Spin-polarization and ferromagnetism of graphitic carbon nitride materials

Polymeric graphitic carbon nitride materials have attracted increasing attention in recent years owning to their potential applications in energy conversion, environment protection, and so on. Here, from first-principles calculations, we report the electronic structure modification of graphitic carbon nitride (g-C3N4) in response to carbon doping. We showed that each dopant atom can induce a local magnetic moment of 1.0 μB in non-magnetic g-C3N4. At the doping concentration of 1/14, the local magnetic moments of the most stable doping configuration which has the dopant atom at the center of heptazine unit prefer to align in a parallel way leading to long-range ferromagnetic (FM) ordering. When the joint N atom is replaced by C atom, the system favors an antiferromagnetic (AFM) ordering at unstrained state, but can be tuned to ferromagnetism (FM) by applying biaxial tensile strain. More interestingly, the FM state of the strained system is half-metallic with abundant states at the Fermi level in one spin channel and a band gap of 1.82 eV in another spin channel. The Curie temperature (Tc) was also evaluated using a mean-field theory and Monte Carlo simulations within the Ising model. Such tunable electron spin-polarization and ferromagnetism are quite promising for the applications of graphitic carbon nitride in spintronics.

Comments on the phase diagrams and crystallisation paths of Y-Ba-Cu-O materials

Our micro structural characterisation of Y-Ba-Cu-O quenched partial melts shows that the BaCuO2 (BC1) phase is crystalline at temperatures as high as 1100°C, and that the partial melt self-establishes a micro structural gradient from the surface towards the interior of the samples, which can be associated with a gradient in an equivalent partial pressure of O2 (pO2). The extension of the Y2BaCuO5-YBa2Cu3O7-x (Y211-Y123) tie-line intersects the primary crystallisation field of BC1 first. The actual peritectic reaction that takes place is Y2BaCuO5(s) + BaCuO2(s) + 2BaCu2O2(L) + 1/2O2 → 2YBa2Cu3O6(s). Two schematic representations which allow an analysis of the pO2 dependence are given. The gradient in micro structure self-established by the sample acts as a driving force for texturing. With this new perspective gained about the actual peritectic reaction and mechanisms of melt-texturing of Y123, it is possible to explain most of the aspects about partial melt-texturing. In addition, it seems possible to devise heat treatments that may allow for the production of well-oriented single domains with very large diameters. © 1999 Elsevier Science B.V.

Observation of exsolution textures within Ba-Cu-O-rich solidified melts of Y-Ba-Cu-O materials and their relationship to Y123 nucleation and texturing

Layers (about 60-100 μm thick) of almost pure BaCuO2 (BC1), as determined using X-ray diffractometry (XRD) and scanning electron microscopy (SEM), coat the surfaces of YBa2Cu3O7-x (Y123) samples partial melt processed using a single-zone vertical furnace. The actual Cu/Ba ratio of the BC1 phase is 1.2-1.3 as determined using energy dispersive X-ray spectrometry (EDS). The nominally BC1 phase displays an exsolution of BC1.5 or BC2 in the form of thin plates (about 50-100 nm thick) along {100}-type cleavage planes or facets. The exsolved phase also fills cracks within the BC1 layer that require it to be in a molten state at some stage of processing. The samples were influenced by Pt contamination from the supporting wire, which may have stabilised the BC1.5 phase. Many of the Y123 grains have the same morphology as the exsolution domains, and run nearly parallel to the thin plates of the exsolved phases, strongly indicating that Y123 nucleation took place at the interface between the BC1 and the BC1.5 or BC2 exsolved phases. The network of nearly parallel exsolved 'channels' provides a matrix and a mechanism through which a high degree of local texture can be initiated in the material.

Studies of the phase evolution of YBCO materials with different additives

Y123 samples with varying amounts of added Y211, PtO 2 and CeO 2 have been melt processed and quenched from temperatures between 960°C and 1100°C. The microstructures of the quenched samples have been characterized using a combination of x-ray diffractometry, optical microscopy, scanning electron microscopy, microprobe analysis, energy-dispersive x-ray spectroscopy and wavelength-dispersive x-ray spectroscopy. The Ba-Cu-O-rich melt undergoes complex changes as a function of temperature and time. A region of stability of BaCuO 2 (BC1) and BaCu 2O 2 (BC2) exists below 1040°C in samples of Y123 + 20 mol% Y211. Ba 2Cu 3O 5 is stabilized by rapid quenching but appears to separate into BC1 and BC2 at lower quenching rates. PtO 2 and CeO 2 additions affect the distribution and volume fractions of the two Ba-Cu-oxide phases.

Effects of PtO2 and CeO2 additives on the microstructures of the quenched melts of Y-Ba-Cu-O materials

The microstructures of the quenched melts of samples of Y123 and Y123+15-20 mol% Y211 with PtO2 and CeO2 additives have been examined with optical microscopy, Scanning Electron Microscopy (SEM), Energy Dispersive X-ray Spectrometry (EDS) and X-ray Diffractometry (XRD). Significantly higher temperatures are required for the formation of dendritic or lamellar eutectic patterns throughout the samples with PtO2 and CeO2 additives as compared to samples without additives. The BaCuO2 (BCl) phase appears first in solid form and, instead of rapidly melting, is slowly dissolving or decomposing in the oxygen depleted melt. PtO2 and CeO2 additives slow down or shift to higher temperatures the dissolution or decomposition process of BCl. A larger fraction of BCl in solid form explains why samples with additives have higher viscosities and hence lower diffusivities than samples without additives. There is also a reduction in the Y solubility to about half the value in samples without additives. The mechanism that limits the Ostwald ripening of the Y211 particles is correlated to the morphology of the quenched partial melt. It is diffusion controlled for a finely mixed morphology and interface-controlled when the melt quenches into dendritic or lamellar eutectic patterns. The change in the morphology of the Y211 particles from blocky to acicular is related to an equivalent undercooling of the Y-Ba-Cu-O partial melt, particularly through the crystallization of BCl.

Morphology changes and mechanistic aspects of the electrochemically-induced reversible solid-solid transformation of microcrystalline TCNQ into Co TCNQ 2-based materials (TCNQ= 7, 7, 8, 8-Tetracyanoquinodimethane)

The chemically reversible solid−solid phase transformation of a TCNQ-modified glassy carbon, indium tin oxide, or metal electrode into Co\[TCNQ]2(H2O)2 material in the presence of Co2+(aq) containing electrolytes has been induced and monitored electrochemically. Voltammetric data reveal that the TCNQ/Co\[TCNQ]2(H2O)2 interconversion process is independent of electrode material and identity of cobalt electrolyte anion. However, a marked dependence on electrolyte concentration, scan rate, and method of electrode modification (drop casting or mechanical attachment) is found. Cyclic voltammetric and double potential step chronoamperometric measurements confirm that formation of Co\[TCNQ]2(H2O)2 occurs through a rate-determining nucleation and growth process that initially involves incorporation of Co2+(aq) ions into the reduced TCNQ crystal lattice at the TCNQ|electrode|electrolyte interface. Similarly, the reverse (oxidation) process, which involves transformation of solid Co\[TCNQ]2(H2O)2 back to parent TCNQ crystals, also is controlled by nucleation−growth kinetics. The overall chemically reversible process that represents this transformation is described by the reaction:  2TCNQ0(s) + 2e- + Co2+(aq) + 2H2O \[Co(TCNQ)2(H2O)2](s). Ex situ SEM images illustrated that this reversible TCNQ/Co\[TCNQ]2(H2O)2 conversion process is accompanied by drastic size and morphology changes in the parent solid TCNQ. In addition, different sizes of needle-shaped nanorod/nanowire crystals of Co\[TCNQ]2(H2O)2 are formed depending on the method of surface immobilization.

Fabrication of metal-nanoparticle-modified semiconducting copper--and silver--TCNQ materials as substrates for the reduction of chromium (VI) using thiosulfate ions at ambient temperature

The formation of readily recoverable and reusable organic semiconducting Cu- and AgTCNQ (TCNQ=7,7,8,8-tetracyanoquinodimethane) microstructures decorated with Pt and Pd metallic nanoparticles is described for the effective reduction of CrVI ions in aqueous solution at room temperature using both formic acid and an environmentally friendly thiosulfate reductant. The M-TCNQ (M=metal) materials were formed by electrocrystallisation onto a glassy carbon surface followed by galvanic replacement in the presence of H2PtCl6 or PdCl2 to form the composite material. It was found that loading of the surface with nanoparticles could easily be controlled by changing the metal salt concentration. Significantly, the M-TCNQ substrates facilitated the formation of well-isolated metal nanoparticles on their surfaces under appropriate galvanic replacement conditions. The semiconductor–metal nanoparticle combination was also found to be critical to the catalyst performance, wherein the best-performing material was CuTCNQ modified by well-isolated Pt nanoparticles with both formic acid and thiosulfate ions as the reductant.

Improved adhesion of active electrode materials to metal electrode substrates

A battery electrode for a lithium ion battery comprising an elec. conductive substrate having an electrode layer applied thereto, characterized in that the electrode layer includes an org. material having high alky., or an org. material which can be dissolved in org. solvents, or an org. material having an imide group(s) and aminoacetal group(s), or an org. material that chelates with or bonds with a metal substrate or that chelates with or bonds with an active material in the electrode layer. The org. material may be guanidine carbonate. [on SciFinder(R)]

Higher-order aberrations and anisometropia

Purpose/aim Myopia incidence is increasing around the world. Myopisation is considered to be caused by a variety of factors. One consideration is whether higher-order aberrations (HOA) influence myopisation. More knowledge of optics in anisometropic eyes might give further insight into the development of refractive error. Materials and methods To analyse the possible influence of HOA on refractive error development, we compared HOA between anisometropes and isometropes. We analysed HOA up to the 4th order for both eyes of 20 anisometropes (mean age: 43 ± 17 years) and 20 isometropes (mean age: 33 ±17 years). HOA were measured with the Shack-Hartman i.Profiler (Carl Zeiss, Germany) and were recalculated for a 4 mm pupil. Mean spherical equivalent (MSE) was based on the subjective refraction. Anisometropia was defined as ≥1D interocular difference in MSE. The mean absolute differences between right and left eyes in spherical equivalent were 0.28 ± 0.21 D in the isometropic group and 2.81 ± 2.04 D in the anisometropic group. Interocular differences in HOA were compared with the interocular difference in MSE using correlations. Results For isometropes oblique trefoil, vertical coma, horizontal coma and spherical aberration showed significant correlations between the two eyes. In anisometropes all analysed higher-order aberrations correlated significantly between the two eyes except oblique secondary astigmatism and secondary astigmatism. When analysing anisometropes and isometropes separately, no significant correlations were found between interocular differences of higher-order aberrations and MSE. For isometropes and anisometropes combined, tetrafoil correlated significantly with MSE in left eyes. Conclusions The present study could not show that interocular differences of higher-order aberrations increase with increasing interocular difference in MSE.

“Which child left behind” : historical issues regarding equity in science assessment

Assessment of learning plays a dominant role in formal education in the forms of determining features of curriculum that are emphasized, pedagogic methods that teachers use with their students, and parents’ and employers’ understanding of how well students have performed. A common perception is that fair assessment applies the same mode of assessment and content focus for all students—the approach of assessments in international comparative studies of science achievement. This article examines research evidence demonstrating that the act of assessment is not neutral—different forms of assessment advantage or disadvantage groups of students on the basis of family backgrounds, gender, race, or disability. Assessment that implicitly or explicitly captures the social capital of the child serves to consolidate, not address, educational equity. The article provides an overview of ways that science curriculum focus and assessment can introduce bias in the identification of student achievement. It examines the effect of changes to curriculum and assessment approaches in science, and relationships between assessment of science and the cultural context of the student. Recommendations are provided for science–assessment research to address bias for different groups of students.

Degradation of simazine from aqueous solutions by diatomite-supported nanosized zero-valent iron composite materials

A novel composite material based on deposition of nanosized zero-valent iron (nZVI) particles on acid-leached diatomite was synthesised for the removal of a chlorinated contaminant in water. The nZVI /diatomite composites were characterized by X-ray diffraction, scanning electron microscopy, elemental analysis, transmission electron microscopy and X-ray photoelectron spectroscopy. Compared with the pure nZVI particles, better dispersion of nZVI particles on the surface or inside the pores of diatom shells was observed. The herbicide simazine was selected as the model chlorinated contaminant and the removal efficiency by nZVI /diatomite composite was compared with that of the pristine nZVI and commercial iron powder. It was found that the diatomite supported nZVI composite material prepared by centrifugation exhibits relatively better efficient activity in decomposition of simazine than commercial Fe, lab synthesized nZVI and composite material prepared via rotary evaporation, and the optimum experimental conditions were obtained based on a series of batch experiments. This study on immobilizing nZVI particles onto diatomite opens a new avenue for the practical application of nZVI and the diatomite-supported nanosized zero-valent iron composite materials have potential applications in environmental remediation.

Fine tuning of elasticity via crosslinking collagen-based materials to mediate mechanotransduction and stability using corona treatment

The common goal of tissue engineering is to develop substitutes that can closely mimic the structure of extracellular matrix (ECM). However, similarly important is the intensive material properties which have often been overlooked, in particular, for soft tissues that are not to bear load assumingly. The mechanostructural properties determine not only the structural stability of biomaterials but also their physiological functionality by directing cellular activity and regulating cell fate decision. The aim here is to emphasize that cells could sense intensive material properties like elasticity and reside, proliferate, migrate and differentiate accordinglyno matter if the construct is from a natural source like cartilage, skin etc. or of synthetic one. Meanwhile, the very objective of this work is to provide a tunable scheme for manipulating the elasticity of collagen-based constructs to be used to demonstrate how to engineer cell behavior and regulate mechanotransduction. Articular cartilage was chosen as it represents one of the most complex hierarchical arrangements of collagen meshwork in both connective tissues and ECM-like biomaterials. Corona discharge treatment was used to produce constructs with varying density of crosslinked collagen and stiffness accordingly. The results demonstrated that elastic modulus increased up to 33% for samples treated up to one minute as crosslink density was found to increase with exposure time. According to the thermal analysis, longer exposure to corona increased crosslink density as the denaturation enthalpy increased. However the spectroscopy results suggested that despite the stabilization of the collagen structure the integrity of the triple helical structure remained intact. The in vitro superficial culture of heterologous chondrocytes also determined that the corona treatment can modulate migration with increased focal adhesion of cells due to enhanced stiffness, without cytotoxicity effects, and providing the basis for reinforcing three-dimensional collagen-based biomaterials in order to direct cell function and mediate mechanotransduction.