Browsing by Author "Mitchell, DRG"
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- ItemBoson peak in ultrathin alumina layers investigated with neutron spectroscopy(American Physical Society, 2020-06-11) Cortie, DL; Cyster, MJ; Ablott, TA; Richardson, C; Smith, JS; Iles, GN; Wang, XL; Mitchell, DRG; Mole, RA; de Souza, NR; Yu, DH; Cole, JHBulk glasses exhibit extra vibrational modes at low energies, collectively known as the boson peak. The vibrational dynamics in nanoscale alumina glasses have an impact on the performance of qubits and other superconducting devices; however, the frequency of the boson peak has not been previously measured. Here we report neutron spectroscopy experiments on Al/Al2O3 nanoparticles consisting of spherical metallic cores with a radii from 20 to 1000 nm surrounded by a 3.5-nm-thick alumina glass. A low-energy peak is observed at ωBP = 2.8 ± 0.6 meV for highly oxidized particles, indicating an excess in the density of states. The intensity of the peak scales inversely with particle size and oxide fraction, indicating a surface origin, and is redshifted by 3 meV with respect to the van Hove singularity of γ -phase Al2O3 nanocrystals. Molecular-dynamics simulations of α-Al2O3, γ -Al2O3 and α-Al2O3 show that the observed boson peak is a signature of the ultrathin glass surface and the characteristic frequency is reduced compared to the peak in the bulk glass. © 2020 The Authors. Published by the American Physical Society under the terms of the Creative Commons Attribution 4.0 International license.
- ItemCharacterisation of epitaxial TiO2 thin films grown on MgO(0 0 1) using atomic layer deposition(Elsevier, 2005-11-15) Mitchell, DRG; Attard, DJ; Triani, GThin films of TiO2 have been deposited onto MgO(0 0 1) substrates using atomic layer deposition at 300 °C. Plan and cross-sectional transmission electron microscopy (TEM), X-ray diffraction and atomic force microscopy have been used to understand the nature of the films. X-ray and electron diffraction showed that a polycrystalline, epitaxial anatase film was produced. The c-axis of the anatase was parallel to the MgO(0 0 1) surface with two orientational variants at right angles to each other in the plane of the film, each aligned with an MgO cube axis. Plan-view and cross-sectional TEM showed that the grain structure of the film reflected this orientation relationship, with the grain morphology comprising two sets of roughly tetragonal grains. Also present was a small fraction of equiaxed, anatase grains which were randomly oriented. Roughness measurement using atomic force microscopy showed that the epitaxial anatase films were quite smooth, in comparison to equivalent non-aligned films grown on silicon. Crown copyright © 2005. Published by Elsevier B.V.
- ItemCreating thin magnetic layers at the surface of Sb2Te3 topological insulators using a low-energy chromium ion beam(AIP Publishing, 2020-05-11) Cortie, DL; Zhao, WY; Yue, Z; Li, Z; Bake, A; Marenych, O; Pastuovic, Z; Nancarrow, M; Zhang, ZM; Qi, DC; Evans, PJ; Mitchell, DRG; Wang, XLThe surfaces of Sb2Te3 topological insulator crystals were implanted using a 40 keV chromium ion beam. To facilitate uniform doping, the Sb2Te3 was passivated with a thin TiO2 film before the implantation step. The resulting chemical structure was studied using atomic-resolution transmission electron microscopy. A fluence of 7 × 1015 ions/cm2 at 40 keV lead to amorphization of the Sb2Te3 surface, with chromium predominantly incorporated in the amorphous layer. Heating to 200 °C caused the amorphous region to recrystallize and led to the formation of a thin chromium-rich interfacial layer. Near-edge x-ray absorption spectroscopy indicates a uniform valence state of Cr3+ throughout, with no evidence of metallic clustering. High-temperature superparamagnetic behavior was detected up to 300 K, with an increased magnetic moment below 50 K. © 2020 Author(s).
- ItemDoes the boson peak survive in an ultrathin oxide glass?(arXiv.org, 2019-07-29) Cortie, DL; Cyster, MJ; Smith, JS; Iles, GN; Wang, XL; Mitchell, DRG; Mole, RA; de Souza, NR; Yu, DH; Cole, JHBulk glasses exhibit extra vibrational modes at low energies, known as the boson peak. The microscopic dynamics in nanoscale alumina impact the performance of qubits and other superconducting devices, however the existence of the boson peak in these glasses has not been previously measured. Here we report neutron spectroscopy on Al/Al2O3−x nanoparticles consisting of spherical metallic cores from 20 to 1000 nm surrounded by a 3.5 nm thick alumina glass. An intense low-energy peak is observed at ωBP = 2.8 ± 0.6 meV for highly oxidised particles, concurrent with an excess in the density of states. The intensity of the peak scales inversely with particle size and oxide fraction indicating a surface origin, and is red-shifted by 3 meV with respect to the van-Hove singularity of γ-phase Al2O3−x nanocrystals. Molecular dynamics simulations of α-Al2O3−x, γ-Al2O3−x and a-Al2O3−x show that the observed boson peak is a signature of the ultrathin glass surface, and the frequency is softened compared to that of the hypothetical bulk glass.
- ItemEffective gel for gold nanoparticle formation, support and metal oxide templating(Royal Society of Chemistry, 2007-08-07) Wang, XD; Egan, CE; Zhou, MF; Prince, KE; Mitchell, DRG; Caruso, RAGold nanoparticles were synthesized using agarose as a reducing agent, which gelled to support the gold nanoparticles, then readily functioned as a template to produce a porous, evenly-distributed Au/TiO2 nano-hybrid. © 2007, Royal Society of Chemistry
- ItemElectrochemical characterization of an aqueous lithium rechargeable battery: the effect of CeO2 additions to the MnO2 cathode(Elsevier, 2009-06-24) Minakshi, M; Nallathamby, K; Mitchell, DRGThe effect of CeO2 additions on an aqueous rechargeable lithium battery has been investigated. The CeO2 additions (0, 2, and 5 wt.%) were made to the manganese dioxide (MnO2) cathode of a cell comprising zinc as an anode and an aqueous saturated lithium hydroxide solution as the electrolyte. The CeO2 enhances the performance of the cell in terms of capacity and resistance to capacity fade with cycling. This effect is only evident after the first charge cycle. The mechanism by which this occurs may be due to suppression of the oxygen evolution reaction during charging. This results in full reversion of the products of discharge (principally LixMnO2) to MnO2 during charging, and suppresses the formation of non-rechargeable oxyhydroxides. CeO2 additions of 2 wt.% were found to be most effective, since additions at the 5 wt.% level caused a decrease in capacity during long-term cycling. This could be due to a synchronizing effect. The effect of additions of a rare earth oxide (CeO2) and an alkaline earth oxide (CaO) on the electrochemical behavior of the cell is also compared and discussed. © 2009, Elsevier Ltd.
- ItemEnhanced thermoelectric performance and mechanical strength of n-type BiTeSe materials produced via a composite strategy(Elsevier, 2022-01) Yang, G; Sang, L; Mitchell, DRG; Yun, FF; See, KW; Ahmed, AJ; Sayyar, S; Bake, A; Liu, P; Chen, L; Yue, ZJ; Cortie, DL; Wang, XLZone-melted Bi2Te2.7Se0.3 (ZM BTS) alloys are typical n-type commercial thermoelectric (TE) materials and are utilized for refrigeration and power generation near room temperature. They usually suffer from poor mechanical performance, as well as having a low figure of merit (ZT). In this work, we report an effective composite strategy to improve both the TE and mechanical performance of n-type BTS materials by incorporating carbon microfibers. The introduction of carbon microfibers in BTS effectively reduces the lattice thermal conductivity due to phonon scattering at multi-scale boundaries and due to the large interfacial thermal resistance arising from phonon mismatch between the constituent phases. Simultaneously, it also gives rise to an enhancement of the electrical conductivity, which originates from the increased carrier density without significant limitation on its weighted mobility. Consequently, a high peak ZT of 1.1 at 400 K and an average ZTave value of 0.95 are achieved in the temperature range 300 ~ 550 K, yielding a calculated efficiency of η = 9%. Moreover, the BTS/carbon microfiber composites show superior compressive strength compared to a commercial ZM BTS sample. This improved strength is highly desirable for real-world TE applications. Our results demonstrate a novel way to produce high-performance TE materials, in which interfaces with large thermal resistance are used to achieve low thermal conductivity without significantly degrading the electrical properties of the materials. © 2021 Elsevier B.V.
- ItemGold nanoparticle incorporation into porous titania networks using an agarose gel templating technique for photocatalytic applications(American Chemical Society, 2008-05-20) Wang, XD; Mitchell, DRG; Prince, KE; Atanacio, AJ; Caruso, RAPorous titania networks containing gold nanoparticles have been synthesized and tested in photocatalytic applications. The porous structure was controlled using a templating technique, while a range of gold concentrations and a variety of routes were investigated to incorporate the gold nanoparticles. The influence of these parameters on the final structure (surface area and pore size), the gold crystal size, distribution, and content, and the photocatalytic activity of the porous materials were investigated. UV−vis diffuse reflectance spectra of the Au/TiO2 materials showed strong absorbance at approximately 580 nm, indicating the successful incorporation of the gold species. X-ray diffraction analysis ascertained that the titania materials were crystalline (anatase phase) with gold peaks observed only when the gold content was greater than 0.25 wt %. Gold distribution and content in the materials were measured using secondary ion mass spectrometry and inductively coupled plasma mass spectrometry. From transmission electron microscopy analysis, the gold particle size and distribution varied with both the material preparation method and the concentration of gold used in the synthesis. Photocatalytic activity was dependent on the gold particle size and gold quantity. The highest photocatalytic activity under UV light irradiation as monitored by the photodecomposition of methylene blue was obtained for the Au/TiO2 sample containing 2.0 wt % gold prepared by the deposition of gold onto prefabricated porous TiO2.© 2008 American Chemical Society
- ItemHydrothermal crystallization of amorphous titania films deposited using low temperature atomic layer deposition(Elsevier, 2008-10-01) Mitchell, DRG; Triani, G; Zhang, ZA two stage process (atomic layer deposition, followed by hydrothermal treatment) for producing crystalline titania thin films at temperatures compatible with polymeric substrates (< 130°C) has been assessed. Titania thin films were deposited at 80°C using atomic layer deposition. They were extremely flat, uniform and almost entirely amorphous. They also contained relatively high levels of residual Cl from the precursor. After hydrothermal treatment at 120°C for 1 day, > 50% of the film had crystallized. Crystallization was complete after 10 days of hydrothermal treatment. Crystallization of the film resulted in the formation of coarse grained anatase. Residual Cl was completely expelled from the film upon crystallization. As a result of the amorphous to crystalline transformation voids formed at the crystallization front. Inward and lateral crystal growth resulted in voids being localized to the film/substrate interface and crystallite perimeters resulting in pinholing. Both these phenomena resulted in films with poor adhesion and film integrity was severely compromised. © 2008, Elsevier Ltd.
- ItemIn situ characterisation of nanostructured multiphase thermoelectric materials at elevated temperatures(Royal Society of Chemistry, 2016-11-17) Aminorroaya Yamini, S; Mitchell, DRG; Avdeev, MMultiphase thermoelectric materials have recently attracted considerable attention due to the high thermoelectric efficiencies which can be achieved in these compounds compared to their single-phase counterparts. However, there is very little known on the structural evolution of these phases as a function of temperature. In this work we performed an in situ high temperature structural characterisation of recently reported high efficiency p-type multiphase (PbTe)0.65(PbS)0.25(PbSe)0.1 compounds by hot stage transmission electron microscopy and high-resolution neutron powder diffraction. We observed the microstructural evolution of precipitates and determined the lattice parameters of phases as a function of temperature for materials, which have been heavily and lightly doped with sodium. The role of the sodium is to optimize the concentration of charge carriers. It has been shown to distribute heterogeneously between the phases in multiphase compounds. The dissolution of secondary phases is found to occur at elevated temperatures. Although sodium concentration produces no significant differences between the lattice constants of the phases and the dissolution sequence of precipitates, it affects quite significantly the kinetics of precipitation. The heavily doped samples reach structural thermodynamic equilibrium more quickly than the lightly doped compound. These results are a step forward in designing high performance multiphase thermoelectric materials. © the Owner Societies 2016
- ItemIron-monosulfide oxidation in natural sediments: resolving microbially mediated S transformations using XANES, electron microscopy, and selective extractions(American Chemical Society, 2009-05-01) Burton, ED; Bush, RT; Sullivan, LA; Hocking, RK; Mitchell, DRG; Johnston, SG; Fitzpatrick, RW; Raven, M; McClure, S; Jang, LYIron-monosulfide oxidation and associated S transformations in a natural sediment were examined by combining selective extractions, electron microscopy and S K-edge X-ray absorption near-edge structure (XANES) spectroscopy. The sediment examined in this study was collected from a waterway receiving acid−sulfate soil drainage. It contained a high acid-volatile sulfide content (1031 μmol g−1), reflecting an abundance of iron-monosulfide. The iron-monosulfide speciation in the initial sediment sample was dominated by nanocrystalline mackinawite (tetragonal FeS). At near-neutral pH and an O2 partial pressure of 0.2 atm, the mackinawite was found to oxidize rapidly, with a half-time of 29 ± 2 min. This oxidation rate did not differ significantly (P < 0.05) between abiotic versus biotic conditions, demonstrating that oxidation of nanocrystalline mackinawite was not microbially mediated. The extraction results suggested that elemental S (S08) was a key intermediate S oxidation product. Transmission electron microscopy showed the S08 to be amorphous nanoglobules, 100−200 nm in diameter. The quantitative importance of S08 was confirmed by linear combination XANES spectroscopy, after accounting for the inherent effect of the nanoscale S08 particle-size on the corresponding XANES spectrum. Both the selective extraction and XANES data showed that oxidation of S08 to SO42− was mediated by microbial activity. In addition to directly revealing important S transformations, the XANES results support the accuracy of the selective extraction scheme employed here. © 2009, American Chemical Society
- ItemLamellae preparation for atomic-resolution STEM imaging from ion-beam-sensitive topological insulator crystals(AIP Publishing, 2022-04-06) Bake, A; Zhao, WY; Mitchell, DRG; Wang, XL; Nancarrow, M; Cortie, DLGood specimen quality is a key factor in achieving successful scanning transmission electron microscope analysis. Thin and damage-free specimens are prerequisites for obtaining atomic-resolution imaging. Topological insulator single crystals and thin films in the chalcogenide family such as Sb2Te3 are sensitive to electron and ion beams. It is, therefore, challenging to prepare a lamella suitable for high-resolution imaging from these topological insulator materials using standard focused ion-beam instruments. We have developed a modified method to fabricate thin focused ion-beam (FIB) lamellae with minimal ion-beam damage and artefacts. The technique described in the current study enables the reliable preparation of high-quality transmission electron microscope (TEM) specimens necessary for studying ultra-thin surface regions. We have successfully demonstrated that the careful selection of FIB milling parameters at each stage minimizes the damage layer without the need for post-treatment. © 2022 Author(s). Published under an exclusive license by the AVS.
- ItemLattice guiding for low temperature crystallization of rhombohedral perovskite-structured oxide thin films(American Chemical Society, 2010-02) Sriram, S; Bhaskaran, M; Mitchell, DRG; Mitchell, ALow temperature crystallization of complex oxide thin films has proved to be a challenge with deposition of such materials often carried out at elevated temperatures in excess of 600°C. This article demonstrates one of the first instances of deposition of preferentially oriented strontium-doped lead zirconate titanate thin films at a relatively low temperature of 300°C. This was achieved by carrying out deposition on gold-coated silicon substrates which exert a guiding influence on thin film growth due to similarity in lattice parameters. The microstructure and preferential orientations were studied using high resolution transmission electron microscopy and X-ray diffraction. These results illustrated the pronounced texture in the deposited thin films due to lattice guiding, with crystal structure simulations also verifying the guiding effect. © 2010, American Chemical Society
- ItemLow temperature bonding of ceramics by sol-gel processing(Springer Nature, 2001-12) Barbé , CJ; Cassidy, DJ; Triani, G; Latella, BA; Mitchell, DRG; Finnie, KS; Bartlett, JR; Woolfrey, JL; Collins, GASol-gel bonds were produced between smooth, clean silicon or polycrystalline alumina substrates by spin-coating solutions containing partially hydrolysed silicon alkoxides onto both substrates. The two coated substrates were assembled and the resulting sandwich was fired at temperatures ranging from 300 to 600°C. The influence of the sol-gel chemistry on the film microstructure and interfacial fracture energy was investigated using a wide range of techniques, including ellipsometry, FTIR, TG-DTA, rheology, TEM and micro-indentation. For silicon wafers, an optimum water-alkoxide molar ratio of 10 and hydrolysis water pH of 2 were found. Such conditions led to relatively dense films (>90%), resulting in bonds with significantly higher fracture energy (3.5 J/m2) than those obtained using classical water bonding (typically 1.5 J/m2). Aging of the coating solution was found to decrease the bond strength. Poly-crystalline alumina substrates were similarly bonded at 600°C; the optimised silica sol-gel chemistry yielded interfaces with fracture energy of 4 J/m2. © 2000 Kluwer Academic Publishers.
- ItemMicrostructural and compositional analysis of strontium-doped lead zirconate titanate thin films on gold-coated silicon substrates(Cambridge University Press, 2009-02) Sriram, S; Bhaskaran, M; Mitchell, DRG; Short, KT; Holland, AS; Mitchell, AThis article discusses the results of transmission electron microscopy (TEM)-based characterization of strontium-doped lead zirconate titanate (PSZT) thin films. The thin films were deposited by radio frequency magnetron sputtering at 300°C on gold-coated silicon substrates, which used a 15 nm titanium adhesion layer between the 150 nm thick gold film and (100) silicon. The TEM analysis was carried out using a combination of high-resolution imaging, energy filtered imaging, energy dispersive X-ray (EDX) analysis, and hollow cone illumination. At the interface between the PSZT films and gold, an amorphous silicon-rich layer (about 4 nm thick) was observed, with the film composition remaining uniform otherwise. The films were found to be polycrystalline with a columnar structure perpendicular to the substrate. Interdiffusion between the bottom metal layers and silicon was observed and was confirmed using secondary ion mass spectrometry. This occurs due to the temperature of deposition (300°C) being close to the eutectic point of gold and silicon (363°C). The diffused regions in silicon were composed primarily of gold (analyzed by EDX) and were bounded by (111) silicon planes, highlighted by the triangular diffused regions observed in the two-dimensional TEM image. © 2009, Cambridge University Press
- ItemMicrostructural and spectroscopic investigations into the effect of CeO2 additions on the performance of a MnO2 aqueous rechargeable battery(Elsevier, 2009-04-30) Minakshi, M; Mitchell, DRG; Carter, ML; Appadoo, D; Nallathamby, KThe influence of CeO2 additions on the electrochemical behaviour of the MnO2 cathode in a Zn–MnO2 battery using lithium hydroxide (LiOH) as an electrolyte is investigated using microscopy and spectroscopic techniques. The results showed that such additions greatly improve the discharge capacity of the battery (from 155 to 190 mAh g−1) but only from the second discharge cycle onwards. Capacity fade with subsequent cycling is also greatly reduced. With an aim to understand the role of CeO2 on the discharge–charge characteristics of MnO2 and its mechanism, we have used a range of microscopy, spectroscopy and diffraction-based techniques to study the process. The CeO2 is not modified by multiple discharged and charged cycles. The CeO2 may enhance the discharge–charge performance of the battery by raising the oxygen evolution potential during charging but does not take part directly in the redox reaction. © 2009, Elsevier Ltd.
- ItemNanocolumnar preferentially oriented PSZT thin films deposited on thermally grown silicon dioxide(Springer, 2009-01) Sriram, S; Bhaskaran, M; Mitchell, A; Mitchell, DRG; Kostovski, GWe report the first instance of deposition of preferentially oriented, nanocrystalline, and nanocolumnar strontium-doped lead zirconate titanate (PSZT) ferroelectric thin films directly on thermal silicon dioxide. No intermediate seed or activation layers were used between PSZT and silicon dioxide. The deposited thin films have been characterised using a combination of diffraction and microscopy techniques. © 2009, Springer.
- ItemPhotocatalytic application of porous Au/TiO2 nano-hybrids prepared by a templating technique(International Conference on the Photochemical Conversion and Storage of Solar Energy, 2008-07-30) Wang, XD; Mitchell, DRG; Prince, KE; Caruso, RAGold doping or deposition in TiO2 can effectively improve the photocatalytic performance of the titania by either modifying the bandgap and thereby inducing photoactivity under visible light or decreasing the recombination of excited electron and hole. Templating techniques can produce materials with designed morphology and porosity. The objective of this project was to couple controlled porosity allowing faster molecule diffusion through the porous channels with gold deposition to further increase the photocatalytic activity of TiO2. Templating and sol-gel techniques were combined to synthesise Au/TiO2 nano-hybrids with improved photocatalytic activity. The porous structures directed by the agarose gel template were examined by SEM. X-ray diffraction analysis ascertained the materials to be anatase phase, and the gold peaks were observed when the gold content was over 0.25 wt%. TEM further confirmed the highly porous structure of the composites (Figure 1). The gold particle sizes, influenced by both the synthesis methods and initial gold content, ranged from ~ 2 to 40 nm. The gold distribution and content were identified by means of secondary ion mass spectrometer and inductively coupled plasma mass spectrometry, respectively. Finally, the catalytic performance of the Au/TiO2 was assessed by photodecomposition of methylene blue under UV light. The influence of parameters such as synthesis methods, material properties and photocatalytic test conditions (e.g., pH, catalyst and dye concentration) on the photocatalytic efficiency was also investigated. The photocatalytic efficiency improved by a maximum 40% for the Au/TiO2 sample with a gold particle size of 2 nm and 2 wt % gold content.
- ItemSpontaneous emergence of optically polarizing nanoscale structures by co-deposition of aluminum with refractory metals: implications for high-temperature polarizers(American Chemical Society, 2022-03-25) Tai, MC; Arnold, MD; Estherby, C; de Silva, KSB; Gentle, AR; Cortie, DL; Mitchell, DRG; Westerhausen, MT; Cortie, MBThe unexpected growth of highly aligned and optically polarizing metallic fins during physical vapor deposition under modestly oblique conditions is investigated. The fins exhibit nanoscale dimensions and are formed when Al is co-sputtered with any of V, Cr, Nb, Mo, Ta, W, Ru, Fe, Ni, Pt, Zr, Mg, and Ti. It is proposed that the phenomenon is caused by anomalously low atomic mobility in the alloys and intermetallic compounds formed by co-depositing with Al. In contrast, when Cu, Ag, and Au (which diffuse more rapidly in Al) are deposited, no fins form. There is a sharp visible transition in optical properties as the ratio of Al to other element is decreased: the color of the sample changes from black to silver-white for compositions containing less than about 55 atom % Al. The region over which the color change occurs is associated with a very strongly polarized reflectance. Cross-sectional elemental mapping and Monte Carlo simulations suggest that growth of the fins may be nucleated by Al hillocks and enhanced by shadowing effects. The diversity of suitable metals makes this a versatile technique for producing nanoscale polarizing surfaces suitable for high-flux and high-temperature applications. © American Chemical Society
- ItemStructure and magnetism of ultra-small cobalt particles assembled at titania surfaces by ion beam synthesis(Elsevier, 2021-12) Bake, A; Rezoanur Rahman, M; Evans, PJ; Cortie, MB; Nancarrow, M; Abrudan, R; Radu, F; Khaydukov, Y; Causer, GL; Callori, SJ; Livesey, KL; Mitchell, DRG; Pastuovic, Z; Wang, XL; Cortie, DLMetallic cobalt nanoparticles offer attractive magnetic properties but are vulnerable to oxidation, which suppresses their magnetization. In this article, we report the use of ion beam synthesis to produce ultra-small, oxidation-resistant, cobalt nanoparticles embedded within substoichiometric TiO2-δ thin films. Using high fluence implantation of cobalt at 20–60 keV, the particles were assembled with an average size of 1.5 ± 1 nm. The geometry and structure of the nanoparticles were studied using scanning transmission electron microscopy. Near-edge X-ray fluorescence spectroscopy on the L2,3 Co edges confirms that the majority of the particles beneath the surface are metallic, unoxidised cobalt. Further evidence of the metallic nature of the small particles is provided via their high magnetization and superparamagnetic response between 3 and 300 K with a low blocking temperature of 4.5 K. The magnetic properties were studied using a combination of vibrating sample magnetometry, element-resolved X-ray magnetic circular dichroism, and depth-resolved polarised neutron reflectometry. These techniques provide a unified picture of the magnetic metallic Co particles. We argue, based on these experimental observations and thermodynamic calculations, that the cobalt is protected against oxidation beneath the surface of titania owing to the enthalpic stability of TiO2 over CoO which inhibits solid state reactions. Crown Copyright © 2021 Published by Elsevier B.V.