Mechanical activation and cation site disorder of spinel-based ceramics

This research focuses on the processing and the effects that has on the cation disorder of magnesium-aluminate spinel based (MgAl2O4) ceramics. The first goal of this project was to determine the effects of high-energy milling, i.e., mechanical activation, on cation disorder (inversion) within the spinel structure. First, 1:1 molar ratios of MgO:Al2O3 ceramics were processed using two green processing methods, ball milling (XD) and SPEX milling (mechanical activation, MA) followed by a subsequent annealing treatment in air to form a single spinel phase in each powder sample. Neutron diffraction analysis was employed to determine the cation site occupancy and revealed that overall mechanical activation resulted in a lower degree of cation site inversion compared to the non-activated materials, about 0.12 was the largest value returned for the MA materials and 0.13 was the lowest value out of the XD samples. The second portion of this project was to investigate the synthesis, densification behavior, and crystallographic site occupancy for a high-entropy spinel (HES) (Co0.2Cu0.2Mg0.2Ni0.2Zn0.2)Al2O4. This was compared to several other compositions including a MgAl2O4, NiAl2O4 and (Mg0.5Ni0.5)Al2O4 (MAS, NAS, NMAS) specimens produced using the same methods. Each composition reacted to form a single phase, but analysis of x-ray diffraction (XRD) patterns revealed that the HES specimen had a degree of inversion of 0.4. The NAS and NMAS samples were also highly inverted whereas the MAS material had minimal cation disorder. --Abstract, page iv

Mechanical Activation and Cation Site Disorder in Mgal2o4

The synthesis and crystallographic site occupancy were investigated for MgAl2O4 with and without mechanical activation of the precursor powders. Heating to 1200 °C or higher resulted in the formation of a single spinel phase regardless of whether the powders were mechanically activated or not. Neutron diffraction analysis was used to determine cation site occupancy and revealed that mechanical activation resulted in a lower degree of cation site inversion compared to the nonactivated materials, which indicated that the powders were closer to thermodynamic equilibrium. This is the first study to characterize the effects of mechanical activation on crystallographic site occupancy in magnesium aluminate spinel using neutron diffraction

Mechanical Activation and Cation Site Disorder in MgAl2O4

The synthesis and crystallographic site occupancy were investigated for MgAl2O4 with and without mechanical activation of the precursor powders. Heating to 1200 °C or higher resulted in the formation of a single spinel phase regardless of whether the powders were mechanically activated or not. Neutron diffraction analysis was used to determine cation site occupancy and revealed that mechanical activation resulted in a lower degree of cation site inversion compared to the nonactivated materials, which indicated that the powders were closer to thermodynamic equilibrium. This is the first study to characterize the effects of mechanical activation on crystallographic site occupancy in magnesium aluminate spinel using neutron diffraction. © 2022 by the authors

Synthesis, densification, and cation inversion in high entropy (Co,Cu,Mg,Ni,Zn)Al2O4 spinel

The synthesis, densification behavior, and crystallographic site occupancy were investigated for four different spinel-based ceramics, including a high-entropy spinel (Co0.2Cu0.2Mg0.2Ni0.2 Zn0.2)Al2O4. Each composition was reacted to form a single phase, but analysis of X-ray diffraction patterns revealed differences in cation site occupancy with the high-entropy spinel being nearly fully normal. Densification behavior was investigated and showed that fully dense ceramics could be produced by hot pressing at temperatures as low as 1375°C for all compositions. Vickers’ hardness values were at least 10 GPa for all compositions. The cations present in the high-entropy spinel appear to have a stabilizing effect that led to nearly normal site occupancy compared to full cation inversion behavior of nickel aluminate spinel. This is the first report that compares cation site occupancy of a high-entropy spinel to conventional spinel ceramics

Microstructural and Optical Properties of MgAl2O4 Spinel: Effects of Mechanical Activation, Y2O3 and Graphene Additions

Magnesium aluminate and other alumina-based spinels attract attention due to their high hardness, high mechanical strength, and low dielectric constant. MgAl2O4 was produced by a solid-state reaction between MgO and α-Al2O3 powders. Mechanical activation for 30 min in a planetary ball mill was used to increase the reactivity of powders. Yttrium oxide and graphene were added to prevent abnormal grain growth during sintering. Samples were sintered by hot pressing under vacuum at 1450 °C. Phase composition and microstructure of sintered specimens were characterized by X-ray powder diffraction and scanning electron microscopy. Rietveld analysis revealed 100% pure spinel phase in all sintered specimens, and a decrease in crystallite size with the addition of yttria or graphene. Density measurements indicated that the mechanically activated specimen reached 99.6% relative density. Furthermore, the highest solar absorbance and highest spectral selectivity as a function of temperature were detected for the mechanically activated specimen with graphene addition. Mechanical activation is an efficient method to improve densification of MgAl2O4 prepared from mixed oxide powders, while additives improve microstructure and optical properties

Shortwave infrared hyperspectral imaging as a novel method to elucidate multi-phase dolomitization, recrystallization, and cementation in carbonate sedimentary rocks

From Springer Nature via Jisc Publications RouterHistory: received 2021-07-08, accepted 2021-10-18, registration 2021-10-25, pub-electronic 2021-11-05, online 2021-11-05, collection 2021-12Publication status: PublishedFunder: Society for Sedimentary Geology Foundation; Grant(s): Student research grantFunder: International Association of Sedimentologists; doi: http://dx.doi.org/10.13039/501100007463; Grant(s): Postgraduate research grantFunder: British Sedimentological Research Group; doi: http://dx.doi.org/10.13039/100011045; Grant(s): Trevor Elliot memorial grantFunder: American Association of Petroleum Geologists Foundation; doi: http://dx.doi.org/10.13039/100013604; Grant(s): Classen Family grantFunder: Canadian Foundation for Innovation; Grant(s): John R. Evans Leaders Fund - Funding for research infrastructure (project 22222)Funder: National Science and Engineering Research Council of Canada; Grant(s): Discovery grantAbstract: Carbonate rocks undergo low-temperature, post-depositional changes, including mineral precipitation, dissolution, or recrystallisation (diagenesis). Unravelling the sequence of these events is time-consuming, expensive, and relies on destructive analytical techniques, yet such characterization is essential to understand their post-depositional history for mineral and energy exploitation and carbon storage. Conversely, hyperspectral imaging offers a rapid, non-destructive method to determine mineralogy, while also providing compositional and textural information. It is commonly employed to differentiate lithology, but it has never been used to discern complex diagenetic phases in a largely monomineralic succession. Using spatial-spectral endmember extraction, we explore the efficacy and limitations of hyperspectral imaging to elucidate multi-phase dolomitization and cementation in the Cathedral Formation (Western Canadian Sedimentary Basin). Spectral endmembers include limestone, two replacement dolomite phases, and three saddle dolomite phases. Endmember distributions were mapped using Spectral Angle Mapper, then sampled and analyzed to investigate the controls on their spectral signatures. The absorption-band position of each phase reveals changes in %Ca (molar Ca/(Ca + Mg)) and trace element substitution, whereas the spectral contrast correlates with texture. The ensuing mineral distribution maps provide meter-scale spatial information on the diagenetic history of the succession that can be used independently and to design a rigorous sampling protocol

Basin scale evolution of zebra textures in fault-controlled, hydrothermal dolomite bodies: insights from the Western Canadian Sedimentary Basin

Structurally controlled dolomitization typically involves the interaction of high-pressure (P), high-temperature (T) fluids with the surrounding host rock. Such reactions are often accompanied by cementation and recrystallization, with the resulting hydrothermal dolomite (HTD) bodies including several ‘diagnostic’ rock textures. Zebra textures, associated with boxwork textures and dolomite breccias, are widely considered to reflect these elevated P/T conditions. Although a range of conceptual models have been proposed to explain the genesis of these rock textures, the processes that control their spatial and temporal evolution are still poorly understood. Through the detailed petrographical and geochemical analysis of HTD bodies, hosted in the Middle Cambrian strata in the Western Canadian Sedimentary Basin, this study demonstrates that a single genetic model cannot be applied to all the characteristics of these rock textures. Instead, a wide array of sedimentological, tectonic and metasomatic processes contribute to their formation; each of which is spatially and temporally variable at the basin scale. Distal to the fluid source, dolomitization is largely stratabound, comprising replacement dolomite, bedding-parallel zebra textures and rare dolomite breccias (non-stratabound, located only proximal to faults). Dolomitization is increasingly non-stratabound with proximity to the fluid source, comprising bedding-inclined zebra textures, boxwork textures and dolomite breccias that have been affected by recrystallization. Petrographical and geochemical evidence suggests that these rock textures were initiated due to dilatational fracturing, brecciation and precipitation of saddle dolomite as a cement, but significant recrystallization occurred during the later stages of dolomitization. These rock textures are closely associated with faults and carbonate-hosted ore deposits (e.g. magnesite, rare earth element and Mississippi Valley–type mineralization), thus providing invaluable information regarding fluid flux and carbonate metasomatism under elevated P/T conditions

U-Pb geochronology reveals that hydrothermal dolomitization was coeval to the deposition of the Burgess Shale lagerstätte

Fault-controlled, hydrothermal dolomitization often occurs at margins between shallow-water carbonate platforms and deep-water sedimentary basins. In western Canada, for example, the platform margin between the Cathedral Formation and the Burgess Shale Formation has been dolomitized at temperatures up to ~200 °C, with local magnesite, talc, and clinochlore mineralization. At the same time, the Burgess Shale Formation includes exceptional fossils that provide key evidence of the radiation of the animal phyla during the Cambrian Period (541 to 485.4 Ma). This lagerstätte and Mg-rich minerals within the adjacent and underlying strata, however, have been critically understudied. Here we show, using carbonate U-Pb geochronology, that western Canada was tectonically active and subject to hydrothermal dolomitization during the Middle Cambrian (Miaolingian Epoch) to Middle Ordovician (488.1 ± 18.8 Ma). These results extend the latest stages of rifting along the western margin of Laurentia into the Paleozoic, while also suggesting that the dolomitization of the Cathedral Formation occurred at the same time as the deposition of the Burgess Shale lagerstätte

Microstructural and optical properties of MgAl2O4 Spinel: Effect of Mechanical Activation, Yttrium and Graphene addition

Magnesium aluminate and other alumina-based spinels attract attention due to their high hardness, high mechanical strength, and low dielectric constant. MgAl2O4 was produced by solid-state reaction between MgO and α-Al2O3 powders. Mechanical activation of 30 minutes in a planetary ball mill was used to increase the reactivity of powders. Yttrium oxide and graphene were added to prevent abnormal grain growth during sintering. Samples were sintered by hot-pressing under vacuum at 1450 °C. Phase composition and microstructure of sintered specimens were characterized by X-ray diffraction analysis and scanning electron microscopy. Rietveld analysis revealed 100 % pure spinel phase in all sintered specimens, and decrease in crystallite size with the addition of yttria or graphene. Density measurements indicated that the mechanically activated specimen reached 99.6 % relative density, while other specimens were above 96.5 % relative density. Furthermore, the highest solar absorbance and highest spectral selectivity as a function of temperature were detected for the mechanically activated specimen with graphene addition. Mechanical activation is an efficient method to improve the densification behaviour of MgAl2O4 produced from mixed oxide powders, while additives improve microstructure and optical properties

Confidence and psychosis: a neuro-computational account of contingency learning disruption by NMDA blockade.

A state of pathological uncertainty about environmental regularities might represent a key step in the pathway to psychotic illness. Early psychosis can be investigated in healthy volunteers under ketamine, an NMDA receptor antagonist. Here, we explored the effects of ketamine on contingency learning using a placebo-controlled, double-blind, crossover design. During functional magnetic resonance imaging, participants performed an instrumental learning task, in which cue-outcome contingencies were probabilistic and reversed between blocks. Bayesian model comparison indicated that in such an unstable environment, reinforcement learning parameters are downregulated depending on confidence level, an adaptive mechanism that was specifically disrupted by ketamine administration. Drug effects were underpinned by altered neural activity in a fronto-parietal network, which reflected the confidence-based shift to exploitation of learned contingencies. Our findings suggest that an early characteristic of psychosis lies in a persistent doubt that undermines the stabilization of behavioral policy resulting in a failure to exploit regularities in the environment.FV was supported by the Groupe Pasteur Mutualité. RG was supported by the Fondation pour la Recherche Médicale and the Fondation Bettencourt Schueller. SP is supported by a Marie Curie Intra-European fellowship (FP7-PEOPLE-2012-IEF). AF was supported by National Health and Medical Research Council grants (IDs : 1050504 and 1066779) and an Australian Research Council Future Fellowship (ID: FT130100589). This work was supported by the Wellcome Trust and the Bernard Wolfe Health Neuroscience Fund.This is the final version of the article. It first appeared from the Nature Publishing Group via http://dx.doi.org/10.1038/mp.2015.7