Mossbauer spectroscopy and chemical bonds in BaFe12O19 hexaferrite

Barium hexaferrite was synthesized by chemical co-precipitation. Its Mossbauer spectra were obtained. A semi-empirical model, based on the Phillips theory of bonding, has been developed for quantitative explanation of the Mossbauer isomer shifts of Fe ions in BaFe12O19 crystals. The results show that, using the relationship between isomer shifts and covalency, the site assignments in hexaferrites will be resolved easily. This paper provides a powerful tool for studying other members of the hexagonal ferrimagnetic oxides family.

Crystal field splitting of Nd3+ ion and chemical bonds on the host crystals

In terms of the theory of chemical bonds on complex crystals(CBCC), the crystal structure and coordination, the chemical bond parameters of a group of ABO(4)-type crystals were calculated in detail, The results show that the relation between the crystal field splitting of Nd3+ ion and the covalency of the crystal is linear.

CHEMICAL-BONDS AND DIELECTRIC-CONSTANTS OF REM (RE=RARE EARTH, M=N, P, AS, SB) CRYSTALS

By using Pillips and van Vechten theory, the chemical bond parameters and dielectric constants of REM (RE=rare earth, M=N, P, As, Sb) crystals were calculated. The values calculated of dielectric constants agree with the experimental values.

Chemical bond properties of rare earth ions in crystals

By using the dielectric description theory of ionicity of solids, chemical bond properties of rare earth ions with various ligands are studied. Calculated results show that chemical bond properties of the same rare earth ion and the same ligand in different crystals depend on the crystal structures. In a series of compounds, chemical bond properties of crystals containing different rare earth ions are similar. The magnitude of covalency of chemical bonds of trivalent rare earth ions and various ligands has an order like F

Dependence of superconducting temperature on chemical bond parameters in YBa2Cu3O6+delta (delta=0-1)

The chemical bond parameters, that is ionicities and average energy gaps, for all types of chemical bonds in YBa2Cu3O6+delta have been investigated with variation of oxygen content delta (delta = 0.0, 0.35, 0.45, 0.58, 0.64, 0.73, 0.78, 0.81, 0.95, 1.00). The theory used is the complex crystal chemical bond theory, which is the development of P-V-L theory. The two plateaus near 90 K and 60 K in superconducting transition temperatures, and the disappearance of superconductivity with the change of oxygen content, were reasonably explained by chemical bond parameters. The results also showed that the Cu-O chains play a vital role in the transition from non-superconductors to superconductors, and the highest transition temperature occurred when the plane-chain reached a coupling state. (C) 1998 Elsevier Science Ltd. All rights reserved.

Chemical bond analysis of nonlinearity of urea crystal

A novel and quantitative study on structure-property relationships has been carried out in urea crystal, based on the dielectric theory of complex crystals and the modified Levine bond charge model, mainly from the chemical bond viewpoint. For the first time, it was treated like this, and the bond parameters and linear and nonlinear characteristics of constituent chemical bonds were presented quantitatively. The theoretical result agrees satisfactorily with the experimental datum and can reasonably explain the nonlinear origin of urea crystal, that is, the C-N bond in the conjugated system of bonds O double left arrow C<--N-H. At the same time, the novel method should be a useful tool toward the future development of the search for new nonlinear optical (NLO) materials in the organic crystal field.

Improved description of chemical barriers with generalized gradient approximations (GGAs) and meta-GGAs

The performance of exchange and correlation (xc) functionals of the generalized gradient approximation (GGA) type and of the meta-GGA type in the calculation of chemical reactions is related to topological features of the electron density which, in turn, are connected to the orbital structure of chemical bonds within the Kohn-Sham (KS) theory. Seventeen GGA and meta-GGA xc functionals are assessed for 15 hydrogen abstraction reactions and 3 symmetrical S(N)2 reactions. Systems that are problematic for standard GGAs characteristically have enhanced values of the dimensionless gradient argument s(sigma)(2) with local maxima in the bonding region. The origin of this topological feature is the occupation of valence KS orbitals with an antibonding or essentially nonbonding character. The local enhancement of s(sigma)(2) yields too negative exchange-correlation energies with standard GGAs for the transition state of the S(N)2 reaction, which leads to the reduced calculated reaction barriers. The unwarranted localization of the effective xc hole of the standard GGAs, i.e., the nondynamical correlation that is built into them but is spurious in this case, wields its effect by their s(sigma)(2) dependence. Barriers are improved for xc functionals with the exchange functional OPTX as x component, which has a modified dependence on s(sigma)(2). Standard GGAs also underestimate the barriers for the hydrogen abstraction reactions. In this case the barriers are improved by correlation functionals, such as the Laplacian-dependent (LAP3) functional, which has a modified dependence on the Coulomb correlation of the opposite- and like-spin electrons. The best overall performance is established for the combination OLAP3 of OPTX and LAP3.

Evaluation of the chemical interaction between carbon nanotubes functionalized with TGDDM tetrafunctional resin and hardener DDS

In this work, the chemical interaction between carbon nanotubes (MWCNT) functionalized with acyl chloride (SOCl2) and polymer chain tetrafuncional N,N,N′,N′-tetraglycidyl-4,4′- diaminodiphenylmethane (TGDDM) and hardener 4,4′diaminodiphenyl sulfone (DDS) has been monitored by Fourier transform infrared spectroscopy (FTIR) with a attenuated total reflectance (ATR) coupled. MWCNT were obtained from the pyrolysis of a mixture of camphor and ferrocene into a oven. The functionalization process was done by oxidative treatment in order to incorporate carboxylic group over the walls of MWCNT, before to be used SOCl2. The functionalized carbon nanotubes were evaluated by X-ray photoelectron spectroscopy (XPS), Raman and transmission electron microscopy (TEM). Nanostructured composites were processed by using epoxy resin with MWCNT in varying percentages. In this work it was observed that different percentages of functionalized nanotubes modify the interaction between the composite matrix and curing agent, where can be observed that in specimens with content less than 1 wt% MWCNT the chemical bond occurs preferentially from the opening of the SO double bond of the hardener and when is used MWCNT content higher than 1 wt% there is little chemical interaction with the SO bond of the hardener and most MWCNT binds to amine. © 2013 Elsevier Ltd.

Chemical Modifications in Styrene-Butadiene Rubber after Microwave Devulcanization

Microwave devulcanization has been studied as a method for elastomer recycling, which is based on the conversion of the reticulated and infusible structure of thermosetting rubbers in free polymeric chains able to be remolded by thermomechanical processing in recycling operations for the manufacture of other products. Elastomeric wastes are often irregularly discarded in nature, producing serious environmental damage, and their mechanical recycling is still considered a challenge. Thus, the development of alternatives for elastomer recycling is directly related to the actions of sustainable development and economic benefits to companies that pay to discard their wastes. The aim of this work is to evaluate the chemical modifications occurring in styrene butadiene rubber (SBR) after microwave devulcanization. Compounds of SBR were vulcanized in the presence of vulcanization agents and variable amounts of carbon black, and then the rubbers were milled and submitted to microwave treatment. Only the SBR with high carbon black content shows some portion of devulcanized material. However, the rubber with lower content of carbon black which was devulcanized by microwave radiation shows an increase in cross-link density. The microwave treatment also causes cross-link breaks mainly in polysulfidic bonds as well as decomposition of chemical groups containing sulfur attached to the chemical structure of SBR, while. the chemical bonds of higher energy such as monosulfidic bonds remain preserved. The improvement of the microwave method for rubber devulcanization represents a way for viable recycling of thermosetting rubbers.

A first principles analysis of the effect of hydrogen concentration in hydrogenated amorphous silicon on the formation of strained Si-Si bonds and the optical and mobility gaps

In this paper, we use a model of hydrogenated amorphous silicon generated from molecular dynamics with density functional theory calculations to examine how the atomic geometry and the optical and mobility gaps are influenced by mild hydrogen oversaturation. The optical and mobility gaps show a volcano curve as the hydrogen content varies from undersaturation to mild oversaturation, with largest gaps obtained at the saturation hydrogen concentration. At the same time, mid-gap states associated with dangling bonds and strained Si-Si bonds disappear at saturation but reappear at mild oversaturation, which is consistent with the evolution of optical gap. The distribution of Si-Si bond distances provides the key to the change in electronic properties. In the undersaturation regime, the new electronic states in the gap arise from the presence of dangling bonds and strained Si-Si bonds, which are longer than the equilibrium Si-Si distance. Increasing hydrogen concentration up to saturation reduces the strained bonds and removes dangling bonds. In the case of mild oversaturation, the mid-gap states arise exclusively from an increase in the density of strained Si-Si bonds. Analysis of our structure shows that the extra hydrogen atoms form a bridge between neighbouring silicon atoms, thus increasing the Si-Si distance and increasing disorder in the sample.

Experimental and theoretical investigation of ligand effects on the synthesis of ZnO nanoparticles

ZnO nanoparticles with highly controllable particle sizes(less than 10 nm) were synthesized using organic capping ligands in Zn(Ac)2 ethanolic solution. The molecular structure of the ligands was found to have significant influence on the particle size. The multi-functional molecule tris(hydroxymethyl)-aminomethane (THMA) favoured smaller particle distributions compared with ligands possessing long hydrocarbon chains that are more frequently employed. The adsorption of capping ligands on ZnnOn crystal nuclei (where n = 4 or 18 molecular clusters of(0001) ZnO surfaces) was modelled by ab initio methods at the density functional theory (DFT) level. For the molecules examined, chemisorption proceeded via the formation of Zn...O, Zn...N, or Zn...S chemical bonds between the ligands and active Zn2+ sites on ZnO surfaces. The DFT results indicated that THMA binds more strongly to the ZnO surface than other ligands, suggesting that this molecule is very effective at stabilizing ZnO nanoparticle surfaces. This study, therefore, provides new insight into the correlation between the molecular structure of capping ligands and the morphology of metal oxide nanostructures formed in their presence.

Dielectric performance of polymer nanocomposites synthesized by atmospheric-pressure plasma-treated silica nanoparticles

In this study, atmospheric-pressure plasmas were applied to modify the surface of silane-coated silica nanoparticles. Subsequently nanocomposites were synthesized by incorporating plasma-treated nanoparticles into an epoxy resin matrix. Electrical testing showed that such novel dielectric materials obtained high partial discharge resistance, high dielectric breakdown strength, and enhanced endurance under highly stressed electric field. Through spectroscopic and microscopic analysis, we found surface groups of nanoparticles were activated and radicals were created after the plasma treatment. Moreover, a uniform dispersion of nanoparticles in nanocomposites was observed. It was expected that the improved dielectric performance of the nanocomposites can attribute to stronger chemical bonds formed between surface groups of plasma-treated nanoparticles and molecules in the matrix. This simple yet effective and environmentally friendly approach aims to synthesize the next generation of high-performance nanocomposite dielectric insulation materials for applications in high-voltage power systems.

3D-hybrid networks with controllable electrical conductivity from the electrochemical deposition of terthiophene-functionalized polyphenylene dendrimers

(Figure Presented) Unusual conductivity effects: Suitably functionalized dendrimers (see picture) are capable of forming truly covalent three-dimensional networks with remarkably high conductivity on electrochemical doping. Depending on the charging level of the electroactive components used as building blocks for the dendrimer core and the perimeter, two separated regimes of electrical conductivity can be observed.

Recent progress on synthesis, multi-scale structure, and properties of Y-Si-O oxides

Yttrium silicates (Y-Si-O oxides), including Y2Si2O7, Y2SiO5, and Y4·67(SiO4)3O apatite, have attracted wide attentions from material scientists and engineers, because of their extensive polymorphisms and important roles as grain boundary phases in improving the high-temperature mechanical/thermal properties of Si3N4and SiC ceramics. Recent interest in these materials has been renewed by their potential applications as high-temperature structural ceramics, oxidation protective coatings, and environmental barrier coatings (EBCs). The salient properties of Y-Si-O oxides are strongly related to their unique chemical bonds and microstructure features. An in-depth understanding on the synthesis - multi-scale structure-property relationships of the Y-Si-O oxides will shine a light on their performance and potential applications. In this review, recent progress of the synthesis, multi-scale structures, and properties of the Y-Si-O oxides are summarised. First, various methods for the synthesis of Y-Si-O ceramics in the forms of powders, bulks, and thin films/coatings are reviewed. Then, the crystal structures, chemical bonds, and atomic microstructures of the polymorphs in the Y-Si-O system are summarised. The third section focuses on the properties of Y-Si-O oxides, involving the mechanical, thermal, dielectric, and tribological properties, their environmental stability, and their structure-property relationships. The outlook for potential applications of Y-Si-O oxides is also highlighted.