| 1. |
- Casillas Trujillo, Luis, et al.
(författare)
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Experimental and theoretical evidence of charge transfer in multi-component alloys : how chemical interactions reduce atomic size mismatch
- 2021
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Ingår i: Materials Chemistry Frontiers. - : Royal Society of Chemistry. - 2052-1537. ; 5:15, s. 5746-5759
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Tidskriftsartikel (refereegranskat)abstract
- Ab initio simulations of a multi-component alloy using density functional theory (DFT) were combined with experiments on thin films of the same material using X-ray photoelectron spectroscopy (XPS) to study the connection between the electronic and atomic structures of multi-component alloys. The DFT simulations were performed on an equimolar HfNbTiVZr multi-component alloy. Structure and charge transfer were evaluated using relaxed, non-relaxed, as well as elemental reference structures. The use of a fixed sphere size model allowed quantification of charge transfer, and separation into different contributions. The charge transfer was generally found to follow electronegativity trends and results in a reduced size mismatch between the elements, and thus causes a considerable reduction of the lattice distortions compared to a traditional assumption based on tabulated atomic radii. A calculation of the average deviation from the average radius (i.e. the so-called δ-parameter) based on the atomic Voronoi volumes gave a reduction of δ from ca. 6% (using the volumes in elemental reference phases) to ca. 2% (using the volumes in the relaxed multi-component alloy phase). The reliability of the theoretical results was confirmed by XPS measurements of a Hf22Nb19Ti18V19Zr21 thin film deposited by sputter deposition. The experimentally observed core level binding energy shifts (CLS), as well as peak broadening due to a range of chemical surroundings, for each element showed good agreement with the calculated DFT values. The single solid solution phase of the sample was confirmed by X-ray diffraction (XRD) and transmission electron microscopy (TEM) including energy dispersive spectroscopy (EDS) with nm-resolution. These observations show that the HfNbTiVZr solid solution phase is non-ideal, and that chemical bonding plays an important part in the structure formation, and presumably also in the properties. Our conclusions should be transferable to other multi-component alloy systems, as well as some other multi-component material systems, and open up interesting possibilities for the design of material properties via the electronic structure and controlled charge transfer between selected metallic elements in the materials.
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| 2. |
- Fritze, Stefan, et al.
(författare)
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Elemental distribution and fracture properties of magnetron sputtered carbon supersaturated tungsten films
- 2024
-
Ingår i: Surface & Coatings Technology. - : Elsevier BV. - 0257-8972 .- 1879-3347. ; 477
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Tidskriftsartikel (refereegranskat)abstract
- The combination of strength and toughness is a major driving force for alloy design of protective coatings, and nanocrystalline tungsten (W)-alloys have shown to be promising candidates for combining strength and toughness. Here we investigate the elemental distribution and the fracture toughness of carbon (C) alloyed W thin films prepared by non-reactive magnetron sputtering. W:C films with up to ~4 at.% C crystallize in a body-centered-cubic structure with a strong 〈hh0〉texture, and no additional carbide phases are observed in the diffraction pattern. Atom probe tomography and X-ray photoelectron spectroscopy confirmed the formation of such a supersaturated solid solution. The pure W film has a hardness ~13 GPa and the W:C films exhibit a peak hardness of ~24 GPa. In-situ micromechanical cantilever bending tests show that the fracture toughness decreases from ~4.5 MPa·m1/2 for the W film to ~3.1 MPa·m1/2 for W:C films. The results show that C can significantly enhance the hardness of W thin films while retaining a high fracture toughness.
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| 3. |
- Kumar, Ankit, et al.
(författare)
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Effect of in situ electric-field-assisted growth on antiphase boundaries in epitaxial Fe3O4 thin films on MgO
- 2018
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Ingår i: Physical Review Materials. - : American Physical Society. - 2475-9953. ; 2:5
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Tidskriftsartikel (refereegranskat)abstract
- Antiphase boundaries (APBs) normally form as a consequence of the initial growth conditions in all spinel ferrite thin films. These boundaries result from the intrinsic nucleation and growth mechanism, and are observed as regions where the periodicity of the crystalline lattice is disrupted. The presence of APBs in epitaxial films of the inverse spinel Fe3O4 alters their electronic and magnetic properties due to strong antiferromagnetic (AF) interactions across these boundaries. We explore the effect of using in-plane in situ electric-field-assisted growth on the formation of APBs in heteroepitaxial Fe3O4(100)/MgO(100) thin films. The electric-field-assisted growth is found to reduce the AF interactions across APBs and, as a consequence, APB-free thin-film-like properties are obtained, which have been probed by electronic, magnetic, and structural characterization. The electric field plays a critical role in controlling the density of APBs during the nucleation process by providing an electrostatic force acting on adatoms and therefore changing their kinetics. This innovative technique can be employed to grow epitaxial spinel thin films with controlled AF interactions across APBs.
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| 4. |
- Lewin, Erik, 1979-
(författare)
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Design of carbide-based nanocomposite coatings
- 2009
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- In this thesis research on synthesis, microstructure and properties of carbide-based coatings is reported. These coatings are electrically conducting, and can be tailored for high hardness, low friction and wear, along with load-adaptive behaviour. Tailoring these properties is achieved by controlling the relative phase content of the material. Coatings have been synthesised by dc magnetron sputtering, and their structures have been characterised, mainly by X-ray photoelectron spectroscopy and X-ray diffraction.It has been shown that nanocomposites comprising of a nanocrystalline transition metal carbide (nc-MeCx, Me = Ti, Nb or V) and an amorphous carbon (a-C) matrix can result in low contact resistance in electrical contacts. Such materials also exhibit low friction and high resistance to wear, making them especially suitable for application in sliding contacts. The lowest contact resistance is attained for small amounts of the amorphous carbon phase.It has been shown that specific bonding structures are present in the interface between nc-TiCx and the a-C phases in the nanocomposite. It was found in particular that Ti3d and C2p states are involved, and that considerable charge transfer occurs across the interface, thereby influencing the structure of the carbide.Further design possibilities were demonstrated for TiCx-based nanocomposites by alloying them with weakly carbide-forming metals, i.e., Me = Ni, Cu or Pt. Metastable supersaturated solid solution carbides, (T1-xMex)Cy, were identified to result from this alloying process. The destabilisation of the TiCx-phase leads to changes in the phase distribution in the deposited nanocomposites, thus providing further control over the amount of carbon phase formed. Additional design possibilities became available through the decomposition of the metastable (Ti1-xMex)Cy phase through an appropriate choice of annealing conditions, yielding either more carbon phase or a new metallic phase involving Me. This alloying concept was also studied theoretically for all 3d transition metals using DFT techniques.It has also been demonstrated that Ar-ion etching (commonly used in the analysis of carbide based nanocomposites) can seriously influence the result of the analysis, especially for materials containing metastable phases. This implies that more sophisticated methods, or considerable care are needed in making these analyses, and that many of the earlier published results could well be in error.
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| 5. |
- Osinger, Barbara, et al.
(författare)
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Charge transfer effects in (HfNbTiVZr)C – shown by ab-initio calculations and X-ray photoelectron spectroscopy
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Tidskriftsartikel (övrigt vetenskapligt/konstnärligt)abstract
- Considering charge transfer effects and the variability of the bonding between elements with different electronegativity opens up a deeper understanding of the electronic structure and as a result many of the properties in high entropy related materials. This study investigates the importance of the diverse bonding and chemical environments when discussing multicomponent carbide materials. A combination of ab initio calculations and X-ray photoelectron spectroscopy (XPS) was used to investigate the electronic structure of multicomponent thin films based on the (HfNbTiVZr)C system. The charge transfer was quantified theoretically using relaxed and non-relaxed multicomponent as well as binary carbide reference structures, employing a fixed sphere model. High-resolution XPS spectra from (HfNbTiVZr)C magnetron sputtered thin films displayed core level binding energy shifts and broadening effects as a result of the complex chemical environment. Charge transfer effects and a changed electronic structure in the multicomponent material, compared with the reference binary carbides, are observed both experimentally and in the DFT simulations. The observed effects loosely follow electronegativity considerations, leading to a deviation from an ideal solid solution structure assuming non-distinguishable chemically equivalent environments.
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| 6. |
- Osinger, Barbara, 1995-
(författare)
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Investigation of compositionally complex refractory metal based thin films
- 2024
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- The search for new and improved materials has led to the discovery and establishment of compositionally complex or high-entropy materials. The work in this thesis is focused on the investigation of new compositionally complex materials based on the refractory metals of groups 4-6. The materials in this work were synthesised using non-reactive dc magnetron sputtering and three material systems have been studied: HfNbTiVZr-C, CrTiTaWNb-C and Nb-Mo-C. In the context of compositionally complex materials, this thesis aims to contribute specifically to questions regarding (i) the prediction of phase formation and stability (ii) the chemical interaction between atoms (iii) the correlation between the material properties and compositional complexity. The prediction of phase formation and stability using calculated phase diagram (CALPHAD) methods was studied in the HfNbTiVZr-C system. The findings suggest that CALPHAD methods are promising predictive tools, although kinetic effects during synthesis need to be taken into consideration. Furthermore, theoretical, and experimental evidence of charge transfer effects was demonstrated within the HfNbTiVZr-C system. The results of ab initio materials simulations and X-ray Photoelectron Spectroscopy (XPS) measurements highlight the importance of understanding and considering the local chemical environment and chemical interactions in compositionally complex materials.The approach of metal alloying according to the valence electron concentration (VEC) to tune the mechanical properties was studied in the Nb-Mo-C system. The findings show the importance of microstructural effects on the mechanical properties in the studied thin film materials, which can overshadow the compositional or VEC variations. The response to Xe heavy-ion irradiation was studied in the CrTiTaWNb-C system using in situ irradiation experiments. This work presents a comparison between three different compositions: a TaW-rich alloy and carbide thin film as well as a near-equimolar carbide film. The findings indicate that both microstructure and chemical homogeneity play important roles when it comes to radiation damage tolerance in compositional complex materials.This thesis demonstrates the elaborate and multifaceted nature of compositionally complex materials. Whether it comes to the fundamental understanding or the effective implementation of a materials design tool, many factors need to be taken into consideration, including chemical interactions between the constituent elements and microstructural effects.
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| 7. |
- Srinath, Aishwarya, et al.
(författare)
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Influence of the nitrogen content on the corrosion resistances of multicomponent AlCrNbYZrN coatings
- 2021
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Ingår i: Corrosion Science. - : Elsevier BV. - 0010-938X .- 1879-0496. ; 188
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Tidskriftsartikel (refereegranskat)abstract
- In this study, the relationship between the nitrogen content and the corrosion resistances of non-equimolar multicomponent AlCrNbYZrN films (N = 13-49 at.%) is probed. While there was no linear relationship between nitrogen content and corrosion resistance, the results clearly show that the corrosion resistances of the films were instead determined by their nitrogen-induced porosities i.e. the less porous the sample, the higher the corrosion resistance. The 23, 30 and 37 at.% N samples were denser while the 13 at.% N sample was porous and the 49 at.% N film had an underdense nanocrystalline columnar cross section permitting the ingress of electrolyte.
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| 8. |
- Srinath, Aishwarya, et al.
(författare)
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Near-surface analysis of magnetron sputtered AlCrNbYZrNx high entropy materials resolved by HAXPES
- 2024
-
Ingår i: Applied Surface Science. - : Elsevier. - 0169-4332 .- 1873-5584. ; 666
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Tidskriftsartikel (refereegranskat)abstract
- Hard X-ray photoelectron spectroscopy (HAXPES) was used to perform a non-destructive depth profile of AlCrNbYZrNx (x = 0 to ∼50 at.%) thin films. The outermost native oxide of the pristine thin films contained the highest coordination oxides of every metal. Substoichiometric oxides or oxynitrides were found underneath. After exposure to 1.0 M HCl, increases in the most highly coordinated oxides of Cr, Nb, and Al in films with up to 37 at.% N were observed, suggesting that the low coordination oxides and oxynitrides in the subsurface had been further oxidised and were intermediary compounds in the passivation process. Al and Y oxides were lost to the HCl electrolyte, in agreement with their respective Pourbaix diagrams. The film with 49 at.% N showed little to no change in the data due to its high porosity which led to the oxide being detected at all probed depths. The metal core level spectra revealed a preferential order in which nitrogen bonded with the different metals. Nitrogen interacted first with Y, then Zr, then Al and Nb, and lastly Cr as the nitrogen content was increased.
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| 9. |
- Zendejas Medina, León, 1993-, et al.
(författare)
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Elemental distribution in carbon-supersaturated high entropy alloycoatings: A synchrotron-based study
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Annan publikation (övrigt vetenskapligt/konstnärligt)abstract
- The properties of high entropy alloys (HEAs) are strongly affected by the addition of carbon past the solubility limit. Despite this is the local chemistry in these meta-stable materials not well-characterized. To better understand how carbon affects the elemental distribution of alloys whose constituent elements have widely varying carbon affinities, this paper studies amorphous sputter-deposited coatings of CoCrFeMnNi with concentrations of up to 11\% carbon. Hard x-ray photoelectron spectroscopy (HAXPES), near-edge x-ray absorption fine structure (NEXAFS), and transmission electron microscopy (TEM) were used to determine how each metallic element is affected by the presence of carbon. As-deposited samples are also compared to annealed samples to study the thermal stability and the Calphad method was used to predict the thermodynamic equilibrium state. All five component metals had weak interaction with carbon, including Ni which had a less metallic character in the carbon-containing samples. While elemental segregation is expected at all temperatures at thermodynamic equilibrium, carbon did not promote segregation in the as-deposited samples. During annealing, however, the elements rearranged and formed a mixture of alloy phases and crystalline Cr-rich carbides. Rearrangement of the elements also occurred in the surface oxide, where Mn became dominant. The combination of techniques to characterize HEAs revealed promising trends for future research into these important materials.
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| 10. |
- Alfakes, Boulos, et al.
(författare)
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Enhanced photoelectrochemical performance of atomic layer deposited Hf-doped ZnO
- 2020
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Ingår i: Surface & Coatings Technology. - : Elsevier BV. - 0257-8972 .- 1879-3347. ; 385
-
Tidskriftsartikel (refereegranskat)abstract
- Generation of hydrogen using photoelectrochemical (PEC) water splitting has attracted researchers for the last two decades. Several materials have been utilized as a photoanode in a water splitting cell, including ZnO due to its abundance, low production cost and suitable electronic structure. Most research attempts focused on doping ZnO to tailor its properties for a specific application. In this work, atomic layer deposition (ALD) was used to precisely dope ZnO with hafnium (Hf) in order to enhance its PEC performance. The resultant doped materials showed a significant improvement in PEC efficiency compared to pristine ZnO, which is linked directly to Hf introduction revealed by detailed optical, structural and electrical analyses. The photocurrent obtained in the best performing Hf-doped sample (0.75 wt% Hf) was roughly threefold higher compared to the undoped ZnO. Electrochemical impedance spectroscopy (EIS) and open-circuit potential-decay (OCPD) measurements confirmed suppression in photocarriers' surface recombination in the doped films, which led to a more efficient PEC water oxidation. The enhanced PEC performance of Hf-doped ZnO and effectiveness of the used metal dopant are credited to the synergistic optimization of chemical composition, which enhanced the electrical, structural including morphological, and optical properties of the final material, making Hf-doping an attractive candidate for novel PEC electrodes.
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| 11. |
- Cedervall, Johan, et al.
(författare)
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On the structural and magnetic properties of the double perovskite Nd2NiMnO6Nd2NiMnO6
- 2019
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Ingår i: Journal of Materials Science: Materials in Electronics. - : Springer Science and Business Media LLC. - 1573-482X .- 0957-4522. ; 30:17, s. 16571-16578
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Tidskriftsartikel (refereegranskat)abstract
- The structural, electronic and magnetic properties of phase pure and stoichiometric samples of the double perovskite Nd 2NiMnO 6 have been investigated with a combination of X-ray and neutron diffraction, X-ray photoelectron spectroscopy and magnetometry. It is found that the monoclinic space group P2 1/ n best describes the crystal structure of Nd 2NiMnO 6. Photoectron spectroscopy revels a mixed valence of the transition metal sites where Ni has 3+/2+ oxidation states and Mn has 3+/4+. The compound orders ferromagnetically at ∼195 K. The magnetic structure was determined from the refinement of the neutron diffraction data. The results suggests that the B-site magnetic moments align along the crystallographic a-direction.
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| 12. |
- Fernandes, Arthur B., et al.
(författare)
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Recoverable and Reusable Polymer Microbead-Supported Metal Nanocatalysts for Redox Chemical Transformations
- 2020
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Ingår i: ACS APPLIED NANO MATERIALS. - : AMER CHEMICAL SOC. - 2574-0970. ; 3:2, s. 1722-1730
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Tidskriftsartikel (refereegranskat)abstract
- Metal nanoparticles have been widely exploited in catalysis, but their full impact on the environment and human health is still under debate. Here we describe the one-step fabrication of recoverable and reusable polymer microbead-supported metal and metal oxide nanocatalysts for application in batch reactions and flow systems. Au, Ag, and Fe3O4 nanoparticles were prepared directly at the surface of commercial benzylamine-coated spherical polymer beads in water by using low-energy microwave radiation for 5 min. The functionalization of microbead surface with betalamic acid, an antioxidant from plant origin, before irradiation changes the morphology and catalytic properties of the grafted nanoparticles. No leaching of the active phase was observed during the application of these effective and ready-to-use nanocatalysts on the reduction of 4-nitrophenol and oxidation of dihydrorhodamine 123. The supported nanocatalysts were recovered by filtration and/or magnetic separation and reused up to three times without significant drop in catalytic performance. These results can stimulate the controlled and facile synthesis of recoverable microbead-supported magnetic and nonmagnetic nanocatalysts that can be applied under myriad reaction conditions and reused multiple times.
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| 13. |
- Fritze, Stefan, et al.
(författare)
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Hard and crack resistant carbon supersaturated refractory nanostructured multicomponent coatings
- 2018
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Ingår i: Scientific Reports. - : NATURE PUBLISHING GROUP. - 2045-2322. ; 8
-
Tidskriftsartikel (refereegranskat)abstract
- The combination of ceramic hardness with high crack resistance is a major challenge in the design of protective thin films. High entropy alloys have shown in earlier studies promising mechanical properties with a potential use as thin film materials. In this study, we show that small amounts of carbon in magnetron-sputtered multicomponent CrNbTaTiW films can lead to a significant increase in hardness. The film properties were strongly dependent on the metal composition and the most promising results were observed for TaW-rich films. They crystallised in a bcc structure with a strong (110) texture and coherent grain boundaries. It was possible to deposit films with 8 at.% C in a supersaturated solid-solution into the bcc structure without carbide formation. A major effect of carbon was a significant grain refinement, reducing the column diameter from approximately 35 to 10 nm. This resulted in an increase in hardness from 14.7 to 19.1 GPa while the reduced E-modulus stayed constant at 322 GPa. The carbon-containing films exhibited extremely little plastic deformation around the indent and no cracks were observed. These results show that supersaturation of carbon into high entropy films can be a promising concept to combine superior hardness with high crack resistance.
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| 14. |
- Fritze, Stefan, et al.
(författare)
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Influence of Carbon on Microstructure and Mechanical Properties of Magnetron Sputtered TaW Coatings
- 2020
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Ingår i: Materials & design. - : Elsevier. - 0264-1275 .- 1873-4197. ; 196
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Tidskriftsartikel (refereegranskat)abstract
- (Ta,W) and (Ta,W):C films with-5 at.% C were deposited by non-reactive magnetron sputtering. They crystallised in a bcc structure with a columnar microstructure. The solid solubility of C in (Ta,W) alloys is very low, which suggests that the (Ta,W):C films are supersaturated with respect to carbon. This was confirmed by diffraction and atom probe tomography (APT) showing that carbon is in the as-deposited (Ta,W):C films homogeneously distributed in the structure without carbide formation or carbon segregation. Annealing at 900 degrees C for 2 h showed no significant column coarsening but an increased defect density at the column boundaries in the (Ta,W):C films. The films were still supersaturated with respect to carbon but APT showed a partial segregation of carbon presumably to defect-rich column boundaries after annealing. The (Ta,W) films exhibited a hardness of-12-13 GPa. Alloying with carbon increased the hardness to-17 GPa. The hardness increased to-19 GPa for the annealed (Ta,W):C films. This annealing-induced hardness increase was explained by C segregation to the more defect-rich column boundaries, which restricts dislocation movements. (Ta,W):C coatings may be a potential alternative to ceramic coatings, worth exploring further by small scale mechanical testing to investigate if these materials are ductile.
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| 15. |
- Fritze, Stefan, et al.
(författare)
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Influence of Deposition Temperature on the Phase Evolution of HfNbTiVZr High-Entropy Thin Films
- 2019
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Ingår i: Materials. - : MDPI. - 1996-1944. ; 12:4
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Tidskriftsartikel (refereegranskat)abstract
- In this study, we show that the phase formation of HfNbTiVZr high-entropy thin films is strongly influenced by the substrate temperature. Films deposited at room temperature exhibit an amorphous microstructure and are 6.5 GPa hard. With increasing substrate temperature (room temperature to 275 degrees C), a transition from an amorphous to a single-phased body-centred cubic (bcc) solid solution occurs, resulting in a hardness increase to 7.9 GPa. A higher deposition temperature (450 degrees C) leads to the formation of C14 or C15 Laves phase precipitates in the bcc matrix and a further enhancement of mechanical properties with a peak hardness value of 9.2 GPa. These results also show that thin films follow different phase formation pathways compared to HfNbTiVZr bulk alloys.
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| 16. |
- Fritze, Stefan, et al.
(författare)
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Magnetron sputtering of carbon supersaturated tungsten films-A chemical approach to increase strength
- 2021
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Ingår i: Materials & design. - : Elsevier. - 0264-1275 .- 1873-4197. ; 208
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Tidskriftsartikel (refereegranskat)abstract
- Tungsten (W)-based materials attract significant attention due to their superior mechanical properties. Here, we present a chemical approach based on the addition of carbon (C) for increased strength via the combination of three strengthening mechanisms in W thin films. W:C thin films with C concentrations up to-4 at.% were deposited by magnetron sputtering. All films exhibit a body-centred-cubic structure with strong texture and columnar growth behaviour. X-ray and electron diffraction measurements suggest the formation of supersaturated W:C solid solution phases. The addition of C reduced the average column width from-133 nm for W to-20 nm for the film containing-4 at.% C. The column refinement is explained by a mechanism where C acts as re-nucleation sites. The W film is-13 GPa hard, while the W:C films achieve a peak hardness of-24 GPa. The W:C films are-11 GPa harder than the W film, which is explained by a combination of grain refinement strengthening, solid solution strengthening and increased dislocation density. Additional micropillar compression tests showed that the flow stress increased upon C addition, from-3.8 to-8.3 GPa and no brittle fracture was observed.
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| 17. |
- Fritze, Stefan
(författare)
-
Microstructure and Mechanical Properties of Magnetron Sputtered Refractory Metal Thin Films
- 2020
-
Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- The design and development of new multifunctional materials that exhibit a combination of high hardness and ductility, as well as a high corrosion resistance and thermal stability, is one of the key challenges in the field of material science. The focus of this thesis is on the development of novel multifunctional magnetron sputtered CrNbTaTiW–C based thin films. Carbon was selected as an alloying element to investigate if it could modify the microstructure (via grain refinement) and improve the properties (e.g. the hardness and ductility).TaW-rich and near-equimolar high entropy alloys in the CrNbTaTiW system were selected as starting points for this study. The latter alloys were predicted, based on empirical design rules, to form a single-phase solid solution. In contrast, thermodynamic calculations showed that the films at equilibrium should be composed of a mixture of several phases at temperatures below 1100 °C. Experimentally, however, a single-phase bcc structure was observed for the deposited films and it was concluded that the films were kinetically and not entropy stabilised. A hypothesis is that the kinetics during sputtering allow a ’direct’ phase selection by tuning the process parameters and evidence of this was found in the HfNbTiVZr alloy system.The CrNbTaTiW–C system is, however, complex and additional studies were carried out on the W–C and TaW–C systems. All metallic films crystallised in a bcc structure with a <110> texture and the column width of these films varied between 25 nm and 80 nm. The films were very hard (~ 13 GPa), which was explained by the small grain size. A single-phase bcc structure was also obtained upon the addition of 5-10 at.% carbon for all compositions except the near-equimolar CrNbTaTiW. X-ray diffraction indicated a unit cell expansion, which was attributed to the formation of a supersaturated solid solution. Additional atom probe tomography (APT) studies on selected samples confirmed the formation of such solid solutions. The supersaturated solid solution is not thermodynamically stable and an annealing study showed that heat treatment yielded segregation and clustering of carbon at the grain boundaries. The addition of carbon had a grain refining effect in the W–C system and the multicomponent CrNbTaTiW–C system. In general, the addition of carbon increased the hardness, which was mainly caused by a reduced grain size in line with the Hall-Petch relationship. Excellent mechanical properties of carbon supersaturated films were further confirmed in pillar tests on W–C films, which showed very high yield strength (~ 9 GPa) and no brittle fracture. The results show that carbon can be used as a chemical approach to control the grain size and properties of these films. Multicomponent carbides with a B1 structure were formed at high carbon concentrations (~ 40 at.%). The microstructure of these films depended strongly on the process parameters and a higher deposition temperature was found to increase the film density and hardness. The TaW-rich carbide exhibited a very high hardness of ~ 35 GPa and excellent corrosion resistance.
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| 18. |
- Glechner, T., et al.
(författare)
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Tuning structure and mechanical properties of Ta-C coatings by N-alloying and vacancy population
- 2018
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Ingår i: Scientific Reports. - : Springer Science and Business Media LLC. - 2045-2322. ; 8
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Tidskriftsartikel (refereegranskat)abstract
- Tailoring mechanical properties of transition metal carbides by substituting carbon with nitrogen atoms is a highly interesting approach, as thereby the bonding state changes towards a more metallic like character and thus ductility can be increased. Based on ab initio calculations we could prove experimentally, that up to a nitrogen content of about 68% on the non-metallic sublattice, Ta-C-N crystals prevail a face centered cubic structure for sputter deposited thin films. The cubic structure is partly stabilized by non-metallic as well as Ta vacancies-the latter are decisive for nitrogen rich compositions. With increasing nitrogen content, the originally super-hard fcc-TaC0.71 thin films soften from 40 GPa to 26 GPa for TaC0.33N0.67, accompanied by a decrease of the indentation modulus. With increasing nitrogen on the non-metallic sublattice (hence, decreasing C) the damage tolerance of Ta-C based coatings increases, when characterized after the Pugh and Pettifor criteria. Consequently, varying the non-metallic sublattice population allows for an effective tuning and designing of intrinsic coating properties.
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| 19. |
- Greczynski, Grzegorz, et al.
(författare)
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X-ray photoelectron spectroscopy of thin films
- 2023
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Ingår i: NATURE REVIEWS METHODS PRIMERS. - : SPRINGERNATURE. - 2662-8449. ; 3:1
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Tidskriftsartikel (refereegranskat)abstract
- X-ray photoelectron spectroscopy (XPS) is a popular analytical technique in materials science as it can assess the surface chemistry of a broad range of samples. This Primer concerns best practice in XPS analysis, aimed at both entry-level and advanced users, with a focus on thin film samples synthesized under vacuum conditions. The high surface to volume ratio of thin films means that factors such as substrate choice and air exposure time are important for the final result. Essential concepts are introduced, such as binding energy, photoelectric effect, spectral referencing and chemical shift, as well as practical aspects including surface sensitivity, probing depth, energy resolution, sample handling and sputter etching. Correct procedures for experimental planning, instrument set-up, sample preparation, data acquisition, results analysis and presentation are reviewed in connection with physical principles and common applications. Typical problems, including charging, spectral overlap, sputter damage and binding energy referencing, are discussed along with possible solutions or workarounds. Finally, a workflow is presented for arriving at high-quality results. X-ray photoelectron spectroscopy (XPS) can be used to investigate chemical bonding and elemental composition. This Primer discusses how XPS can be used to characterize thin films, including key considerations for sample preparation, experimental set-up and data analysis.
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| 20. |
- Hanifpour, Fatemeh, et al.
(författare)
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Investigation into the mechanism of electrochemical nitrogen reduction reaction to ammonia using niobium oxynitride thin-film catalysts
- 2022
-
Ingår i: Electrochimica Acta. - : Elsevier. - 0013-4686 .- 1873-3859. ; 403
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Tidskriftsartikel (refereegranskat)abstract
- Niobium oxynitride (NbOxNy) thin films with varying combined non-metal vs. metal stoichiometries ( x + y ) and N/O stoichiometric ratios (y/x) are investigated for their ability to catalyze the nitrogen re-duction reaction and ammonia synthesis at ambient conditions. Electrochemical impedance spectroscopy and ammonia measurements show stark differences both in nitrogen vs. argon media on each surface and on the surfaces in the series when the combined stoichiometry of N + O vs. Nb increases. Surface stability checks at fixed intervals during the experiments and surface characterization after the experiments us -ing X-ray diffraction reveal the least changes occurred to the surface with the highest N + O stoichiometry. Based on these observations, an ammonia synthesis mechanism is proposed. Isotope labeling experiments on the most promising surface of the series, however, show no sign of catalytically produced ammonia, possibly due to the lack of stability of the surface to endure through the ammonia production cycle.
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| 21. |
- Hanifpour, Fatemeh, et al.
(författare)
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Operando quantification of ammonia produced from computationally-derived transition metal nitride electro-catalysts
- 2022
-
Ingår i: Journal of Catalysis. - : Elsevier. - 0021-9517 .- 1090-2694. ; 413, s. 956-967
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Tidskriftsartikel (refereegranskat)abstract
- Electrochemical reduction of dinitrogen to ammonia is investigated in a micro-reactor flow-cell using thin films of VN, CrN, NbN and ZrN. Chronoamperometry loops are used for ammonia production analysis. Operando ammonia quantification is accomplished in a flow injection analyzer. Results show the effect of presence/absence of N-2(g) within both the electrochemical characterization and ammonia production for ZrN. However, no ammonia is detected from studies on CrN. VN and NbN are inactivated upon reacting their N atoms of the surface top layer(s). Results obtained from ammonia measurements, electrochemical impedance spectroscopy analysis, surface stability checks, and surface characterization using X-ray reflectivity, reveal certain trends indicating catalytic behavior for ZrN. However, the concentration of produced ammonia is below the detection limit of the methods devised to analyze the samples from isotope labeling experiments. The onset of ammonia production on ZrN appears to be in close agreement with that predicted previously by computational studies.
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| 22. |
- Huang, Yu-Kai
(författare)
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Advancements in Lithium-Based Batteries : Unraveling and Mitigating Performance-Limiting Phenomena in Negative Electrodes
- 2023
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- The development of lithium-based batteries, especially lithium-ion batteries, has changed our daily lives significantly. The technologies first enabled by lithium-based batteries are now in turn creating a demand for better lithium-based batteries with higher energy densities and longer cycling lifetimes. This requires studies and development of negative electrodes, with a particular focus on gaining a better and more complete understanding of all performance-limiting phenomena and to develop appropriate mitigation strategies.For negative electrodes based on alloy-forming materials such as silicon, aluminum and tin, it has, recently been shown that capacities losses can result from diffusion-controlled trapping of lithium due to an incomplete delithiation of the electrodes. In the first part of the thesis, it is demonstrated explicitly that such a lithium trapping effect also is seen for conventional graphite electrodes. This effect is further demonstrated to greatly affect the cycle life performance of NMC811/graphite full cells during high-rate cycling. However, it is also demonstrated that the inclusion of constant-voltage delithiation steps can increase the delithiation efficiency and decrease the influence of the trapping effect. The use of silicon electrodes based on silicon nanoparticles is also revisited. It is proposed that the influence of the lithium trapping effect seen for such electrodes is affected by the size of the employed silicon nanoparticles, most likely, via its influence on the electrode microstructure. Replacing the currently used negative electrodes with lithium-metal electrodes, especially in a “anode-free” configuration, can significantly increase the energy densities of lithium-based batteries due to the high capacity and low electrochemical potential of elemental lithium. However, the inhomogeneous lithium deposition and stripping greatly limit the cycling performance. In the second part of this thesis, strategies focusing on electrochemically controlling the nucleation and growth of lithium are proposed to improve the deposition of lithium on lithium-metal electrodes as well as directly on copper current collectors. In the former study, it is shown that forming a great number of homogeneously distributed nucleation sites across the entire electrode surface, via the introduction of a one-second long potentiostatic oxidation pulse, subsequently yields more homogeneous lithium deposition. In the second study, it is found that the nucleation of lithium on copper current collectors can be affected by the diffusion of lithium into the current collectors. It is also demonstrated that the influence of this effect can be decreased by chemically prelithiating the current collectors so that more homogeneous lithium deposition can be attained.
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| 23. |
- Ivanov, Sergey, et al.
(författare)
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Temperature-dependent structural and magnetic properties of R2MMnO6 double perovskites (R=Dy, Gd; M=Ni, Co)
- 2018
-
Ingår i: Journal of Materials Science: Materials in Electronics. - : Springer Science and Business Media LLC. - 1573-482X .- 0957-4522. ; 29:21, s. 18581-18592
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Tidskriftsartikel (refereegranskat)abstract
- The structural and magnetic properties of the Dy2CoMnO6, Dy2NiMnO6 and Gd2CoMnO6 double perovskites are investigated using X-ray powder diffraction and squid magnetometry. The materials adopt an orthorhombic structure (space ground Pnma) with disordered Co(Ni)/Mn cations, and exhibit ferrimagnetic transitions near T(C)85, 95, and 115K respectively. T-C was found to monotonously depend on the orthorhombic distortion (a-c)/(a+c) of the compounds. The crystal structure of the compounds was investigated as a function of temperature (16-1100K range), evidencing changes in the BO6 octahedron near T-C. The magnetic entropy changes are estimated for comparison of the magnetocaloric properties to those from literature.
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| 24. |
- Jansson, Ulf, 1960-, et al.
(författare)
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Carbon-containing multi-component thin films
- 2019
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Ingår i: Thin Solid Films. - : Elsevier BV. - 0040-6090 .- 1879-2731. ; 688
-
Forskningsöversikt (refereegranskat)abstract
- High entropy alloys (HEAs) have been a hot research area for many years. They are solid solutions of at least five elements in approximately equimolar compositions. The HEAs are assumed to be stabilized by a high entropy of mixing favouring a solid solution phase instead of a mixture of intermetallic phases. The importance of entropy of mixing and the true nature of HEAs are debated but the concept has contributed to an interesting development of new alloys. They idea of stabilizing solid solutions with many elements have recently been expanded to nitrides, borides, oxides and carbides. Furthermore, a growing number of thin film studies of these compounds are now published. In this paper we summarise recent results from studies of carbon-containing multi-component thin films based on the HEA concept. We will summarise some general observations connected to "high-entropy" materials. We also describe some general trends in metal-carbon interactions for transition metals and discuss how they should influence the formation of multi-component carbides. A summary of results on bulk multi-component carbide materials is also presented. We review published studies of carbon-containing multi-component thin films mainly deposited with magnetron-sputtering. The crystal structure, microstructure and properties of these films are described. Finally, we highlight some interesting topics for future research.
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| 25. |
- Johansson, Kristina, et al.
(författare)
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Influence of oxygen content on structure and material properties of reactively sputtered Al-Ge-O-N thin films
- 2018
-
Ingår i: Journal of Alloys and Compounds. - : ELSEVIER SCIENCE SA. - 0925-8388 .- 1873-4669. ; 738, s. 515-527
-
Tidskriftsartikel (refereegranskat)abstract
- Ternary Al-Ge-N and quaternary Al-Ge-O-N coatings were deposited by reactive dc magnetron cosputtering of Al and Ge targets in an Ar/N-2 or Ar/N-2/O-2 atmosphere at a substrate temperature of 250 degrees C. The structure and material properties of the coatings were investigated by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), nanoindentation, UV-vis spectroscopy and optical profilometry. In agreement with literature, the ternary Al-Ge-N coatings were found to be nanocomposite materials with nanocrystalline (Al1-xGex) N-y solid solution phase in a Ge3N4-z amorphous matrix. The Al-Ge-O-N coatings consisted of a nanocrystalline wurzite-type (Al1-xGex)( N1-yOy) solid solution phase for low oxygen concentrations with a possible co-existence of an amorphous Ge-N matrix phase. For higher O contents, the coatings became X-ray amorphous. The mechanical properties of the Al-Ge-O-N films were improved for low oxygen content, as compared to the ternary Al-Ge-N samples, showing an increase in hardness up to 29 GPa and Young's modulus to 320 GPa. The oxygen addition also resulted in an additional design parameter of the optical properties compared to the ternary Al-Ge-N films. The optical absorption edge was thus tuneable towards both shorter and longer wavelength by changing the O and Ge content respectively, and ranged from 302 to 373 nm, corresponding to an optical bandgap (E-04) between 4.1 and 3.3 eV. After annealing of the Al-Ge-O-N coatings in ultra-high vacuum at 500 degrees C, indications of increased thermal stability for the coating with high oxygen content were observed. For the annealed Al-Ge-O-N films the mechanical properties were improved upon heat treatment, while the optical properties were only slightly changed. These results suggests that coatings of the Al-Ge-O-N system could be suitable as protective optical coatings at elevated temperatures.
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| 26. |
- Johansson, Kristina, et al.
(författare)
-
Multicomponent Hf-Nb-Ti-V-Zr nitride coatings by reactive magnetron sputter deposition
- 2018
-
Ingår i: Surface & Coatings Technology. - : ELSEVIER SCIENCE SA. - 0257-8972 .- 1879-3347. ; 349, s. 529-539
-
Tidskriftsartikel (refereegranskat)abstract
- Multicomponent nitride coatings of the Hf-Nb-Ti-V-Zr system with different Hf content (0-18 at.%) were deposited using reactive dc magnetron sputtering. Coatings with lower Hf content (0-7 at.%) were found to consist of a single solid solution phase with NaCl-type structure (space group Fm-3m). Coatings with higher Hf content (10-18 at.%) showed a two-phase material consisting of cubic Fm-3m and tetragonal I4/m:run solid solution phase. The lattice distortion, estimated by calculating the delta-parameter under the assumption of a single solid solution phase, varied between 3.8 and 4.0% and slightly decreased with increasing Hf content. SEM and TEM cross section images showed a columnar microstructure with columns that were frayed on the surface or throughout the whole column. The column size decreased as Hf content increased. The hardness increased from 8 to 19 GPa with increased Hf content, which most probably is related to the change in microstructure rather than change in lattice distortion. The electrical resistivity for all samples ranged between 231 and 286 mu Omega cm.
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| 27. |
- Lewin, Erik, Dr. 1979-
(författare)
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Multi-component and high-entropy nitride coatings : A promising field in need of a novel approach
- 2020
-
Ingår i: Journal of Applied Physics. - : AMER INST PHYSICS. - 0021-8979 .- 1089-7550. ; 127:16
-
Tidskriftsartikel (refereegranskat)abstract
- Multi-component and high-entropy nitrides are a growing field with a promise of new functional materials. The interest in the field was sparked by the adjacent field of high-entropy and multi-component alloys, and the promise consists of both demonstrated properties and a possibly very large freedom for materials design. These promises, however, also come with new challenges connected to the vast available experimental space, which is inherent in multi-component materials. Traditional materials science methodologies will be slow to make appreciable progress in such an environment. A novel approach is needed to meet the challenges of the hyperdimensional compositional space. Recent developments within the fields of information technology can give materials science the tools needed. This Perspective article summarizes the state of the art in the field of multi-component nitride materials, focusing on coatings where solid solution phases with simple crystal structures are formed. Furthermore, it outlines the present research challenges that need to be addressed to move the field forward and suggests that there is a need to combine the traditional knowledge-driven materials science methodology with new data-driven methodologies. The latter would include advanced data-handling with artificial intelligence and machine learning to assist in the evaluation of large, shared datasets from both experimental and theoretical work. Such a change in the methodology will be a challenge but will be needed in order to fully realize the full potential of multi-component (nitride) materials.
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| 28. |
- Lewin, Erik, Dr. 1979-
(författare)
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Oordning ger nya material
- 2022
-
Ingår i: Allkemi. - : IKEM – Innovations- och kemiindustrierna i Sverige. - 2003-6817 .- 2003-6825. ; :1, s. 10-11
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Tidskriftsartikel (populärvet., debatt m.m.)abstract
- Intresset är stort för de nya högentropilegeringarna som består av fem eller fler grundämnen i en kombination av ordning oordning. Nya egenskaper har observerats – men väntar ännu på sin förklaring.
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| 29. |
- Lewin, Erik, Dr. 1979-
(författare)
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Oordning skapar nya material
- 2022
-
Ingår i: Kemisk tidskrift. - : Svenska Kemisamfundet. - 2003-2722. ; :1, s. 20-23
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Tidskriftsartikel (populärvet., debatt m.m.)abstract
- Förhoppningarna är stora på de nya, heta HÖGENTROPIMATERIALEN – som består av fem eller fler grundämnen. De har egenskaper som gör dem intressanta för exempelvis omvandling, lagring och transport av energi.
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| 30. |
- Lewin, Erik, Dr. 1979-, et al.
(författare)
-
Spectral artefacts post sputter-etching and how to cope with them - A case study of XPS on nitride-based coatings using monoatomic and cluster ion beams
- 2018
-
Ingår i: Applied Surface Science. - : ELSEVIER SCIENCE BV. - 0169-4332 .- 1873-5584. ; 442, s. 487-500
-
Tidskriftsartikel (refereegranskat)abstract
- The issue of artefacts due to sputter-etching has been investigated for a group of AlN-based thin film materials with varying thermodynamical stability. Stability of the materials was controlled by alloying AlN with the group 14 elements Si, Ge or Sn in two different concentrations. The coatings were sputter-etched with monoatomic Ar+ with energies between 0.2 and 4.0 keV to study the sensitivity of the materials for sputter damage. The use of Ar-n(+) clusters to remove an oxidised surface layer was also evaluated for a selected sample. The spectra were compared to pristine spectra obtained after in-vacuo sample transfer from the synthesis chamber to the analysis instrument. It was found that the all samples were affected by high energy (4 keV) Ar+ ions to varying degrees. The determining factors for the amount of observed damage were found to be the materials' enthalpy of formation, where a threshold value seems to exist at approximately -1.25 eV/atom (similar to-120 kJ/mol atoms). For each sample, the observed amount of damage was found to have a linear dependence to the energy deposited by the ion beam per volume removed material. Despite the occurrence of sputter-damage in all samples, etching settings that result in almost artefact-free spectral data were found; using either very low energy (i.e. 200 eV) monoatomic ions, or an appropriate combination of ion cluster size and energy. The present study underlines that analysis post sputter-etching must be carried out with an awareness of possible sputter-induced artefacts.
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| 31. |
- Malinovskis, Paulius, et al.
(författare)
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Synthesis and Characterisation of Nanocomposite Mo-Fe-B Thin Films Deposited by Magnetron Sputtering
- 2021
-
Ingår i: Materials. - : MDPI. - 1996-1944. ; 14:7
-
Tidskriftsartikel (refereegranskat)abstract
- Several ternary phases are known in the Mo-Fe-B system. Previous ab initio calculations have predicted that they should exhibit a tempting mix of mechanical and magnetic properties. In this study, we have deposited Mo-Fe-B films with a Fe-content varying from 0-37 at.% using non-reactive DC (direct current) magnetron sputtering. The phase composition, microstructure, and mechanical properties were investigated using X-ray diffraction, scanning transmission electron microscopy, and nanoindentation measurements. Films deposited at 300 degrees C and with >7 at.% Fe are nanocomposites consisting of two amorphous phases: a metal-rich phase and a metal-deficient phase. Hardness and elastic modulus were reduced with increasing Fe-content from similar to 29 to similar to 19 GPa and similar to 526 to similar to 353 GPa, respectively. These values result in H-3/E-2 ratios of 0.089-0.052 GPa, thereby indicating brittle behaviour of the films. Also, no indication of crystalline ternary phases was observed at temperatures up to 600 degrees C, suggesting that higher temperatures are required for such films to form.
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| 32. |
- Malinovskis, Paulius, et al.
(författare)
-
Synthesis and characterization of multicomponent (CrNbTaTiW)C films for increased hardness and corrosion resistance
- 2018
-
Ingår i: Materials & design. - : Elsevier BV. - 0264-1275 .- 1873-4197. ; 149, s. 51-62
-
Tidskriftsartikel (refereegranskat)abstract
- Multicomponent carbide thin films of (CrNbTaTiW)C (30–40 at.% C) with different metal contents were depos-ited at different temperatures using non-reactive DC magnetron sputtering. The lattice distortion for the metallattice was estimated to vary from about 3 to 5%. Most films crystallized in the cubic B1 structure but Ta/W-rich films deposited at 600 °C exhibited a tetra gonal distortion. X-ray diffraction results sh ow that near-equimolar films exhibited a strong (111) texture. In contrast, Ta/W-rich films exhibited a shift from (111) to(100) texture at 450 °C. The in-plane relationship was determined to MC(111)[-12-1]//Al2O3(001)[110] with alattice mismatch of about 11% along the Al2O3[110] direction. A segregation of Cr to the grain boundaries was ob-served in all films. The microstructure was found to be the most important factor for high hardness. Less denseNb-rich and near-equimolar films deposited at low tem peratures exhib ited the low est hardnes s (12 GPa),while very dense Ta/W-rich high temperature films were found to be the hardest (36 GPa). No correlation wasfound between the lattice distortion and the hardness. Corrosion studies revealed that the multicomponentfilms exhibited excellent corrosion resistance, superior to that of a reference hyper-duplex stainless steel, in1.0 M HCl.
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| 33. |
- Mukhamedov, Boburjon, et al.
(författare)
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Tetragonal distortion in magnetron sputtered bcc-W films with supersaturated carbon
- 2022
-
Ingår i: Materials & design. - : Elsevier Science Ltd. - 0264-1275 .- 1873-4197. ; 214
-
Tidskriftsartikel (refereegranskat)abstract
- Carbon has a low solid solubility in bcc tungsten at equilibrium. However, metastable supersaturated solid solutions can be synthesized with magnetron sputtering. Here, we present a systematic study on the phase stability and mechanical properties of such supersaturated W-C solid solutions. H-2h scans show a split of the 200/020 and the 002 peaks for supersaturated films which is explained by a tetragonal distortion of the bcc structure. This split increases with increasing C content and is maximized at 4 at.% C, where we observe an a/b axis of 3.15-3.16 A and a c-axis of 3.21-3.22 A. We performed first-principles calculations of lattice parameters, mixing enthalpies, elastic constants and polycrystalline elastic moduli for cubic and tetragonal W-C solid solutions. Calculations show that tetragonal structure is more stable than the bcc supersaturated solid solution and the calculated lattice parameters and Youngs moduli follow the same trends as the experimental ones as a function of C concentration. The results suggest that supersaturated films with lattice distortion can be used as a design approach to improve the properties of transition metal films with a bcc structure. (c) 2022 The Authors. Published by Elsevier Ltd.
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| 34. |
- Oladipo, Habeebllah, et al.
(författare)
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Unveiling the role of bisulfide in the photocatalytic splitting of H2S in aqueous solutions
- 2020
-
Ingår i: Applied Catalysis B. - : ELSEVIER. - 0926-3373 .- 1873-3883. ; 270
-
Tidskriftsartikel (refereegranskat)abstract
- Anaerobic photocatalytic conversion of aqueous H2S to H-2 was tested on Pt-decorated N-doped TiO2 grown on graphene. The hydrogen production increased linearly (rate: 32.3 mu mol/h/g, quantum yield: 1.4 x 10(-4)) with HS- concentration, until the critical value of 0.029 mol/dm(3), after which it declined to negligible values. The latter was attributed to photon-blockage caused by sulfur-containing species formed on catalyst surface, which could be removed by simple washing of the catalyst leading to its regeneration, as highlighted by the characterization of fresh and used catalyst. Similar tests performed at constant HS- concentration and variable pH did not yield a correlation, thus suggesting HS- as the major source of H-2, and not H+. A new kinetic model assessing the competitive adsorption mechanism reiterated the important role of sulfide ionic species in hydrogen production. A strong correlation between the latter and HS- concentration was established based on the reactivity results and proposed mechanism.
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| 35. |
- Osinger, Barbara, et al.
(författare)
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Investigation of the phase formation in magnetron sputtered hard multicomponent (HfNbTiVZr)C coatings
- 2022
-
Ingår i: Materials & design. - : ELSEVIER SCI LTD. - 0264-1275 .- 1873-4197. ; 221
-
Tidskriftsartikel (refereegranskat)abstract
- Multicomponent carbides have gained interest especially for ultra-high temperature applications, due to their ceramic hardness, good oxidation resistance and enhanced strength. In this study the phase forma-tion, stability and mechanical properties of (HfNbTiVZr)C multicomponent carbide coatings were inves-tigated. Phase stability was predicted by the CALPHAD (CALculation of PHAse Diagrams) methods. This revealed that the multicomponent solid solution phase is only stable at elevated temperatures, namely above 2400 degrees C. At lower temperatures a phase mixture was predicted, with a particular tendency for V to segregate. Magnetron sputtered thin films deposited at 300 degrees C exhibited a single NaCl-type multicom-ponent carbide phase, which attributes to the kinetic stabilisation of simple structures during thin film growth. Films deposited at 700 degrees C, or exposed to UHV annealing at 1000 degrees C, however, revealed the decom-position of the single-phase multicomponent carbide by partial elemental segregation and formation of additional phases. Thus, confirming the CALPHAD predictions. These results underscore the importance of explicitly considering temperature when discussing the stability of multicomponent carbide materials, as well as the applicability of CALPHAD methods for predicting phase formation and driving forces in these materials. The latter being crucial for designing materials, such as carbides, that are used in appli-cations at elevated temperatures.
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| 36. |
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| 37. |
- Osinger, Barbara, et al.
(författare)
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Structural and mechanical properties of magnetron sputtered (NbxMo1-x)C thin films
- 2024
-
Ingår i: Vacuum. - : Elsevier. - 0042-207X .- 1879-2715. ; 224
-
Tidskriftsartikel (refereegranskat)abstract
- While transition metal carbides (TMCs) exhibit favourable mechanical properties, alloying according to the valence electron concentration (VEC) has the potential to further enhance the properties of these hard but inherently brittle materials. This study investigates the influence of alloying on the microstructure and mechanical properties of (NbxMo1-x)C carbide films, including binary references and ternary compositions with varying metal ratios (x between 0.35 and 0.53). Furthermore, the influence of various substrate materials is studied by comparing films deposited on Al2O3, MgO and SiO2. All films exhibit a NaCl-type carbide structure and X-ray photoelectron spectroscopy revealed the presence of small amounts of an additional amorphous carbon (a-C) phase. Hardness values around 20 ± 2 GPa were obtained for the films on Al2O3 and MgO, whereas a reduced hardness of 11 ± 1 GPa was observed for the films on SiO2 which is attributed to larger crystallite size and more polycrystalline structure. Overall no clear trend as a function of composition can be noted, indicating that microstructure effects dominate the mechanical properties in this study overshadowing the effect of varying the metal content.
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| 38. |
- Saldan, Ivan, et al.
(författare)
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Surface analysis of nickel nanomaterials electrodeposited on graphite surface
- 2019
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Ingår i: Micro & Nano Letters. - : INST ENGINEERING TECHNOLOGY-IET. - 1750-0443. ; 14:12, s. 1233-1237
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Tidskriftsartikel (refereegranskat)abstract
- Pure Nickel (Ni) and Nickel-Palladium (Ni-Pd) alloy were electrodeposited on graphite surface via pulse electrolysis in dimethyl sulfoxide in form of rods and nanoparticles with a diameter of similar to 100-350 and similar to 10-35 nm, respectively. X-ray photoelectron spectroscopy (XPS) spectra of Ni 2p(3/2) region for these nanomaterials suggests on their surface Ni2+ precursor while after Ar+ ion-etching metallic nickel starts to be dominated. Both Pd-0 and Pd2+ for XPS spectra of Pd 3d(5/2) and 3d(3/2) were observed after electrodeposition. Scanning electron microscope-energy dispersive X-ray and XPS analysis confirmed electrodeposition of nickel nanomaterials in non-aqueous electrolyte. Using a lower concentration of Ni2+ precursor, nanoparticles with an average particle size of similar to 10-23 nm were prepared on a graphite surface.
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| 39. |
- Sarkar, Tapati, et al.
(författare)
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Compositional dependence of the magnetic state of Co3-xZnxTeO6 solid solutions
- 2021
-
Ingår i: Journal of Alloys and Compounds. - : Elsevier. - 0925-8388 .- 1873-4669. ; 884
-
Tidskriftsartikel (refereegranskat)abstract
- The magnetic properties of phase-pure solid solutions of Co3-xZnxTeO6 are investigated using magnetometry (single crystals) and neutron diffraction (polycrystalline powders), and compared to results of detailed crystallographic studies. There are five unique Co sites in Co3TeO6, including a tetrahedrally coordinated Co-2 site which Zn preferentially occupies. The magnetic interaction is found to monotonically decrease as the Co-2-O bond length decreases with increasing Zn content. The results suggest a modification of the magnetic structure in the samples containing Zn.
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| 40. |
- Shu, Rui, et al.
(författare)
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Microstructure and mechanical, electrical, and electrochemical properties of sputter-deposited multicomponent (TiNbZrTa)N-x coatings
- 2020
-
Ingår i: Surface & Coatings Technology. - : ELSEVIER SCIENCE SA. - 0257-8972 .- 1879-3347. ; 389
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Tidskriftsartikel (refereegranskat)abstract
- A series of (TiNbZrTa)Nx coatings with a thickness of similar to 1.1 mu m were deposited using reactive magnetron sputtering with segmented targets. The deposition temperature was varied from room temperature to 700 degrees C resulting in coatings with different microstructures. The coatings were characterized by electron microscopy, atomic force microscopy, compositional analysis, and X-ray diffraction. Effects of the deposition temperature on the electrical, mechanical and corrosion properties were studied with four-point probe, nanoindentation and potentiodynamic polarization measurements, respectively. X-ray photoelectron spectroscopy (XPS) analyses reveal a gradual change in the chemical state of all elements with increasing growth temperature from nitridic at room temperature to metallic at 700 degrees C. A NaCl-type structure with (001) preferred orientation was observed in the coating deposited at 400 degrees C, while an hcp structure was found for the coatings deposited above 400 degrees C. The resistivities of the TiNbZrTa nitride coatings were found to be around 200 mu Ocm. In 0.1 M H2SO4 aqueous solution, a corrosion current density of 2.8 x 10(-8) A/cm(2) and a passive behaviour up to 1.5 V vs. Ag/AgCl were found for the most corrosion resistant coating. The latter corrosion current is about two orders of magnitude lower than that found for a reference hyper-duplex stainless steel.
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| 41. |
- Tunes, Matheus A., et al.
(författare)
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From high-entropy alloys to high-entropy ceramics : The radiation-resistant highly concentrated refractory carbide (CrNbTaTiW)C
- 2023
-
Ingår i: Acta Materialia. - : Elsevier. - 1359-6454 .- 1873-2453. ; 250
-
Tidskriftsartikel (refereegranskat)abstract
- High-entropy materials represent the state-of-the-art on the alloy design strategy for future applications in extreme environments. Recent data indicates that high-entropy alloys (HEAs) exhibit outstanding radiation resistance in face of existing diluted alloy counterparts due to suppressed damage formation and evolution. An extension of the HEA concept is presented in this paper towards the synthesis and characterization of novel high-entropy ceramics as emergent materials for application in environments where energetic particle irradiation is a major concern. A novel carbide within the quinary refractory system CrNbTaTiW has been synthesized using magnetron-sputtering. The material exhibited nanocrystalline grains, single-phase crystal structure and C content around 50 at.%. Heavy-ion irradiation with in-situ Transmission Electron Microscopy was used to assess the irradiation response of the new high-entropy carbide (HEC) at 573 K and a comparison with the HEA within the system is made. No displacement damage effects appear within the microstructures of both HEA and HEC up to a dose of 10 displacements-per-atom. Surprisingly, the HEC has not amorphized under the investigated conditions. Xe was implanted in both materials and bubbles nucleated, but smaller sizes compared with conventional nuclear materials shedding light they are potential candidates for use in nuclear energy.
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| 42. |
- von Fieandt, Kristina, et al.
(författare)
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Influence of N content on structure and mechanical properties of multi-component Al-Cr-Nb-Y-Zr based thin films by reactive magnetron sputtering
- 2020
-
Ingår i: Surface & Coatings Technology. - : ELSEVIER SCIENCE SA. - 0257-8972 .- 1879-3347. ; 389
-
Tidskriftsartikel (refereegranskat)abstract
- Al-Cr-Nb-Y-Zr-N films have been deposited with reactive dc magnetron sputtering at various N-2 flow ratios to achieve films with different nitrogen content, from purely metallic to fully nitrided films. The structure evolved from mainly amorphous with a minor crystalline intermetallic phase for the film without nitrogen, to nanocomposites with a cubic crystalline phase in an amorphous matrix for intermediate nitrogen content (15-41 at.% N), and at higher nitrogen content (46-51 at.% N) to crystalline solid solution nitrides with a NaCl-type structure. Partial elemental segregation on the nanoscale was found in all studied samples and the films exhibited different segregation behaviour depending on the nitrogen content, implying that the structural evolution on the nanoscale of films in this material system complex and highly composition-dependent. The hardness increased with increasing nitrogen content, reaching a maximum at about 30 GPa at for the nitride films with 50 at.% N. Deformation behaviour, studied by indentation measurements, of the nitride films was found to be ductile, where no sign of crack formation could be observed. This can be attributed to a metallic phase in the columnar boundaries caused by partial elemental segregation of mainly yttrium. Hence, films within in this material system, although the nanostructure is found to be relatively complex, show very promising mechanical properties and the structural complexity can be used as a guide for designing nitride materials that combine high hardness with ductility.
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| 43. |
- von Fieandt, Kristina, et al.
(författare)
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Optical and electrical properties of hard (Hf,Nb,Ti,V,Zr)N-x thin films
- 2021
-
Ingår i: Vacuum. - : Elsevier. - 0042-207X .- 1879-2715. ; 193
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Tidskriftsartikel (refereegranskat)abstract
- (Hf,Nb,Ti,V,Zr)N-x coatings with nitrogen content between 0 and 49 at.% were deposited by sputter deposition, and thoroughly characterised. Nitrogen-free coatings were found to have a bcc structure, low hardness (8 GPa), and an electrical resistivity of 144 mu Omega cm. The nitride coatings (43-49 at.% N) had NaCl-type structure, consistent with a multi-component solid solution phase. Photoelectron core level binding energies indicate that the electronic structure of the multi-component nitride differs from that of the binary nitrides, probably a result of charge transfer between the metal atoms. The nitride coatings exhibited a dense microstructure and a hardness between 29 and 33 GPa, and electrical resistivities of 141-254 mu Omega cm. They also exhibited a minimum in the optical reflectance, similar to that of TiN, indicating plasmonic properties. The position of this minimum was found to be shifted to smaller wavelengths (272-339 nm) compared to a TiN reference (428 nm) and varied with nitrogen content. The tuneability of the optical properties, in combination with the potential to influence the electronic structure through charge transfer between metal atoms point to new interesting routes to design optical materials, and a new class of optical materials based on the concept of multi-component nitrides.
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| 44. |
- von Fieant, Kristina, et al.
(författare)
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In Situ Formation of Ge Nanoparticles by Annealing of Al-Ge‑N ThinFilms Followed by HAXPES and XRD
- 2019
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Ingår i: Inorganic Chemistry. - : American Chemical Society (ACS). - 0020-1669 .- 1520-510X. ; 58:16, s. 11100-11109
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Tidskriftsartikel (refereegranskat)abstract
- Ge nanoparticles embedded in thin films have attracted a lot of attention due to their promising optical and electronic properties that can be tuned by varying the particle size and choice of matrix material. In this study, Ge nanoparticle formation was investigated for Al-Ge-N based thin films by simultaneous measurements of HAXPES and grazing incidence XRD during in situ annealing in vacuum conditions. As-deposited Al-Ge-N thin films, synthesized by reactive dc magnetron sputtering, consisted of a nanocrystalline (Al1–xGex)Ny solid solution and an amorphous tissue phase of Ge3Ny. Upon annealing to 750 °C, elemental Ge was formed shown by both HAXPES and XRD measurements, and N2 gas was released as measured by a mass spectrometer. Postannealed ex situ analysis by SEM and TEM showed that the elemental Ge phase formed spherical nanoparticles on the surface of the film, with an average size of 210 nm. As the annealing temperature increased further to 850 °C, the Ge particles on the film surface evaporated, while the phase segregation of Ge still could be observed within the film. Thus, these results show the possibility for a controlled synthesis of Ge nanoparticles through annealing of Al-Ge-N thin films to produce materials suitable for use in electronic or optoelectronic devices.
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| 45. |
- von Fieant, Kristina, et al.
(författare)
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Multi-component (Al,Cr,Nb,Y,Zr)N thin films by reactive magnetron sputter deposition for increased hardness and corrosion resistance
- 2020
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Ingår i: Thin Solid Films. - : Elsevier BV. - 0040-6090 .- 1879-2731. ; 693
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Tidskriftsartikel (refereegranskat)abstract
- Multi-component nitride thin films in the Al-Cr-Nb-Y-Zr system with non-equimolar composition have been deposited by reactive dc magnetron sputtering. The substrate temperature and substrate bias have been varied, from room temperature to 700 degrees C and from 0 to -200 V respectively. The relationship between these varied growth conditions on the structure, morphology, mechanical and corrosion properties of the films have been probed. All films consisted of a single solid solution with a NaCl-type structure, as shown by X-ray diffraction. However, elemental energy dispersive spectroscopy maps, obtained in the scanning transmission electron microscope, indicated that there could be partial segregation of Al, Cr and Y atoms within the grains. The microstructure of the films became denser, more fine-grained and smoother as the bias and temperature were increased. Nanoindentation showed that the hardness of the films increased with both bias and temperature, reaching a maximum of 27 +/- 2 GPa. The corrosion resistance of the films, studied by performing potentiodynamic polarisation curves in 1 M HCl, was also found to be improved when compared to a commercially available hyper-duplex stainless steel and a ternary reference (Nb,Zr)N thin film as well.
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| 46. |
- Yurdakal, Sedat, et al.
(författare)
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Selective photocatalytic oxidation of 3-pyridinemethanol on platinized acid/base modified TiO2
- 2021
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Ingår i: Catalysis Science & Technology. - : Royal Society of Chemistry. - 2044-4753 .- 2044-4761. ; 11:13, s. 4549-4559
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Tidskriftsartikel (refereegranskat)abstract
- TiO2 catalysts, modified with acidic or alkaline solutions and then platinized, were used for the partial photocatalytic oxidation of 3-pyridinemethanol to 3-pyridinemethanal and vitamin B-3 under environmentally friendly conditions. The reaction took place in water under UVA light and air oxygen. Catalysts were characterized by TEM, photoluminescence, DRIFT-IR, Raman, DRS, XPS, and photocurrent measurements. The photocatalytic activity results show that Pt loading of untreated samples leads to a significant activity improvement (hence product yield) as much as acid and alkaline treatments do. Moreover, the alkaline treated TiO2 samples exhibit a further increase in activity after loading with Pt. Pt acts as an electron scavenger promoting electron transfer from the TiO2 conduction band, consequently boosting the photogenerated pair numbers available for the reactive process. Photocurrent measurements show that the TiO2 photocatalysts' active sites increase significantly after platinization and alkaline/acid treatment. The treated and/or Pt loaded catalysts showed good thermal stability (at least up to 400 degrees C).
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