Size-dependent pressure-induced amorphization in nanoscale TiO2

We investigated the size-dependent high-pressure phase transition behavior of nanocrystalline anatase TiO2 with synchrotron x-ray diffraction and Raman spectroscopy to 45 GPa at ambient temperature. Pressure-induced amorphization results in a high-density amorphous (HDA) form when the starting crystallite size is < 10 mm. The HDA-TiO2 transforms to a low-density amorphous form at lower pressures. Harnessing the nanometer length scale thus provides a new window for experimental investigation of amorphization in poor glass formers and a synthesis route for new amorphous materials.     

“Can you help me count these pennies?”: Surfacing preschoolers’ understandings of counting

ABSTRACT

Capturing the breadth and variety of children’s understanding is critical if studies of children’s mathematical thinking are to inform policy and practice in early childhood education. This article presents an investigation of young children’s counting. Detailed coding and analyses of assessment interviews with 476 preschoolers revealed understandings that would be overlooked by solely assessing the accuracy of their responses. In particular, many children demonstrated understandings of counting principles on a challenging task that were not captured by other, simpler tasks. We conclude that common approaches to capturing young children’s mathematical understanding are likely underestimating their capabilities. This study contributes to researchers’ understanding of what making sense of counting looks and sounds like for preschool age children (3–5 years), the development and relations among counting principles (one-to-one, cardinal, and patterns of the number sequence), and the affordances of challenging, open-ended tasks. We close by considering the implications of recognizing and building from what children know and can do for researchers, practitioners, and policymakers.     

Direct density determination of low- and high-density glassy polyamorphs following a liquid–liquid phase transition in Y2O3–Al2O3 supercooled liquids

Evidence has been presented for a density-driven phase transition occurring between supercooled liquids in the system Y₂O₃–Al₂O₃. The high- and low-density liquids were quenched to metastably coexisting glasses. Chemical analysis showed the compositions of the two glasses to be identical, and it was inferred that they differed in their densities and entropies. The entropy difference has been verified by calorimetry. Here, we confirm that the chemical compositions of the glassy materials derived from the high- and low-temperature liquids are identical. We present a direct density determination of the two glasses using sink-float techniques. The measured densities are 3.72(3) g/cm³ for the glass derived from the high-temperature liquid (i.e., the high-density amorphous or HDA polyamorph), and 3.58(1) g/cm³ for the low-temperature (low-density, LDA) polyamorph.     

Smart and green interfaces: From single bubbles/drops to industrial environmental and biomedical applications

Interfaces can be called Smart and Green (S&G) when tailored such that the required technologies can be implemented with high efficiency, adaptability and selectivity. At the same time they also have to be eco-friendly, i.e. products must be biodegradable, reusable or simply more durable. Bubble and drop interfaces are in many of these smart technologies the fundamental entities and help develop smart products of the everyday life.     

Fast Exfoliation and Functionalisation of Two‐Dimensional Crystalline Carbon Nitride by Framework Charging

Two‐dimensional (2D) layered graphitic carbon nitride (gCN) nanosheets offer intriguing electronic and chemical properties. However, the exfoliation and functionalisation of gCN for specific applications remain challenging. We report a scalable one‐pot reductive method to produce solutions of single‐ and few‐layer 2D gCN nanosheets with excellent stability in a high mass yield (35 %) from polytriazine imide. High‐resolution imaging confirmed the intact crystalline structure and identified an AB stacking for gCN layers. The charge allows deliberate organic functionalisation of dissolved gCN, providing a general route to adjust their properties.     

Enhanced hydrogen storage in Ni/Ce composite oxides

The properties of dried (but not calcined) coprecipitated nickel ceria systems have been investigated in terms of their hydrogen emission characteristics following activation in hydrogen. XRD and BET data obtained on the powders show similarities to calcined ceria but it is likely that the majority of the material produced by the coprecipitation process is largely of an amorphous nature. XPS data indicate very little nickel is present on the outermost surface of the particles. Nevertheless, the thermal analytical techniques (TGA, DSC and TPD-MS) indicate that the hydrogen has access to the catalyst present and the nickel is able to generate hydrogen species capable of interacting with the support. Both unactivated and activated materials show two hydrogen emission features, viz. low temperature and high temperature emissions (LTE and HTE, respectively) over the temperature range 50 and 500 degrees C. A clear effect of hydrogen interaction with the material is that the activated sample not only emits much more hydrogen than the corresponding unactivated one but also at lower temperatures. H(2) dissociation occurs on the reduced catalyst surface and the spillover mechanism transfers this active hydrogen into the ceria, possibly via the formation and migration of OH(-) species. The amount of hydrogen obtained (~0.24 wt%) is approximately 10x higher than those observed for calcined materials and would suggest that the amorphous phase plays a critical role in this process. The affiliated emissions of CO and CO(2) with that of the HTE hydrogen (and consumption of water) strongly suggests a proportion of the hydrogen emission at this point arises from the water gas shift type reaction. It has not been possible from the present data to delineate between the various hydrogen storage mechanisms reported for ceria.     

Suzuki-Miyaura coupling of 2-bromopyridine with 2-formylphenylboronic acid

Suzuki-Miyaura coupling of 2-bromopyridine 1b with 2-formylphenylboronic acid 2 under standard conditions, gives 2-[4-(2-pyridin-2-yl-benzyl)-pyridin-2-yl]benzoic acid 5b. A similar reaction is observed for 2-bromo-6-methylpyridine 1c. A mechanistic rationale for these unusual observations is suggested.     

Crystal structure and high-pressure properties of γ-Mo2N determined by neutron powder diffraction and X-ray diffraction

We prepared samples of cubic γ-MoN_x (x∼0.5) by high-pressure-high-temperature synthesis. N atom site occupancies within the defect rock salt structure were determined from time-of-flight neutron diffraction and powder X-ray diffraction data by Rietveld analysis. The results show that N atoms occupy only octahedral sites within the structure. The semi-metallic compound is a superconductor, with determined by SQUID magnetometry. The compressibility of the material was determined by synchrotron X-ray diffraction measurements at high pressure in the diamond anvil cell. The vibrational density of states was studied by Raman scattering spectroscopy.