| 1. |
- Halim, Joseph, 1985-
(författare)
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Synthesis and Characterization of 2D Nanocrystals and Thin Films of Transition Metal Carbides (MXenes)
- 2014
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Licentiatavhandling (övrigt vetenskapligt/konstnärligt)abstract
- Two dimensional (2D) materials have received growing interest because of their unique properties compared to their bulk counterparts. Graphene is the archetype 2D solid, but other materials beyond graphene, such as MoS2 and BN have become potential candidates for several applications. Recently, a new family of 2D materials of early transition metal carbides and carbonitrides (Ti2CTx, Ti3C2Tx, Ti3CNTx, Ta4C3Tx, and more), labelled MXenes, has been discovered, where T stands for the surface-terminating groups.Before the present work, MXenes had only been synthesized in the form of exfoliated and delaminated powders, which is not suitable for electronic applications. In this thesis, I demonstrate the synthesis of MXenes as epitaxial thin films, a more suitable form for electronic and photonic applications. Results show that 2D epitaxial Ti3C2Tx films - produced by HF and NH4HF2 etching of magnetron sputter-grown Ti3AlC2 - exhibit metallic conductive behaviour down to 100 K and are 90% transparent to light in the visible-infrared range. The results from this work may open the door for MXenes as potential candidates for transparent conductive electrodes as well as in electronic, photonic and sensing applications.MXenes have been shown to intercalate cations and molecules between their layers that in turn can alter the surface termination groups. There is therefore a need to study the surface chemistries of synthetized MXenes to be able to study the effect of intercalation as well as altering the surface termination groups on the electronic structure and chemical states of the elements present in MXene layers. X-ray Photoelectron Spectroscopy (XPS) in-depth characterization was used to investigate surface chemistries of Ti3C2Tx and Ti2CTx. This thesis includes the discussion of the effect of Ar+ sputtering and the number of layers on the surface chemistry of MXenes. This study serves as a baseline for chemical modification and tailoring of the surface chemistry groups to potential uses and applications.New MXene phases, Nb2CTx and V2CTx, are shown in this thesis to be produced from HF chemical etching of Nb2AlC and V2AlC powders. Characterization of the produced MXenes was carried out using Scanning Electron Microscopy (SEM), X-Ray Diffraction (XRD), Transmission Electron Microscope (TEM) and XPS. Nb2CTx and V2CTx showed promising performance as electrodes for Li-ion batteries.In this thesis, electrochemical etching was used in an attempt to produce 2D metal carbides (MXene) from their ternary metal carbides, Ti3SiC2, Ti3AlC2 and Ti2AlC MAX phases. MAX phases in the form of highly dense bulk produced by Hot Isostatic Press. Several etching solutions were used such as HF, NaCl and HCl. Unlike the HF chemical etching of MAX phases, which results in MXenes, the electrochemical etching resulted in Carbide Derived Carbon (CDC). Here, I show the characterization of the produced CDC using several techniques such as XRD, TEM, Raman spectroscopy, and XPS. Electrochemical characterization was performed in the form of cyclic voltammetry, which sheds light on the etching mechanism.
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| 2. |
- Kerdsongpanya, Sit
(författare)
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Scandium Nitride Thin Films for Thermoelectrics
- 2012
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Licentiatavhandling (övrigt vetenskapligt/konstnärligt)abstract
- Thermoelectric devices are one of the promising energy harvesting technologies, since they can convert heat (i.e. a temperature gradient) to electricity. This result leads us to use them to harvest waste heat from heat engines or in power plants to generate usable electricity. Moreover, thermoelectric devices can also perform cooling. The conversion process is clean, with no emission of greenhouse gases during the process. However, the converting efficiency of thermoelectrics is very low because of the materials limitations of the thermoelectric figure of merit (ZTm). Thus, there is high demand to maximize the ZTm.I have discovered that ScN has high power factor 2.5 mW/(mK2) at 800 K, due to low metalliclike electrical resistivity (∼3.0 μΩm) with retained relatively large Seebeck coefficient of -86 μV/K. The ScN thin films were grown by reactive dc magnetron sputtering from Sc targets. For ScN, X-ray diffraction, supported by transmission electron microscopy, show that we can obtain epitaxial ScN(111) on Al2O3(0001). We also reported effects on thermoelectric properties of ScN with small changes in the composition with the power factor changing one order of magnitude depending on e.g. oxygen, carbon and fluorine content which were determined by elastic recoil detection analysis. The presence of impurities may influence the electronic density of states or Fermi level (EF) which could yield enhancement of power factor.Therefore, the effects of defects and impurities on the electronic density of states of scandium nitride were investigated using first-principles calculations with general gradient approximation and hybrid functionals for the exchange correlation energy. Our results show that for Sc and N vacancies can introduce asymmetric peaks in the density of states close to the Fermi level. We also find that the N vacancy states are sensitive to total electron concentration of the system due to their possibility for spin polarization. Substitutional point defects shift the Fermi level in the electronic band according to their valence but do not introduce sharp features. The energetics and electronic structure of defect pairs are also studied. By using hybrid functionals, a correct description of the open band gap of scandium nitride is obtained, in contrast to regular general gradient approximation. Our results envisage ways for improving the thermoelectric figure of merit of ScN by electronic structure engineering through stoichiometry tuning and doping.
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| 3. |
- Gharavi, Mohammad Amin
(författare)
-
Nitride Thin Films for Thermoelectric Applications : Synthesis, Characterization and Theoretical Predictions
- 2017
-
Licentiatavhandling (övrigt vetenskapligt/konstnärligt)abstract
- Thermoelectrics is the reversible process which transforms a temperature gradient across a material into an external voltage through a phenomenon known as the Seebeck effect. This has resulted in niche applications such as solid-state cooling for electronic and optoelectronic devices which exclude the need for a coolant or any moving parts and long-lasting, maintenance-free radioisotope thermoelectric generators used for deep-space exploration. However, the high price and low efficiency of thermoelectric generators have prompted scientists to search for new materials and/or methods to improve the efficiency of the already existing ones. Thermoelectric efficiency is governed by the dimensionless figure of merit ??, which depends on the electrical conductivity, thermal conductivity and Seebeck coefficient value of the material and has rarely surpassed unity.In order to address these issues, research conducted on early transition metal nitrides spearheaded by cubic scandium nitride (ScN) thin films showed promising results with high power factors close to 3000 μWm−1K−2 at 500 °C. In this thesis, rock-salt cubic chromium nitride (CrN) deposited in the form of thin films by reactive magnetron sputtering was chosen for its large Seebeck coefficient of approximately -200 μV/K and low thermal conductivity between 2 and 4 Wm−1K−1. The results show that CrN in single crystal form has a low electrical resistivity below 1 mΩcm, a Seebeck coefficient value of -230 μV/K and a power factor close to 5000 μWm−1K−2 at room temperature. These promising results could lead to CrN based thermoelectric modules which are cheaper and more stable compared to traditional thermoelectric material such as bismuth telluride (Bi2Te3) and lead telluride (PbTe).In addition, the project resulting this thesis was prompted to investigate prospective ternary nitrides equivalent to ScN with (hopefully) better thermoelectric properties. Scandium nitride has a relatively high thermal conductivity value (close to 10 Wm−1K−1), resulting in a low ??. A hypothetical ternary equivalent to ScN may have a similar electronic band structure and large power factor, but with a lower thermal conductivity value leading to better thermoelectric properties. Thus the elements magnesium, titanium, zirconium and hafnium were chosen for this purpose. DFT calculations were used to simulate TiMgN2, ZrMgN2 and HfMgN2. The results show the MeMgN2 stoichiometry to be stable, with two rivaling crystal structures: trigonal NaCrS2 and monoclinic LiUN2.
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| 4. |
- Kerdsongpanya, Sit, 1985-
(författare)
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Design of Transition-Metal Nitride Thin Films for Thermoelectrics
- 2015
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- Thermoelectric devices are one of the promising energy harvesting technologies, because of their ability to convert heat (temperature gradient) to electricity by the Seebeck effect. Furthermore, thermoelectric devices can be used for cooling or heating by the inverse effect (Peltier effect). Since this conversion process is clean, with no emission of greenhouse gases during the process, this technology is attractive for recovering waste heat in automobiles or industries into usable electricity. However, the conversion efficiency of such devices is rather low due to fundamental materials limitations manifested through the thermoelectric figure of merit (ZT). Thus, there is high demand on finding materials with high ZT or strategies to improve ZT of materials.In this thesis, I discuss the basics of thermoelectrics and how to improve ZT of materials, including present-day strategies. Based on these ideas, I propose a new class of materials for thermoelectric applications: transition-metal nitrides, mainly ScN, CrN and their solid solutions. Here, I employed both experimental and theoretical methods to synthesize and study their thermoelectric properties. My study envisages ways for improving the thermoelectric figure of merit of ScN and possible new materials for thermoelectric applications.The results of my studies show that ScN is a promising thermoelectric material since it exhibits high thermoelectric power factor 2.5x10-3 Wm-1K-2 at 800 K, due to low metallic-like electrical resistivity while retained relatively large Seebeck coefficient. My studies on thermal conductivity of ScN also suggest a possibility to control thermal conductivity by tailoring the microstructure of ScN thin films. Furthermore, my theoretical studies on effects of impurities and stoichiometry on the electronic structure of ScN suggest the possibly to improve ScN ZT by stoichiometry tuning and doping. For CrN and Cr1-xScxN solid solution thin films, the results show that the power factor of CrN (8x10-4 Wm-1K-2 at 770 K) can be retained for the solid solution Cr0.92Sc0.08N. Finally, density functional theory was used to enable a systematic predictionbased strategy for optimizing ScN thermoelectric properties via phase stability of solid solutions. Sc1-xGdxN and Sc1-xLuxN are stabilized as disordered solid solutions, while in the Sc-Nb-N and Sc-Ta-N systems, the inherently layered ternary structures ScNbN2 and ScTaN2 are stable.
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| 5. |
- Landälv, Ludvig, 1982-
(författare)
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Physical vapor deposition and thermal stability of hard oxide coatings
- 2019
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- The state-of-the-art tools for machining metals are primarily based on a metal-ceramic composite (WC-Co) coated with different combinations of carbide, nitride, and oxide coatings. Combinations of these coating materials are optimized to withstand specific wear conditions. Oxide coatings, mainly α-Al2O3, are especially desired because of their high hot-hardness, chemical inertness with respect to the workpiece, and their low friction. The search for possible alloy elements, which may facilitate the deposition of such oxides by means of physical vapor deposition (PVD) techniques, has been the goal of this thesis. The sought alloy should form thermodynamically stable or metastable compounds, compatible with the temperature of use in metal cutting application. This thesis deals with process development and coating characterization of such new oxide alloy thin films, focusing on the Al-V-O, Al-Cr-Si-O, and Cr-Zr-O systems.Alloying aluminum oxide with iso-valent vanadium is a candidate for forming the desired alloys. Therefore, coatings of (Al1-xVx)2O3, with x ranging from 0 to 1, were deposited with reactive sputter deposition. X-ray diffraction showed three different crystal structures depending on V-metal fraction in the coating: α-V2O3 rhombohedral structure for 100 at.% V, a defect spinel structure for the intermediate region, (63 - 42 at.% V), and a gamma-alumina-like solid solution at lower V-content, (18 and 7 at.%), were observed, the later was shifted to larger d-spacing compared to the pure γ-Al2O3 sample obtained if deposited with only Al-target. Annealing the Al-rich coatings in air resulted in formation of V2O5 crystals on the surface of the coating after annealing to 500 °C for 42 at.% V and 700 °C for 18 at.% V metal fraction respectively. The highest thermal stability was shown for pure γ-Al2O3-coating which transformed to α-Al2O3 after annealing to 1100° C. Highest hardness was observed for the Al-rich oxides, ~24 GPa. The hardness then decreases with increasing V-content, larger than 7 at.% V metal fraction. Doping the Al2O3 coating with 7 at.% V resulted in a significant surface smoothening compared to the binary oxide. The measured hardness after annealing in air decreased in conjunction with the onset of further oxidation of the coatings. This work increases the understanding of this complicated material system with respect to possible phases formed with pulsed DC magnetron sputtering deposition as well as their response to annealing in air.The inherent difficulties of depositing insulating oxide films with PVD, requiring a closed electrical circuit, makes the investigation of process stability an important part of this research. In this context, I investigated the influence of adding small amount of Si in Al-Cr cathode on the coating properties in a pulsed DC industrial cathodic arc system and the plasma characteristics, process parameters, and coating properties in a lab DC cathodic arc system. Si was chosen here due to a previous study showing improved erosion behavior of Al-Cr-Si over pure Al-Cr cathode without Si incorporation in the coating. The effect of Si in the Al-Cr cathode in the industrial cathodic arc system showed slight improvements on the cathode erosion but Si was found in all coatings where Si was added in the cathode. The Si addition promoted the formation of the B1-like metastable cubic oxide phase and the incorporation led to reduced or equal hardness values compared to the corresponding Si-free processes. The DC-arc plasma study on the same material system showed only small improvements in the cathode erosion and process stability (lower pressure and cathode voltage) when introducing 5 at.% Si in the Al70Cr30-cathode. The presence of volatile SiO species could be confirmed through plasma analysis, but the loss of Si through these species was negligible, since the coating composition matched the cathode composition also under these conditions. The positive effect of added Si on the process stability at the cathode surface, should be weighed against Si incorporation in the coating. This incorporation seems to lead to a reduction in mechanical properties in the as-deposited coatings and promote the formation of a B1-like cubic metastable oxide structure for the (Al,Cr)2O3 oxide. This formation may or may not be beneficial for the final application since literature indicates a slight stabilization of the metastable phase upon Si-incorporation, contrary to the effect of Cr, which stabilizes the α-phase.The thermal stability of alloys for metal cutting application is crucial for their use. Previous studies on another alloy system, Cr-Zr-O, had shown solid solution, for Cr-rich compositions in that material system, in the sought corundum structure. The thermal stability of α-Cr0.28Zr0.10O0.61 coating deposited by reactive radio frequency (RF)-magnetron sputtering at 500 °C was therefore investigated here after annealing in vacuum up to 870 °C. The annealed samples showed transformation of α-(Cr,Zr)2O3 and amorphous ZrOx-rich areas into tetragonal ZrO2 and bcc-Cr. The instability of the α-(Cr,Zr)2O3 is surprising and possibly related to the annealing being done under vacuum, facilitating the loss of oxygen. Further in situ synchrotron XRD annealing studies on the α-Cr0.28Zr0.10O0.61 coating in air and in vacuum showed increased stability for the air annealed sample up to at least 975 °C, accompanied with a slight increase in ex-situ measured nanohardness. The onset temperature for formation of tetragonal ZrO2 was similar to that for isothermally vacuum annealing. The synchrotron-vacuum annealed coating again decomposed into bcc-Cr and t-ZrO2, with an addition of monoclinic–ZrO2 due to grain growth. The stabilization of the room temperature metastable tetragonal ZrO2 phase, due to surface energy effects present with small grains sizes, may prove to be useful for metal cutting applications. The observed phase segregation of α-(Cr,Zr)2O3 and formation of tetragonal ZrO2 with corresponding increase in hardness for this pseudobinary oxide system also opens up design routes for pseudobinary oxides with tunable microstructural and mechanical properties.
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| 6. |
- Lauridsen, Jonas, 1983-
(författare)
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TiC-based nanocomposite coatings as electrical contacts
- 2011
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- This Thesis concerns the advanced surface engineering of novel TiC-based nanocomposite and AgI electrical contact materials. The objective is to make industrially applicable coatings that are electrically conductive and wear-resistant, and have a low coefficient of friction. I have studied electrical contact systems consisting of a Cu substrate with a Ni diffusion barrier and loading support, and a conductive top coating. The contact systems were characterized by x-ray diffraction and photoelectron spectroscopy, analytical electron microscopy, ion beam analysis, nanoindentation, resistivity, and contact resistance measurements. Nc-TiC/a-C/SiC nanocomposite coatings consisting of nanocrystalline (nc) TiC embedded in an amorphous (a) matrix of C/SiC were deposited by magnetron sputtering with rates as high as 16 μm/h. These coatings have a contact resistance comparable with Ag at high loads (~800 N) and a resistivity of 160-770 μΩcm. The electrical properties of the contact can be improved by adding Ag to make nc-Ag/nc-TiC/a-SiC nanocomposites. It is possible to tailor the size and distribution of the Ag grains by varying the fraction of amorphous matrix, so as to achieve good conductivity in all directions in the coatings. Ti-Si-C-Ag coatings have a contact resistance that is one magnitude larger than Ag at lower loads (~1 N), and a resistivity of 77-142 μΩcm. The conductivity of the matrix phase can be increased by substituting Ge, Sn or Cu for Si, which also reduces the Ag grain growth. This yields coatings with a contact resistance twice as high as Ag at loads of 1 N, and a resistivity 274-1013 μΩcm. The application of a conductive top layer of Ag-Pd upon a Ti-Si-C-Ag:Pd coating can further reduce the contact resistance. For barrier materials against Cu interdiffusion, it is shown that conventional electroplating of Ni can be replaced with sputtering of Ni or Ti layers. This is an advantage since both contact and barrier layers can now be deposited in and by the same deposition process. For Ti-B-C coatings deposited by magnetron sputtering, I demonstrate promising electrical properties in a materials system otherwise known for its good mechanical properties. In coatings of low B concentration, the B is incorporated into the TiC phase, probably by enrichment on the TiC{111} planes. The corresponding disturbance of the cubic symmetry results in a rhombohedral TiC:B structure. Finally, it is shown that AgI coatings consisting of weakly agglomerated AgI grains function as solid lubricant on Ag contacts. In an Ag sliding electrical contact, AgI decreases the friction coefficient from ~1.2 to ~0.4. After a few hundred operations, AgI grains have deagglomerated and Ag from the underlying layer is exposed on the surface and the contact resistance decreases to < 100 μΩ.
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| 7. |
- Fashandi, Hossein
(författare)
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Functional Nanostructures for Gas Sensors
- 2015
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Licentiatavhandling (övrigt vetenskapligt/konstnärligt)abstract
- This research focuses on three main topics within the aims of FUNMAT, which are:Ohmic contacts to high-temperature chemical gas sensors.Studies of catalytic monolayers on active gate metal in SiC-based gas sensors.Investigating potential sensing properties of the nanoscale material MXene.Within the first research topic, we study the growth of Ohmic contacts to 4H-SiC for high temperature and corrosive environment applications, being a need in chemical gas sensors e.g. for automotive industry. For this purpose, common commercially-synthesized contacts are not suitable, due to either the presence of low-melting point elements or rapid oxidation. Improving the previously reported growth methods, designing durable oxygen-barrier capping layers, and synthesizing new contact-materials are our main focuses.For the second research topic, we investigate the improvement of the sensing performance of platinum-based sensing layers in silicon carbide field-effect gas sensors, which have many industrial applications. This project started with modification of field-effect-based metal oxide semiconductor CO sensors by the synthesis of one monolayer iron oxide on the platinum sensing layers of the sensors. Monolayer metal oxides have been reported to enhance the catalytic properties of platinum which is a promising result to be used in improving the performance of gas sensors.And finally, the third research topic covers studies of newly synthesized materials to be explored for any potential sensing property. Our focus is on metal carbide nano-sheets known as MXene phases and to study their gas adsorption properties. Due to several uninvestigated features of newly synthesized materials, ab.initio. theoretical studies are of importance.
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| 8. |
- Fashandi, Hossein, 1984-
(författare)
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Novel Layered and 2D Materials for Functionality Enhancement of Contacts and Gas Sensors
- 2016
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- Chemical gas sensors are widely-used electronic devices for detecting or measuring the density levels of desired gas species. In this study, materials with established or potential applications for gas sensors are treated. For the case of high-temperature applications (≈ 600 °C), semiconductor-based gas sensors suffer from rapid oxidation of the metallic ohmic contacts, the same cause-of-failure as for the general case of high-temperature semiconductor electronics. 4H-SiC is an ideal semiconductor for high-temperature applications. Ti3SiC2 is a known ohmic contact to 4H-SiC with the known two-step synthesis process of post-annealing of pre-deposited Ti/Al multilayers or sputter-deposition of Ti3SiC2 films at > 900 °C. Here, sputter-deposition of Ti on 4H-SiC at > 900 °C is presented as a novel single-step method for the synthesis of Ti3SiC2 ohmic contacts, based on a concurrent reaction between sputter-deposited Ti and 4HSiC. Ti3SiC2, similar to any other known ohmic contact, degrade rapidly in high-temperature oxidizing ambient. To try to overcome this obstacle, noble metal diffusion into Ti3SiC2 has been s studied with the goal to retain ohmic properties of Ti3SiC2 and harnessing oxidation resistivity of noble metals. A novel exchange intercalation between Ti3SiC2 and Au is discovered which results in the almost complete exchange of Si with Au giving rise to novel Ti3AuC2 and Ti3Au2C2. Ti3IrC2 is also synthesized through exchange intercalation of Ir into Ti3Au2C2. All the aforementioned phases showed ohmic properties to 4H-SiC. This technique is also studied based on Ti2AlC and Ti3AlC2 resulting in the synthesis of novel Ti2Au2C and Ti3Au2C2, respectively. Using Ti3AuC2 and an Au/IrOx capping layer, an ohmic contact was manufactured, which maintained ohmic properties and showed no structural defects after 1000 h of aging at 600 °C air.Ti3SiC2 is a member of a large family of materials known as Mn+1AXn phases. While exchange reactions of Si (or Al) planes in Ti3SiC2 (Ti2AlC and Ti3AlC2) is presented here, a world-wide research already exists on chemical removal of the same atomic planes from different Mn+1AXn phases and the synthesis of Mn+1Xn sheets known as MXenes. I performed a theoretical study regarding simulation of electronic and structural properties of more than120 different possible MXene phases. The results show that some MXene phases, when terminated by particular gas species, turn into Dirac materials. That is, they possess massless Dirac fermions with different properties compared to graphene such as higher number of Dirac points at the Fermi level, giant spin orbit splitting, and preserved 2D-type electronic properties by extending the dimensionality. The general substantial change of the electronic properties of MXenes under different gas adsorption configurations stands out and can thus be harnessed for sensing applications.Growth of monolayer iron oxide on porous Pt sensing layers is another novel approach used in this study for applying the unique properties of 2D materials for gas sensors. A low temperature shift in CO oxidation characteristics is presented. The approach is similar to that previously reported using bulk single crystal Pt substrate, the latter being an unrealistic model for sensors and catalysts. Monolayer-coated Pt sensing layers were fabricated as the metal component of a metal oxide semiconductor (MOS) capacitor device, whereby the electrical response of the MOS device could be used to map out the catalytic properties of the sensing layer. The monolayer-coated Pt surface showed to be stable with retained improved catalytic properties for > 200 h. The MOS device measurements are here utilized as a handy method for in-situ monitoring of the surface chemical properties of the monolayer-coated Pt and the approach is highly functional for use and characterization of monolayer coatings of widely used sensingor catalytic layers.
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| 9. |
- Frodelius, Jenny, 1978-
(författare)
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Thick and Thin Ti2AlC Coatings
- 2010
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- This Thesis explores the deposition techniques of magnetron sputtering and high velocity oxy-fuel (HVOF) spraying for Ti2AlC as a promising high-temperature material. Magnetron sputtering aims at producing thin (≤1 μm) Ti2AlC films of high crystal quality for use as a model system in understanding the material’s basic properties. HVOF is a new method for deposition of thick (≥200 μm) coatings by spraying Ti2AlC powder, with the aim of transferring the good bulk properties to coatings. The oxidation behavior of Ti2AlC coatings has been investigated for temperatures up to 1200 °C in air. As-deposited Ti2AlC(0001) thin films decompose into TiC during vacuum annealing at 700 °C by out-diffusion of Al as shown by x-ray diffraction analysis. The release of Al starts already at 500 °C in ambient air as driven by aluminum oxide formation on the film surface where the oxide initially forms clusters as observed by electron microscopy. While sputtering from a Ti2AlC target is simpler than by using different elemental targets, the resulting film composition differs from the target stoichiometry. This is due to differences in energy and angular distribution of the sputtered species and evaporation of Al at substrate temperatures above 700 °C. The composition can be compensated for by adding Ti to bind the Al and obtain phase-pure Ti2AlC coatings. For HVOF, I demonstrate how the total gas flow of a H2/O2 mixture (441-953 liter/min) and the powder grain size (30-56 μm) determine the thickness, density, and microstructure of the coatings. High gas flow and small grain size yield thick coatings of 210 μm with a low porosity of 2-8 % and a tensile stress of ≥80 MPa. A fraction of the Ti2AlC powder decomposes during spraying into TiC, Ti3AlC2, and Ti-Al alloys. The coatings also contain as much as 25 at.% O since the powder partly oxidizes during the spraying process. Increasing the powder size and decreasing the total gas flow yield a higher amount of Ti2AlC, but produces thinner coatings with lower cohesion. Post-annealing of the coatings at 900 °C in vacuum increases the Ti2AlC content due to a reversible phase transformation of the as-sprayed material. The high oxygen content, however, hinders the coating to completely transform into Ti2AlC and deteriorates its oxidation resistance. The work thus offers insights to the key parameters for optimizing Ti2AlC coating processing.
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| 10. |
- Khatibi, Ali, 1982-
(författare)
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Deposition and Phase Transformations of Ternary Al-Cr-O Thin Films
- 2011
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Licentiatavhandling (övrigt vetenskapligt/konstnärligt)abstract
- This thesis concerns the ternary Al-Cr-O system. (Al1-xCrx)2O3 solid solution thin films with 0.62 gas mixture. As-deposited and annealed (Al1-xCrx)2O3 thin films were analyzed by x-ray diffraction, elastic recoil detection analysis, scanning electron microscopy, transmission electron microscopy, and nanoindentation. (Al1-xCrx)2O3 showed to have face centered cubic structure with lattice parameter of 4.04 Å, which is in contrast to the typical corundum structure reported for these films. The as-deposited films exhibited hardness of ~ 26 GPa and elastic modulus of 220-235 GPa. Phase transformation from cubic to corundum (Al0.32Cr0.68)2O3 starts at 925 °C. Annealing at 1000 °C resulted in complete phase transformation, while no precipitates of alumina and chromia were observed. Studies on kinetics of phase transformation showed a two-step thermally activated process; phase transformation and grain growth with the apparent activation energies 213±162 and 945±27 kJ/mol, respectively.
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| 11. |
- Khatibi, Ali, 1982-
(författare)
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Growth and Heat Treatment Studies of Al-Cr-O and Al-Cr-O-N Thin Films
- 2013
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- Aluminum oxide based thin films are applied on cutting tool inserts as a top layer to protect the underlying nitride or carbide functional layer from the harsh working environment in terms of abrasive and chemical wear under thermal and pressure load. This Thesis explores the synthesis and characterization of the next generations of multifunctional wear-resistant thin film coatings in the form of Al-Cr-O and Al-Cr-O-N compounds. The experiments include the deposition of oxide films by reactive magnetron sputtering and cathodic arc evaporation as well as investigation of structural and mechanical properties in as-deposited and annealed states. Ternary (Al1-xCrx)2+yO3-y films were deposited on Si(001) and WC-Co substrates kept at 400-575 °C from elemental Al and Cr or alloyed Al/Cr cathodes in Ar/O2, O2/N2, and pure O2 atmospheres. Also, quaternary (Al1-xCrx)2+z(O1-yNy)3-z films were deposited at substrate temperature of ~400 °C on WC-Co substrates in O2/N2 atmosphere. X-ray diffraction and analytical electron microscopy combined with ab initio calculations showed the existence of a new face centered cubic (Al,Cr)2O3 phase with 33% vacancies on the metallic Al/Cr sites. Increasing the temperature during annealing of these metastable cubic films resulted in phase transformation to corundum solid solution in the temperature range of 900-1100 °C. The apparent activation energy of this phase transformation process was calculated as 380-480 kJ/mol by using the Johnson-Mehl-Avrami model. The mechanical properties of the cubic and corundum oxide films were measured in terms of nanoindentation hardness and metal cutting performance. The cubic and corundum films showed hardness values of 26-28 GPa and 28-30 GPa, respectively. The oxynitride solid solution films showed to be predominantly cubic Al-Cr-N and cubic-(Al,Cr)2O3 and secondary corundum-(Al,Cr)2O3 with a hardness of ~30 GPa, slightly higher than Al-rich ternary oxides. Metal cutting performance tests showed that the good wear properties are mainly correlated to the oxygen-rich coatings, regardless of the cubic or corundum fractions.
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| 12. |
- Sønderby, Steffen
(författare)
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Physical Vapor Deposition of Yttria-Stabilized Zirconia and Gadolinia-Doped Ceria Thin Films for Fuel Cell Applications
- 2012
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Licentiatavhandling (övrigt vetenskapligt/konstnärligt)abstract
- In this thesis, reactive sputter deposition of yttria-stabilized zirconia (YSZ) and cerium gadolinium oxide (CGO) thin films for solid oxide fuel cell (SOFC) applications have been studied. All films have been deposited under industrial conditions.YSZ films were deposited on silicon wafers as well as commercial NiO-YSZ fuel cell anodes. The texture, morphology, and composition of the deposited films were investigated with respect to deposition parameters such as bias voltage which was identified as a key parameter to tailor the texture of the film and promote less columnar coatings when depositing on Si. In contrast, films grown on NiO-YSZ fuel cell anodes were seen to be randomly orientated when deposited at low substrate bias voltages. When the bias voltage was increased the film took over the orientation of underlying substrate due to substrate template effects. The deposited coatings were found to be homogeneous large areas within the coating zone, which is highly important for industrial applications.The performance of sputtered CGO thin films as diffusion barriers for stopping Sr diffusion between SOFC cathodes and electrolytes was also studied. This was done by introducing the sputtered CGO films in a metal-based SOFC setup. The performance depended on the density of the barrier layer, signifying that Sr diffusion and SrZrO3 formation is an issue. Area specific resistances down to 0.27 Ωcm2, corresponding to a maximum power density up to 1.14 W cm−2 at 650 °C could be obtained with sputtered CGO barrier layers in combination with Sr-doped lanthanum cobalt oxide cathodes which is a significant improvement compared conventional ceramic SOFCs.The diffusion mechanism of Sr through sputtered CGO films was investigated. For this purpose, a model system simulating a SOFC was prepared by depositing CGO and YSZ on cathode material. This setup allowed observation of Sr diffusion by observing SrZrO3 formation using X-ray diffraction while annealing. Electron microscopy was subsequently performed to confirm the results. It was found that Sr diffused along column/grain boundaries in the CGO films but by modifying the film thickness and microstructure the breaking temperature of the barrier could be increased.
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| 13. |
- Tengstrand, Olof
(författare)
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Me-Si-C (Me= Nb, Ti or Zr) : Nanocomposite and Amorphous Thin Films
- 2012
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Licentiatavhandling (övrigt vetenskapligt/konstnärligt)abstract
- This thesis investigates thin films of the transition metal carbide systems Ti-Si-C, Nb-Si-C, and Zr-Si-C, deposited at a low substrate temperature (350 °C) with dc magnetron sputtering in an Ar discharge. Both the electrical and mechanical properties of these systems are highly affected by their structure. For Nb-Si-C, both the ternary Nb-Si-C and the binary Nb-C are studied. I show pure NbC films to consist of crystalline NbC grains embedded in a matrix of amorphous carbon. The best combination of hardness and electrical resistivity are for ~15 at.% a-C phase. The properties of nc-NbC/a-C are similar to films consisting of nc-TiC/a-C. I further show that in a model system of epitaxial TiCx (x ~0.7) up to 5 at.% Si can be incorporated. At higher Si content, Si starts segregate out from the TiCx to the grain boundaries causing a loss of epitaxy. Higher amounts of Si into the Nb-Si-C and Zr-Si-C systems make them become amorphous. These amorphous structures are unstable under electron irradiation were they crystallize. I show that the cause of crystallization is driven by atomic displacement events.
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| 14. |
- Tengstrand, Olof, 1983-
(författare)
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Transition metal carbide nanocomposite and amorphous thin films
- 2014
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- This thesis explores thin films of binary and ternary transition metal carbides, in the Nb-C, Ti-Si-C, Nb-Si-C, Zr-Si-C, and Nb-Ge-C systems. The electrical and mechanical properties of these systems are affected by their structure and here both nanocomposite and amorphous thin films are thus investigated. By appropriate choice of transition metal and composition the films can be designed to be multifunctional with a combination of properties, such as low electric resistivity, low contact resistance and high mechanical strength. Electrical contacts are one example of application that has been of special interest in this thesis. Since some industrially important substrates used in electrical contacts soften at higher temperature, all films were deposited with dc magnetron sputtering at a low substrate temperature (200-350 °C).I show that the electrical resistivity and mechanical properties of composites consisting of nanocrystalline NbC grains (nc-NbC) in a matrix of amorphous C (a-C) depend strongly on the amount of amorphous C. The best combination of hardness (23 GPa) and electrical resistivity (260 μΩ*cm) are found in films with ~15 at.% a-C phase. This is a higher hardness and lower resistivity than measured for the more well studied Ti-C system if deposited under similar conditions. The better results can be explained by a thinner matrix of amorphous C phase in the case of NbC. The nc-NbC/a-C is therefore interesting as a material in electrical contacts.Si can be added to further control the structure and thereby the properties of binary Me-C systems. There are however, different opinions in the literature of whether Si is incorporated on the Ti or C site in the cubic NaCl (B1) structure of TiC. In order to understand how Si is incorporated in a Me-Si-C material I use a model system of epitaxial TiCx (x ~0.7). In this model system a few atomic percent of Si can be incorporated in the cubic TiC structure. The experimental results together with theoretical stability calculations suggest that the Si is positioned at the C sites forming Ti(Si,C)x. The calculation further shows a strong tendency for Si segregation, which is seen at higher Si contents in the experiments, where Si starts segregate out from the TiCx to the grain boundaries causing a loss of epitaxy.If Si is added to an Nb-C nanocomposite, it hinders the grain growth and thus a reduced size of the NbC grains is observed. The Si segregates to the amorphous matrix forming a-SiC. At the same time the resistivity increases and the hardness is reduced. With even higher amounts of Si (>25 at.%) into the Nb-Si-C material, grain growth is no longer possible and the material becomes amorphous. In order to separate between effects from the addition of Si and the choice of transition metal I compare the Nb-Si-C system to already published results for the Zr-Si-C system. I find that the hardness of the material depends on the amount of strong Si-C bonds rather than the type of transition metal. The reduced elastic modulus is, however, dependent on the choice of transition metal. I therefore suggest that it is possible to make Me-Si-C films with high wear resistance by an appropriate choice of transition metal and composition.Electron microscopy was of importance for determining amorphous structures of Nb-Si-C and Zr-Si-C at high Si contents. However, the investigations were obstructed by electron beam induced crystallization. Further investigations show that the energy transferred from the beam electrons to C and Si atoms in the material is enough to cause atomic displacements. The displacements cause volume fluctuations and thereby enhance the mobility of all the atoms in the material. The result is formation of MeC grains, which are stable to further irradiation.Finally, I have studied substitution of Ge for Si in a ternary system looking at Nb-Ge-C thin films. I show that the films consist of nc-NbC/a-C/a-Ge and that Ge in a similar way to Si decreases the size of the crystalline NbC grains. However, a transition to a completely amorphous material is not seen even at high Ge contents (~30 at.%). Another dissimilarity is that while Si bonds to C and forms a matrix of a-SiC, Ge tends to bond to Ge.
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| 15. |
- Buchholt, Kristina, 1978-
(författare)
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Nanostructured materials for gas sensing applications
- 2011
-
Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- In this Thesis I have investigated the use of nanostructured films as sensing and contact layers for field effect gas sensors in order to achieve high sensitivity, selectivity, and long term stability of the devices in corrosive environments at elevated temperatures. Electrochemically synthesized Pd and Au nanoparticles deposited as sensing layers on capacitive field effect devices were found to give a significant response to NOx with small, or no responses to H2, NH3, and C3H6. Pt nanoparticles incorporated in a TiC matrix are catalytically active, but the agglomeration and migration of the Pt particles towards the substrate surface reduces the activity of the sensing layer. Magnetron sputtered epitaxial films from the Ti-Si-C and the Ti-Ge-C systems were grown on 4H-SiC substrates in order to explore their potential as high temperature stable ohmic contact materials to SiC based field effect gas sensors. Ti3SiC2 thin films deposited on 4H-SiC substrates were found to yield ohmic contacts to n-type SiC after a high temperature rapid thermal anneal at 950 ºC. Investigations on the growth mode of Ti3SiC2 thin films with varying Si content on 4H-SiC substrates showed the growth to be lateral step-flow with the propagation of steps with a height as small as half a unit cell. The amount of Si present during deposition leads to differences in surface faceting of the films and Si-supersaturation conditions gives growth of Ti3SiC2 films with the presence of TiSi2 crystallites. Current-voltage measurements of the as-deposited Ti3GeC2 films indicate that this material is also a promising candidate for achieving long term stable contact layers to 4H-SiC for operation at elevated temperatures in corrosive environments. Further investigations into the Ti-Ge-C system showed that the previously unreported solid solutions of (Ti,V)2GeC, (Ti,V)3GeC2 and (Ti,V)4GeC3 can be synthesized, and it was found that the growth of these films is affected by the nature of the substrate.
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| 16. |
- Hatefipour, Saeid, 1970-
(författare)
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Facilitation of Industrial Symbiosis Development in a Swedish Region
- 2012
-
Licentiatavhandling (övrigt vetenskapligt/konstnärligt)abstract
- Today, sustainability of industrial regions and industrial networks is a challenge for business developers, policy makers, regional planners, local and governmental authorities and academic researchers. Because growing cities and industrial regions worldwide are intertwined with social, environmental, and economic advantages/disadvantages and challenges, in recent decades the ambition of industrial development and economic growth without environmental destruction has become a worldwide topic. To address this issue, a number of theories and pathways such as Industrial Ecology (IE) and its subfield Industrial Symbiosis (IS) toward sustainability of industrial regions and networks are being researched, examined and implemented.The overall aim of this thesis is to explore how local connectedness amongst locally distributed firms in industrial areas can be facilitated using industrial symbiosis theory and tools. To address the overall aim, the facilitation of IS development in this thesis includes three focus areas: 1) using IS theory and tools for categorization, characterization, and definitions of different lines of IS development; 2) matching the supply and demand potential of regional CO2 resources through industrial collaboration; and 3) using geographic information systems (GIS).Based on the research findings it is concluded that one approach for facilitating IS development is to apply IS theory and tools in an industrial region to find out whether any forms of IS already exist and what definitions of IS fit the area. Furthermore, it is also concluded that another approach for facilitating IS development could be matching the supply and demand potential of resources within industrial collaborations. However, availability and provision of relevant data and information plays an important role. In addition, it is seen that handling and developing existing regional data and information into a GIS-based format could contribute to facilitation of IS development. In general, it is seen that facilitating mechanism and facilitating organization are available, and should be coordinated.
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| 17. |
- Jóhannesson, Gauti, 1979-
(författare)
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Intraocular pressure : clinical aspects and new measurement methods
- 2011
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- Intraocular pressure (IOP) measurement is a routine procedure and a fundament in glaucoma care. Elevated IOP is the main risk factor for glaucoma, and to date, reduction of IOP is the only possible treatment. In a retrospective clinical material, the prevalence of open angle glaucoma was estimated on the west coast of Iceland. IOP measurement and optic nerve head examination were used to capture glaucoma suspects, within the compulsory ophthalmological examination for the prescription of eye glasses. The results were mainly in agreement with a recent prospective study in the same region. This indicated that retrospective data, under certain conditions, may contribute with useful information on the prevalence of glaucoma. However, normal tension glaucoma is underestimated if perimetry and/or fundus photography are not included in the examination. Three studies focused on the measurement of IOP. Goldmann applanation tonometry (GAT) is the standard method. GAT is affected by corneal properties, e.g. central corneal thickness (CCT) and corneal curvature (CC). Refractive surgery changes these properties. This has put focus on how corneal biomechanics translate into tonometric errors and stimulated the development of new methods. As a result, Pascal ® Dynamic Contour Tonometry (PDCT) and Icare® rebound tonometry have been introduced. A method under development by our research group is Applanation Resonance Tonometry (ART). It is based on resonance technology and estimates IOP from continuous measurement of force and contact area. Comparison of PDCT, Icare and GAT in a prospective study showed that the concordance to GAT was close to the limits set by the International Standard Organization (ISO) for PDCT, while Icare was outside the limits. To investigate if laser-assisted subepithelial keratectomy (LASEK) affects tonometry, a study was performed where measurements with GAT, PDCT and ART were obtained before, three and six months after LASEK. The hypothesis was that PDCT and ART would be less affected by LASEK than GAT. The results showed a statistically significant reduction of measured IOP three and six months after LASEK for all tonometry methods. Change in visual acuity and IOP between three and six months suggested a prolonged postoperative process. A servo-controlled prototype (ART servo) was developed. A study was undertaken to assess the agreement of ARTservo and a further developed v manual prototype (ART manual) with GAT. The study design was in accordance with the requirements of the ISO standard for tonometers. ARTmanual fulfilled the precision requirements of the ISO standard. ARTservo did not meet all the requirements of the standard at the highest pressure levels. Four tonometry methods, GAT, PDCT, Icare and ART, were investigated. None of them was independent of both CCT and CC. The inconsistencies in the results emphasize the importance of study design. A meta-analysis comprising healthy eyes (IOP ≤ 21 mmHg) in the three papers, revealed age as an important confounder. In summary, glaucoma prevalence in Iceland was investigated and the results indicated that a retrospective approach can contribute with meaningful information. ART and PDCT had a similar agreement to GAT. ART manual fulfilled the precision requirements set by the ISO-standard, ARTservo and PDCT were close, while Icare was distinctly outside the limits. All tonometry methods were affected by LASEK and no method was completely independent of corneal properties.
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| 18. |
- Lai, Chung-Chuan
(författare)
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Phase Formation of Nanolaminated Transition Metal Carbide Thin Films
- 2017
-
Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- Research on inherently nanolaminated transition metal carbides is inspired by their unique properties combining metals and ceramics, such as higher damage tolerance, better machinability and lower brittleness compared to the binary counterparts, yet retaining the metallic conductivity. The interesting properties are related to their laminated structure, composed of transition-metalcarbide layers interleaved by non-transition-metal (carbide) layers. These materials in thin-film form are particularly interesting for potential applications such as protective coatings and electrical contacts. The goal of this work is to explore nanolaminated transition metal carbides from the aspects of phase formation and crystal growth during thin-film synthesis. This was realized by studying phases in select material systems synthesized from two major approaches, namely, fromdirect-deposition and post-deposition treatment.The first approach was used in studies on the Mo-Ga-C and Zr-Al-C systems. In the former system, intriguing properties have been predicted for the 3D phases and their 2D derivatives (socalled MXenes), while in the latter system, the phases are interesting for nuclear applications. In this work, the discovery of a new Mo-based nanolaminated ternary carbide, Mo2Ga2C, is evidenced from thin-film and bulk processes. Its structure was determined using theoretical and experimental techniques, showing that Mo2Ga2C has Ga double-layers in simple hexagonal stacking between adjacent Mo2C layers, and therefore is structurally very similar to Mo2GaC, except for the additional Ga layers. For the Zr-Al-C system, the optimization of phase composition and structure of Zr2Al3C4 in a thin-film deposition process was studied by evaluating the effect of deposition parameters. I concluded that the formation of Zr2Al3C4 is favored with a plasma flux overstoichiometric in Al, and with a minimum lattice-mismatch to the substrates. Consequently, epitaxial Zr2Al3C4 thin film of high quality were deposited on 4H-SiC(001) substrates at 800 °C.With the approach of post-deposition treatment, the studies were focused on a new method of thermally-induced selective substitution reaction of Au for the non-transition-metal layers in nanolaminated carbides. Here, the reaction mechanism has been explored in Al-containing (Ti2AlCand Ti3AlC2) and Ga-containing (Mo2GaC and Mo2Ga2C) phases. The Al and Ga in these phases were selectively replaced by Au while the carbide layers remained intact, resulting in the formation of new layered phases, Ti2Au2C, Ti3Au2C2, Mo2AuC, and Mo2(Au1-xGax)2C, respectively. The substitution reaction was explained by fast outward diffusion of the Al or Ga being attracted to the surface Au, in combination with back-filling of Au, which is chemically inert to the carbide layers,to the vacancies.The substitution reaction was further applied to Ga-containing nanolaminated carbides, (Cr0.5Mn0.5)2GaC and Mo2GaC, motivated by development of novel magnetic nanolaminates. The former experiment resulted in the formation of (Cr0.5Mn0.5)2AuC, where the retained (Cr0.5Mn0.5)2C layers allowed a comparative study on the magnetic properties under the exchange of Ga for Au. After Au substitution, reduction in the Curie temperature and the saturation magnetization were observed, showing a weakened magnetic exchange interaction of the magnetic (Cr0.5Mn0.5)2 Clayers across the Au. In the Mo2GaC case, an Fe-containing MAX phase, Mo2AC with 50 at.% of Fe on the A site, was synthesized through selective substitution of Au-Fe alloy for the Ga layers, showing the first direct evidence for Fe in the MAX-phase structure. The substitution of Fe did not take place on another Mo2GaC sample tested for Fe exchange only, indicating the essential role of Au in catalyzing the Fe-substitution reaction.The knowledge gained from this thesis work contributes to improved approaches for attaining thin films of nanolaminated transition metal carbides with desired phase composition and crystal quality. The reports on the new nanolaminated phases through exchange interactions are likely to expand the family of nanolaminated carbides and advance their properties, and trigger more studies on related (quasi-) 2D materials.
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| 19. |
- Lai, Chung-Chuan, 1988-
(författare)
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Thin Film Synthesis of New Nanolaminated Ternary Carbides
- 2016
-
Licentiatavhandling (övrigt vetenskapligt/konstnärligt)abstract
- Ternary transition metal carbides with inherently nanolaminated crystal structure are a class of materials with typically higher damage tolerance, better machinability and lower brittleness compared to the binary counterparts, yet retaining their satisfactory electrical and thermal conductivity. Their interesting properties can be related to the laminated structure. Though studies of their properties based on calculations and bulk materials have suggested potential thin film applications, such as high temperature hard coatings and electrical contacts, a relatively small number of these phases have been synthesized as thin films. Investigation of thin film deposition of these inherently nanolaminated materials further the understanding of their phase formation and crystal growth.Motivated by predicted superconductivity and thermoelectric properties of molybdenum carbides and related layered molybdenum compounds, nanolaminated materials in the Mo-Ga-C ternary system were studied. Apart from the previously reported Mo2GaC, a new layered carbide, Mo2Ga2C, was synthesized in both thin film and bulk form with a postulated crystal structure related to Mo2GaC. The proposed structure was further validated by first principles calculations, showing higher stability compared to other crystal structure as well as other competing phases. The calculated lattice parameters were consistent with values from Rietveld analysis of X-ray and neutron diffraction patterns. In addition, both scanning transmission electron microscopy and X-ray photoelectron spectroscopy showed experimental evidence of the close structural-chemical relation between Mo2Ga2C and Mo2GaC.Driven by a need of high temperature protective coatings in nuclear applications, Zr-based nanolaminated carbides have become more attractive. In this work, another nanolaminated carbide, Zr2Al3C4, was synthesized in thin film form by pulsed cathodic arc deposition. Formation of the Zr2Al3C4 phase and its competing phases was studied with X-ray diffraction of thin films deposited with varying incoming flux compositions, temperatures and substrate materials. On 4H-SiC(001) substrates, highly phase-pure epitaxial Zr2Al3C4 films were formed, whereas depositions on Al2O3(001) substrates resulted in competing phases. A growth behavior similar to that of nanolaminated Mn+1AXn phases (M is a group 3-7 transition metal; A is commonly a group 13-14 element; X is C or N; n = 1 - 3) was observed, despite the structuraland chemical differences between Zr2Al3C4 and MAX phases.
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| 20. |
- Landälv, Ludvig, 1982-
(författare)
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Thin Film and Plasma Characterization of PVD Oxides
- 2017
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Licentiatavhandling (övrigt vetenskapligt/konstnärligt)abstract
- The state-of-the-art tools for machining metals are primarily based on a metal-ceramic composite(WC-Co) coated with different combinations of carbide, nitride and oxide coatings. Combinations of these coating materials are optimized to withstand specific wear conditions. Oxide coatings are especially desired because of their possible high hot hardness, chemical inertness with respect to the workpiece, and their low friction.This thesis deals with process and coating characterization of new oxide coatings deposited by physical vapor deposition (PVD) techniques, focusing on the Cr-Zr-O and Al-Cr-Si-O systems.The thermal stability of α-Cr0.28Zr0.10O0.61 deposited by reactive radio frequency (RF)-magnetron sputtering at 500 °C was investigated after annealing up to 870 °C. The annealed samples showed transformation of α-(Cr,Zr)2O3 and amorphous ZrOx-rich areas into tetragonal ZrO2 and bcc Cr. The instability of the α-(Cr,Zr)2O3 is surprising and possibly related to the annealing being done under vacuum, facilitating the loss of oxygen. The stabilization of the room temperature metastable tetragonal ZrO2 phase, due to surface energy effects, may prove to be useful for metal cutting applications. The observed phase segregation of α-(Cr,Zr)2O3 and formation of tetragonal ZrO2 with corresponding increase in hardness for this pseudo-binary oxide system also opens up design routes for pseudo-binary oxides with tunable microstructural and mechanical properties.The inherent difficulties of depositing insulating oxide films with PVD, demanding a closed circuit, makes the investigation of process stability an important part of this research. In this context, we investigated the influence of adding small amount of Si in Al-Cr cathode on plasma characteristics ,process parameters, and coating properties. Si was chosen here due to a previous study showing improved erosion behavior of Al-Cr-Si over pure Al-Cr cathode without Si incorporation in the coating.This work shows small improvements in cathode erosion and process stability (lower pressure and cathode voltage) when introducing 5 at % Si in the Al70Cr30-cathode. This also led to fewer droplets at low cathode current and intermediate O2 flow. A larger positive effect on cathode erosion was observed with respect to cleaning the cathode from oxide contamination by increasing cathode current with 50%. However, higher cathode current also resulted in increased amount of droplets in the coating which is undesirable. Through plasma analysis the presence of volatile SiO species could be confirmed but the loss of Si through volatile SiO species was negligible, since the coating composition matched the cathode composition. The positive effect of added Si on the process stability at the cathode surface should be weighed against Si incorporation in the coating. This incorporation may or may not be beneficial for the final application since literature states that Si promotes the metastable γ-phase over the thermodynamically stable α-phase of pure Al2O3, contrary to the effect of Cr, which stabilizes the α-phase.
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| 21. |
- 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
-
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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| 22. |
- Sønderby, Steffen, 1984-
(författare)
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Yttria-Stabilized Zirconia and Gadolinia-Doped Ceria Thin Films for Fuel Cell Applications
- 2014
-
Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- Solid oxide fuel cells convert chemical energy directly into electrical energy with high efficiency and low emission of pollutants. However, before fuel cell technology can gain a significant share of the electrical power market, the operation temperature needs to be reduced in order to decrease costs and improve the durability of the cells. Application of thin film electrolytes and barrier coatings is a way of achieving this goal.In this thesis, I have investigated film growth and microstructure of yttria-stabilized zirconia (YSZ) and gadolinia-doped ceria (CGO) thin films deposited by physical vapor deposition. The aim is to make industrially applicable coatings suitable for application in solid oxide fuel cells (SOFCs). For this purpose, the coatings need to be thin and dense. YSZ coatings were prepared by pulsed direct current (DC) magnetron sputtering and high power impulse magnetron sputtering (HiPIMS) in both laboratory- and industrial-scale setups.Industrial-scale pulsed DC magnetron sputtering of YSZ showed that homogenous coating over large areas was possible. In order to increase film density of the YSZ, HiPIMS was used. By tuning deposition pressure, peak power density and substrate bias voltage it was possible to deposit noncolumnar thin films without voids and cracks as desired for SOFC applications.CGO coatings were deposited by pulsed DC magnetron sputtering with the purpose of implementing diffusion barriers to prevent reactions between Sr from the SOFC cathode and the electrolyte. A model system simulating a SOFC was prepared by depositing thin CGO and YSZ layers on cathode material. This setup allowed the study of Sr diffusion by observing SrZrO3 formation using X-ray diffraction while annealing. Electron microscopy was subsequently performed to confirm the results. The study revealed Sr to diffuse along column/grain boundaries in the CGO films but by modifying the film thickness and microstructure the breaking temperature of the barrier could be increased.CGO thin films were implemented in metal-based SOFC and the influence of film microstructure and thickness on the electrochemical performance of the cell was studied. Cell tests showed that an area specific resistance (ASR) down to 0.27 Ωcm2 could be obtained 650 °C with sputtered CGO barrier layers in combination with a lanthanum strontium cobaltite cathode. In comparison a spin-coated CGO barrier resulted in an ASR value of 0.50 Ωcm2. This shows the high effectiveness of the sputtered barrier in obtaining state-of-the-art performance.In summary, this work provides fundamental understanding of the deposition and growth of YSZ and CGO thins films and proves the prospective of employing thin film barrier coating in order to obtain high-performing SOFCs.
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