Computational study of boron nitride nanotube synthesis: how catalyst morphology stabilizes the boron nitride bond

In an attempt to understand why catalytic methods for the growth of boron nitride nanotubes work much worse than for their carbon counterparts, we use first-principles calculations to study the energetics of elemental reactions forming N2, B2 and BN molecules on an iron catalyst. We observe that in the case of these small molecules, the catalytic activity is hindered by the formation of B2 on the iron surface. We also observe that the local morphology of a step edge present in our nanoparticle model stabilizes the boron nitride molecule with respect to B2 due to the ability of the step edge to offer sites with different coordination simultaneously for nitrogen and boron. Our results emphasize the importance of atomic steps for a high yield chemical vapor deposition growth of BN nanotubes and may outline new directions for improving the efficiency of the method.Comment: submitted to physical review

Structural models for the Si(553)-Au atomic chain reconstruction

Recent photoemission experiments on the Si(553)-Au reconstruction show a one-dimensional band with a peculiar ~1/4 filling. This band could provide an opportunity for observing large spin-charge separation if electron-electron interactions could be increased. To this end, it is necessary to understand in detail the origin of this surface band. A first step is the determination of the structure of the reconstruction. We present here a study of several structural models using first-principles density functional calculations. Our models are based on a plausible analogy with the similar and better known Si(557)-Au surface, and compared against the sole structure proposed to date for the Si(553)-Au system [Crain JN et al., 2004 Phys. Rev. B 69 125401 ]. Results for the energetics and the band structures are given. Lines for the future investigation are also sketched

Submonolayers of carbon on alpha-Fe facets: An ab initio study

Motivated by recent in situ studies of carbon nanotube growth from large transition-metal nanoparticles, we study various α-iron (ferrite) facets at different carbon concentrations using ab initio methods. The studied (110), (100), and (111) facets show qualitatively different behavior when carbon concentration changes. In particular, adsorbed carbon atoms repel each other on the (110) facet, resulting in carbon dimer and graphitic material formation. Carbon on the (100) facet forms stable structures at concentrations of about 0.5 monolayer and at 1.0 monolayer this facet becomes unstable due to a frustration of the top-layer iron atoms. The stability of the (111) facet is weakly affected by the amount of adsorbed carbon and its stability increases further with respect to the (100) facet with increasing carbon concentration. The exchange of carbon atoms between the surface and subsurface regions on the (111) facet is easier than on the other facets and the formation of carbon dimers is exothermic. These findings are in accordance with a recent in situ experimental study where the existence of graphene-decorated (111) facets is related to increased carbon concentration.Peer reviewe

Boron nitride formation on magnesium studied by ab initio calculations

Motivated by the state of the art method for producing boron nitride nanotubes in which magnesium has been speculated to act as a catalyst, we study the elemental chemistry of boron and nitrogen on the Mg(0001) surface using ab initio methods. We do this by considering the energetics of individual boron and nitrogen atoms, and the smallest boron and nitrogen containing molecules. We observe that magnesium promotes boron-nitride (BN) molecule formation on the catalyst surface. Based on the analysis of the behavior of BN molecules on the catalyst surface, we propose a possible route for further development of hexagonal BN sheets mediated by the catalystPeer reviewe

Metal-insulator transition in the In/Si(111) surface

The metal-insulator transition observed in the In/Si(111)-4x1 reconstruction is studied by means of ab initio calculations of a simplified model of the surface. Different surface bands are identified and classified according to their origin and their response to several structural distortions. We support the, recently proposed [New J. of Phys. 7 (2005) 100], combination of a shear and a Peierls distortions as the origin of the metal-insulator transition. Our results also seem to favor an electronic driving force for the transition.Comment: Presented in the 23 European Conference in Surface Science, Berlin, September 2005. Submitted to Surface Science (proceedings of the conference) in August 200

First-principles study of the atomic and electronic structure of the Si(111)-(5x2-Au surface reconstruction

We present a systematic study of the atomic and electronic structure of the Si(111)-(5x2)-Au reconstruction using first-principles electronic structure calculations based on the density functional theory. We analyze the structural models proposed by Marks and Plass [Phys. Rev. Lett.75, 2172 (1995)], those proposed recently by Erwin [Phys. Rev. Lett.91, 206101 (2003)], and a completely new structure that was found during our structural optimizations. We study in detail the energetics and the structural and electronic properties of the different models. For the two most stable models, we also calculate the change in the surface energy as a function of the content of silicon adatoms for a realistic range of concentrations. Our new model is the energetically most favorable in the range of low adatom concentrations, while Erwin's "5x2" model becomes favorable for larger adatom concentrations. The crossing between the surface energies of both structures is found close to 1/2 adatoms per 5x2 unit cell, i.e. near the maximum adatom coverage observed in the experiments. Both models, the new structure and Erwin's "5x2" model, seem to provide a good description of many of the available experimental data, particularly of the angle-resolved photoemission measurements

Sub-monolayers of carbon on alpha-iron facets: an ab-initio study

Motivated by recent in situ studies of carbon nanotube growth from large transition-metal nanoparticles, we study various alpha-iron (ferrite) facets at different carbon concentrations using ab initio methods. The studied (110), (100) and (111) facets show qualitatively different behaviour when carbon concentration changes. In particular, adsorbed carbon atoms repel each other on the (110) facet, resulting in carbon dimer and graphitic material formation. Carbon on the (100) facet forms stable structures at concentrations of about 0.5 monolayer and at 1.0 monolayer this facet becomes unstable due to a frustration of the top layer iron atoms. The stability of the (111) facet is weakly affected by the amount of adsorbed carbon and its stability increases further with respect to the (100) facet with increasing carbon concentration. The exchange of carbon atoms between the surface and sub-surface regions on the (111) facet is easier than on the other facets and the formation of carbon dimers is exothermic. These findings are in accordance with a recent in situ experimental study where the existence of graphene decorated (111) facets is related to increased carbon concentration

Quantum fluctuations in ultranarrow superconducting nanowires

Progressive reduction of the effective diameter of a nanowire is applied to trace evolution of the shape of superconducting transition $R(T)$ in quasi-one-dimensional aluminum structures. In nanowires with effective diameter $\leq$ 15 nm the $R(T)$ dependences are much wider than predicted by the model of thermally activated phase slips. The effect can be explained by quantum fluctuations of the order parameter. Negative magnetoresistance is observed in the thinest samples. Experimental results are in reasonable agreement with existing theoretical models. The effect should have a universal validity indicating a breakdown of zero resistance state in a superconductor below a certain scale.Comment: 18 pages, 5 figure

Epistemic roles of materiality within a collaborative invention project at a secondary school

In this study, we examined maker‐centred learning from an epistemic perspective, highlighting the agentic role of material engagement and artefacts in learning and creativity. The use of physical materials plays a crucial role in maker activities where the socio‐epistemic aspects of knowledge creation entangle with the designing and making of physical artefacts. By taking a case study perspective, we analysed video data from nine design sessions involving a team of students (aged 13 to 14) developing an invention. First, we analysed knowledge that was built during the process. Our analysis revealed how design ideas evolved from preliminary to final stages and, together with the expressed design problems and conversations preceding the ideas, formed an epistemic object pursued by the team. Next, we included non‐human agencies into the analysis to understand the role of materials in the process. Features of materials and human design intentions both constrained and enabled idea improvement and knowledge creation, intermixing meanings and materials. Material making invited the students to not only rely on human rationalisation, but also to think together with the materials.In this study, we examined maker-centred learning from an epistemic perspective, highlighting the agentic role of material engagement and artefacts in learning and creativity. The use of physical materials plays a crucial role in maker activities where the socio-epistemic aspects of knowledge creation entangle with the designing and making of physical artefacts. By taking a case study perspective, we analysed video data from nine design sessions involving a team of students (aged 13 to 14) developing an invention. First, we analysed knowledge that was built during the process. Our analysis revealed how design ideas evolved from preliminary to final stages and, together with the expressed design problems and conversations preceding the ideas, formed an epistemic object pursued by the team. Next, we included non-human agencies into the analysis to understand the role of materials in the process. Features of materials and human design intentions both constrained and enabled idea improvement and knowledge creation, intermixing meanings and materials. Material making invited the students to not only rely on human rationalisation, but also to think together with the materials.Peer reviewe

Keratoendotheliitis Fugax Hereditaria : A Novel Cryopyrin-Associated Periodic Syndrome Caused by a Mutation in the Nucleotide-Binding Domain, Leucine-Rich Repeat Family, Pyrin Domain-Containing 3 (NLRP3) Gene

PURPOSE: To describe the phenotype and the genetic defect in keratoendotheliitis fugax hereditaria, an autosomal dominant keratitis that periodically affects the corneal endothelium and stroma, leading in some patients to opacities and decreased visual acuity. DESIGN: Cross-sectional, hospital-based study. METHODS: PATIENT POPULATION: Thirty affected and 7 unaffected subjects from 7 families, and 4 sporadic patients from Finland. OBSERVATION PROCEDURES: Ophthalmic examination and photography, corneal topography, specular microscopy, and optical coherence tomography in 34 patients, whole exome sequencing in 10 patients, and Sanger sequencing in 34 patients. MAIN OUTCOME MEASURES: Clinical phenotype, disease causing genetic variants. RESULTS: Unilateral attacks of keratoendotheliitis typically occurred 1-6 times a year (median, 2.5), starting at a median age of 11 years (range, 5-28 years), and lasted for 1-2 days. The attacks were characterized by cornea pseudoguttata and haze in the posterior corneal stroma, sometimes with a mild anterior chamber reaction, and got milder and less frequent in middle age. Seventeen (50%) patients had bilateral stroma! opacities. The disease was inherited as an autosomal dominant trait. A likely pathogenic variant c.61G > C in the NLRP3 gene, encoding cryopyrin, was detected in all 34 tested patients and segregated with the disease. This variant is present in both Finnish and non-Finnish European populations at a frequency of about 0.02% and 0.01%, respectively. CONCLUSION: Keratoendotheliitis fugax hereditaria is an autoinflammatory cryopyrin-associated periodic syndrome caused by a missense mutation c.61G > C in exon 1 of NLRP3 in Finnish patients. It is additionally expected to occur in other populations of European descent. ((c) 2018 The Author(s). Published by Elsevier Inc.Peer reviewe