materials Science and Engineering (DocMASE); Swedish Research Council [621-2012-4401]; Swedish government strategic research area grant AFM - SFO MatLiU [2009-00971]; VINNOVA [2013-02355]; DFG; federal state government of Saarland [INST 256/298-1 FUGG]; European Regional Development Fund [AME-Lab C/4-EFRE-13/2009/Br]

The influence of pulsed substrate bias duty cycle on the growth, microstructure, and defects of Ti1-xAlxN coatings grown by cathodic arc deposition was investigated. Ti1-xAlxN coatings of varying compositions (x = 0.56, 0.38, 0.23) were deposited on cemented carbide substrates with 10, 25, 50, and 95% duty cycles of 50 V pulsed-bias under 10 Pa of pure N-2 gas. Coatings grown at low duty cycles (10 and 25%) showed strongly textured, underdense coatings with facetted columns and low amount of lattice defects. Applying higher duty cycles (50 and 95%) produced coatings that have denser microstructures, less preferred orientation, increasing compressive stresses and increased lattice defect densities. Our study elucidates how duty cycle variation not only changes the overall average energy supplied at the growth front but also kinetically influences the coating growth and thus microstructure and defect structure. ; Funding Agencies|VINNOVA (FunMat-II)Vinnova [2016-05156]; Swedish Research CouncilSwedish Research CouncilEuropean Commission [2017-03813, 2017-06701]; Swedish government strategic research area grant AFM -SFO MatLiU [200900971]; Swedish Research Council VR-RFISwedish Research Council [201700646_9]; Swedish Foundation for Strategic ResearchSwedish Foundation for Strategic Research [RIF14-0053]