https://ogma.newcastle.edu.au/vital/access/ /manager/Index ${session.getAttribute("locale")} 5 https://ogma.newcastle.edu.au/vital/access/ /manager/Repository/uon:34338 Wed 24 Jul 2019 13:04:50 AEST ]]> https://ogma.newcastle.edu.au/vital/access/ /manager/Repository/uon:34062 Wed 24 Jul 2019 12:58:07 AEST ]]> https://ogma.newcastle.edu.au/vital/access/ /manager/Repository/uon:35395 Na > Li), as are stronger-interacting substrates (e.g. Ni > Cu). Despite the electropositivity of these alkali metal adsorbates, analysis of charge transfer between the alkali metal, the substrate and the adsorbed graphene layer indicates that charge transfer does not give rise to the observed regioselective reactivity. Instead, the increased reactivity induced in the graphene structure is shown to arise from the geometrical distortion of the graphene layer imposed by the intercalated adsorbed atom. We show that this strategy can be used with arbitrary adsorbates and substrate defects, provided such structures are stable, towards controlling the mesoscale patterning and chemical functionalisation of graphene structures.]]> Wed 24 Jul 2019 12:34:22 AEST ]]> https://ogma.newcastle.edu.au/vital/access/ /manager/Repository/uon:51167 Wed 23 Aug 2023 17:30:44 AEST ]]> https://ogma.newcastle.edu.au/vital/access/ /manager/Repository/uon:21264 q) functions derived from diffraction and scattering data (HEXRD and SAXS/WAXS). The competition between the glyme molecules and the salt anions for the coordination to the lithium cations is quantified by comprehensive aggregate analyses. Lithium-glyme solvates are dominant in the lithium bis(trifluoromethylsulfonyl)imide systems and much less so in systems based on the other two salts. The aggregation studies also emphasize the existence of complex coordination patterns between the different species (cations, anions, glyme molecules) present in the studied fluid media. The analysis of such complex behavior is extended to the conformational landscape of the anions and glyme molecules and to the dynamics (solvate diffusion) of the bis(trifluoromethylsulfonyl)imide plus triglyme system.]]> Wed 11 Apr 2018 16:08:15 AEST ]]> https://ogma.newcastle.edu.au/vital/access/ /manager/Repository/uon:10812 Wed 11 Apr 2018 15:38:48 AEST ]]> https://ogma.newcastle.edu.au/vital/access/ /manager/Repository/uon:23022 g) and viscosity as a function of polymer concentration allow the overlap concentrations, c* and c**, to be identified at 13 mg mL⁻¹ and 50 mg mL⁻¹, respectively, which are similar to values reported previously for conventional ionic liquids. Unlike water and conventional ionic liquids, [Li(G4)]TFSI cannot form hydrogen bonds with PEO. Thermal gravimetric analysis indicates that the solvation of PEO by [Li(G4)]TFSI is a consequence of PEO forming coordinate bonds with the lithium by displacing the anion, but without displacing the glyme molecule.]]> Wed 11 Apr 2018 15:11:45 AEST ]]> https://ogma.newcastle.edu.au/vital/access/ /manager/Repository/uon:17008 Wed 11 Apr 2018 15:02:33 AEST ]]> https://ogma.newcastle.edu.au/vital/access/ /manager/Repository/uon:20590 Wed 11 Apr 2018 13:52:57 AEST ]]> https://ogma.newcastle.edu.au/vital/access/ /manager/Repository/uon:21211 Wed 11 Apr 2018 12:40:02 AEST ]]> https://ogma.newcastle.edu.au/vital/access/ /manager/Repository/uon:24748 Wed 11 Apr 2018 12:25:09 AEST ]]> https://ogma.newcastle.edu.au/vital/access/ /manager/Repository/uon:26887 Wed 11 Apr 2018 11:23:56 AEST ]]> https://ogma.newcastle.edu.au/vital/access/ /manager/Repository/uon:13680 − anion-enriched layer is more lubricating than either the [BMIM]⁺ or FAP^- layers. The effect of cation charged group (charge-delocalised versus charged-localised) was investigated by comparing [BMIM] FAP with 1-butyl-1-methylpyrrolidinium tris(pentafluoroethyl)trifluorophosphate ([Py] FAP). [BMIM] FAP is less lubricating at negative potentials, but more lubricating at positive potentials. This indicated that even at positive potentials the cation concentration in the boundary layer is sufficiently high to influence lubricity. The influence of sliding velocity on lateral force was investigated for the [EMIM] FAP–Au(111) system. At neutral potentials the behaviour is consistent with a discontinuous sliding process. When a positive or negative potential bias is applied, this effect is less pronounced as the colloid probe slides along a better defined ion plane.]]> Wed 11 Apr 2018 10:53:59 AEST ]]> https://ogma.newcastle.edu.au/vital/access/ /manager/Repository/uon:13681 + cations in the interfacial layer are orientated towards the Au(111) surface, and this more parallel orientation is favourable for templating structure. [HMIM] FAP is more strongly structured than [BMIM] FAP because the longer cation alkyl chain increases solvophobic interactions which lead to better defined near surface structure. The response of [BMIM] I to changes in potential is opposite to that of the FAP⁻ ILs. [BMIM] I interfacial nanostructure is stronger at positive potentials, because I− anions pack more neatly at the Au(111) surface than [BMIM]⁺ cations, which templates stronger structure in subsequent layers.]]> Wed 11 Apr 2018 10:11:54 AEST ]]> https://ogma.newcastle.edu.au/vital/access/ /manager/Repository/uon:31333 1,4]TFSA). AFM measurements reveal that the imidazolium cation adsorbs at the H-Si(111)/[EMIm]TFSA interface leading to an ordered clustered facet structure of ∼3.8 nm in size. In comparison, the Si(111)/[Py_1,4]TFSA interface appeared the same as the native surface in argon. For both pure ILs, repulsive forces were measured as the tip approached the surface. On addition of LiTFSA attractive forces were measured, revealing marked changes in the interfacial structure.]]> Wed 11 Apr 2018 09:55:10 AEST ]]> https://ogma.newcastle.edu.au/vital/access/ /manager/Repository/uon:13677 Tue 16 Jan 2024 16:24:28 AEDT ]]> https://ogma.newcastle.edu.au/vital/access/ /manager/Repository/uon:33941 Thu 24 Jan 2019 12:19:56 AEDT ]]> https://ogma.newcastle.edu.au/vital/access/ /manager/Repository/uon:13730 Sat 24 Mar 2018 10:41:01 AEDT ]]> https://ogma.newcastle.edu.au/vital/access/ /manager/Repository/uon:13706 Sat 24 Mar 2018 10:38:08 AEDT ]]> https://ogma.newcastle.edu.au/vital/access/ /manager/Repository/uon:13606 Sat 24 Mar 2018 10:35:51 AEDT ]]> https://ogma.newcastle.edu.au/vital/access/ /manager/Repository/uon:13598 Sat 24 Mar 2018 10:35:07 AEDT ]]> https://ogma.newcastle.edu.au/vital/access/ /manager/Repository/uon:13602 Sat 24 Mar 2018 10:35:07 AEDT ]]> https://ogma.newcastle.edu.au/vital/access/ /manager/Repository/uon:7764 Sat 24 Mar 2018 08:41:56 AEDT ]]> https://ogma.newcastle.edu.au/vital/access/ /manager/Repository/uon:7765 Sat 24 Mar 2018 08:41:56 AEDT ]]> https://ogma.newcastle.edu.au/vital/access/ /manager/Repository/uon:7791 Sat 24 Mar 2018 08:39:20 AEDT ]]> https://ogma.newcastle.edu.au/vital/access/ /manager/Repository/uon:1678 Sat 24 Mar 2018 08:30:26 AEDT ]]> https://ogma.newcastle.edu.au/vital/access/ /manager/Repository/uon:2420 Sat 24 Mar 2018 08:29:24 AEDT ]]> https://ogma.newcastle.edu.au/vital/access/ /manager/Repository/uon:13704 Sat 24 Mar 2018 08:19:53 AEDT ]]> https://ogma.newcastle.edu.au/vital/access/ /manager/Repository/uon:10811 Sat 24 Mar 2018 08:13:23 AEDT ]]> https://ogma.newcastle.edu.au/vital/access/ /manager/Repository/uon:10981 Sat 24 Mar 2018 08:07:57 AEDT ]]> https://ogma.newcastle.edu.au/vital/access/ /manager/Repository/uon:18108 Sat 24 Mar 2018 08:04:54 AEDT ]]> https://ogma.newcastle.edu.au/vital/access/ /manager/Repository/uon:18160 Sat 24 Mar 2018 08:04:38 AEDT ]]> https://ogma.newcastle.edu.au/vital/access/ /manager/Repository/uon:19916 Sat 24 Mar 2018 08:03:45 AEDT ]]> https://ogma.newcastle.edu.au/vital/access/ /manager/Repository/uon:20347 6h-symmetry is determined by two factors - viz. the disruption of the p-conjugation of the HGF and the geometrical deformation of the HGF structure. The thermodynamically most stable structure is achieved when the former factor is minimized, and the latter factor is simultaneously maximized. Infrared (IR) spectra computed using DFT and DFTB reveal a close correlation between the relative thermodynamic stabilities of the oxidized HGF structures and their IR spectral activities. The most stable oxidized structures exhibit significant IR activity between 600 and 1800 cm⁻¹, whereas less stable oxidized structures exhibit little to no activity in this region. In contrast, Raman spectra are found to be less informative in this respect.]]> Sat 24 Mar 2018 08:02:57 AEDT ]]> https://ogma.newcastle.edu.au/vital/access/ /manager/Repository/uon:17930 Sat 24 Mar 2018 07:56:36 AEDT ]]> https://ogma.newcastle.edu.au/vital/access/ /manager/Repository/uon:20325 Sat 24 Mar 2018 07:55:10 AEDT ]]> https://ogma.newcastle.edu.au/vital/access/ /manager/Repository/uon:21212 Sat 24 Mar 2018 07:52:53 AEDT ]]> https://ogma.newcastle.edu.au/vital/access/ /manager/Repository/uon:18538 Sat 24 Mar 2018 07:50:11 AEDT ]]> https://ogma.newcastle.edu.au/vital/access/ /manager/Repository/uon:5144 Sat 24 Mar 2018 07:49:43 AEDT ]]> https://ogma.newcastle.edu.au/vital/access/ /manager/Repository/uon:5192 0.25 ML) only intact water is observed. Under UHV conditions these higher coverages can only be reached on the 4d metals, the 5d metals are, therefore, not passivated.]]> Sat 24 Mar 2018 07:47:44 AEDT ]]> https://ogma.newcastle.edu.au/vital/access/ /manager/Repository/uon:26104 Sat 24 Mar 2018 07:39:52 AEDT ]]> https://ogma.newcastle.edu.au/vital/access/ /manager/Repository/uon:27922 [Li(G4)]ClO₄ > [Li(G3)]TFSI due to decreased availability of Li⁺ for PEO coordination. For the same glyme length, the solvent qualities of SILs with TFSI⁻ and BETI⁻ anions ([Li(G4)]TFSI and [Li(G4)]BETI) are very similar because they weakly coordinate with Li⁺, which facilitates Li⁺–PEO interactions. [Li(G4)]ClO₄ presents a poorer solvent environment for PEO than [Li(G4)]BETI because ClO₄⁻ binds more strongly to Li⁺ and thereby hinders interactions with PEO. [Li(G3)]TFSI is the poorest PEO solvent of these SILs because G3 binds more strongly to Li⁺ than G4. Rheological and radius of gyration (R_g) data as a function of PEO concentration show that the PEO overlap concentrations, c* and c**, are similar in the three SILs.]]> Sat 24 Mar 2018 07:36:08 AEDT ]]> https://ogma.newcastle.edu.au/vital/access/ /manager/Repository/uon:27674 Sat 24 Mar 2018 07:33:52 AEDT ]]> https://ogma.newcastle.edu.au/vital/access/ /manager/Repository/uon:29604 Sat 24 Mar 2018 07:32:11 AEDT ]]> https://ogma.newcastle.edu.au/vital/access/ /manager/Repository/uon:30074 2]). The thermoelectrochemical process is entropically-driven by release of the glyme from the lithium–glyme complex cation, due to electrodeposition of lithium metal at the hotter lithium electrode with concomitant electrodissolution at the cooler lithium electrode. The optimum ratio for thermochemical electricity generation is not the solvate ionic liquid (equimolar mixture of Li[NTf₂] and glyme), but rather one Li[NTf₂] to four G4, due to the mixtures relatively high ionic conductivity and good apparent Seebeck coefficient (+1.4 mV K⁻¹). Determination of the lithium–glyme mixture thermal conductivity enabled full assessment of the Figure of Merit (ZT), and the efficiency relative to the Carnot efficiency to be determined. As the lithium electrodeposits are porous, alternating the temperature gradient results in a system that actually improves with repeated use.]]> Sat 24 Mar 2018 07:31:16 AEDT ]]> https://ogma.newcastle.edu.au/vital/access/ /manager/Repository/uon:27760 Sat 24 Mar 2018 07:27:43 AEDT ]]> https://ogma.newcastle.edu.au/vital/access/ /manager/Repository/uon:26535 Sat 24 Mar 2018 07:23:27 AEDT ]]> https://ogma.newcastle.edu.au/vital/access/ /manager/Repository/uon:26538 Sat 24 Mar 2018 07:23:26 AEDT ]]> https://ogma.newcastle.edu.au/vital/access/ /manager/Repository/uon:3286 Sat 24 Mar 2018 07:22:22 AEDT ]]> https://ogma.newcastle.edu.au/vital/access/ /manager/Repository/uon:3227 Sat 24 Mar 2018 07:22:15 AEDT ]]> https://ogma.newcastle.edu.au/vital/access/ /manager/Repository/uon:3252 ←<0,1,0>) and (<0,1,0>←<0,0,0>) bands. These band centers are calculated at 309.5 and 330.4 cm⁻¹ respectively. The strongest band is identified with the (<0,2,0>←<0,0,0>) transition with a band center of 625.1 cm⁻¹ and line strength of 2.58 × 10⁻¹⁹ cm molecule⁻¹ for the (4₄₀←4₄₁) transition.]]> Sat 24 Mar 2018 07:21:21 AEDT ]]> https://ogma.newcastle.edu.au/vital/access/ /manager/Repository/uon:3251 Sat 24 Mar 2018 07:21:20 AEDT ]]> https://ogma.newcastle.edu.au/vital/access/ /manager/Repository/uon:3472 Sat 24 Mar 2018 07:20:29 AEDT ]]> https://ogma.newcastle.edu.au/vital/access/ /manager/Repository/uon:22642 ab initio calculations. The generated samples, the dimensionality of which was determined by appropriate periodic boundary conditions imposed upon the generated supercells, were initially either perfectly ordered in the c-variant L1₀ superstructure ((001)-oriented monatomic planes), or completely disordered in the fcc crystalline structure. Vacancy-mediated creation of equilibrium atomic configurations was modelled by relaxing the systems at temperatures below the 'order-disorder' transition point using the Glauber algorithm implemented with the vacancy mechanism of atomic migration. The (100)-type-surface-induced heterogeneous nucleation of L1₀-order domains was observed and quantified by means of an original parameterization enabling selective determination of volume fractions of particular L1₀-variants. Due to the specific competition between the three kinds of (100)-type free surfaces, the initial c-L1₀ variant long-range order appeared to be the most stable in the cubic nanoparticle. The initially disordered samples were transformed by the creation of a specific L1₀ domain structure with a mosaic of particular L1₀-variant domains at the surfaces and almost homogeneous long-range order in the inner volume. The analysis of correlation effects revealed that chemical ordering was initiated at the free surfaces.]]> Sat 24 Mar 2018 07:17:03 AEDT ]]> https://ogma.newcastle.edu.au/vital/access/ /manager/Repository/uon:23523 Sat 24 Mar 2018 07:13:46 AEDT ]]> https://ogma.newcastle.edu.au/vital/access/ /manager/Repository/uon:24549 Sat 24 Mar 2018 07:11:33 AEDT ]]> https://ogma.newcastle.edu.au/vital/access/ /manager/Repository/uon:48227 Sat 11 Mar 2023 12:43:36 AEDT ]]> https://ogma.newcastle.edu.au/vital/access/ /manager/Repository/uon:48733 Mon 29 Jan 2024 18:04:30 AEDT ]]> https://ogma.newcastle.edu.au/vital/access/ /manager/Repository/uon:35470 3−δ perovskites are attractive candidates for high-temperature mixed ionic electronic conduction processes, due to their ability to produce mixed oxidation states and accommodate oxygen vacancies. Here, we examine the electronic structure and high-temperature thermochemistry of stoichiometric and non-stoichiometric cubic BaZrO_3−δ perovskites for high defect concentration (δ = 0-0.5) using first-principles density functional theory (DFT) and density functional perturbation theory (DFPT) calculations. Our results show that the electronic structures of these perovskites under increasing oxygen deficiency are characterized by highly localized reduction of Zr⁴⁺ t_2g orbitals in the vicinity of the oxygen defects, irrespective of the value of δ. Temperature dependent thermodynamic properties of pristine- and defective-BaZrO_3−δ show consistency with oxygen vacancy concentration. A comparison of predicted thermochemical properties with and without explicit vibrational corrections demonstrates their relative stability and implications at high-temperatures, as reduction Gibbs free energies in BaZrO_3−δ exhibit large deviations above 1000 K. We elucidate the physical origins of these deviations via a phonon mode analysis.]]> Mon 22 Jun 2020 13:28:55 AEST ]]> https://ogma.newcastle.edu.au/vital/access/ /manager/Repository/uon:34701 Mon 15 Apr 2019 09:12:07 AEST ]]> https://ogma.newcastle.edu.au/vital/access/ /manager/Repository/uon:51979 Mon 13 Nov 2023 08:48:07 AEDT ]]> https://ogma.newcastle.edu.au/vital/access/ /manager/Repository/uon:24518 in situ ellipsometry, quartz crystal microbalance with dissipation (QCM-D) and static contact angle measurements between 20 and 45 °C in the presence of up to 250 mM acetate and thiocyanate anions in water. The thickness and changes in dissipation exhibited a broad swelling transition spanning approximately 15 °C from collapsed (high temperatures) to swollen conformation (low temperatures) while the brush surface wettability changed over approximately 2 °C. In the presence of the kosmotropic acetate anions, the measured lower critical solution temperature (LCST) by the three techniques was very similar and decreased linearly as a function of ionic strength. Conversely, increasing the concentration of the chaotropic thiocyanate anions raised the LCST of the pNIPAM brushes with variation in the measured LCST between the three techniques increasing with ionic strength. The thickness of the pNIPAM brush was seen to progressively increase with increasing thiocyanate concentration at all temperatures. It is proposed that specific ion binding of the chaotropic thiocyanate anion with pNIPAM amide moieties increases the electrostatic intra- and intermolecular repulsion within and between pNIPAM chains. This allows the brush to begin to swell at higher temperatures and to an overall greater extent.]]> Fri 28 Jun 2019 11:04:06 AEST ]]> https://ogma.newcastle.edu.au/vital/access/ /manager/Repository/uon:42233 3COO, causes collapse) and thiocyanate (KSCN, causes swelling), two ions at opposite ends of the Hofmeister series, has been monitored with neutron reflectometry (NR) and quartz crystal microbalance with dissipation (QCM-D). These techniques revealed that the balance of the swelling/collapse influence of the two ions on the structure of the brush is temperature dependent. At low temperatures in mixed salt environments, the influence of the acetate and thiocyanate ions appears additive, antagonistic and approximately equal in magnitude, with brush thickness and dissipation similar to the brush in the absence of electrolyte. At higher temperatures, the influence of the acetate ion diminishes, resulting in an increase in the relative influence of the thiocyanate ion on the brush conformation. These temperature dependent specific ion effects are attributed to increased steric crowding in the brush, along with an increased affinity of the thiocyanate ion for the polymer at higher temperatures.]]> Fri 19 Aug 2022 11:42:19 AEST ]]> https://ogma.newcastle.edu.au/vital/access/ /manager/Repository/uon:53224 Fri 17 Nov 2023 12:06:37 AEDT ]]>