Anisotropic surface broken bond properties and wettability of calcite and fluorite crystals

Anisotropic surface broken bond densities of six different surfaces of calcite and three surfaces of fluorite were calculated. In terms of the calculated results, the commonly exposed surfaces of the two minerals were predicted and the relations between surface broken bonds densities and surface energies were analyzed. Then the anisotropic wettability of the commonly exposed surfaces was studied by means of contact angle measurement. The calculation results show that the （101^-4）, （213^-4）and （01 1^-8）surfaces for calcite and （111） for fluorite are the most commonly exposed surfaces and there is a good rectilinear relation between surface broken bond density and surface energy with correlation of determination （R^2） of 0.9613 and 0.9969, respectively. The anisotropic wettability of different surfaces after immersing in distilled water and sodium oleate solutions at different concentrations can be explained by anisotropic surface broken bond densities and active Ca sites densities, respectively.

Mineral cleavage nature and surface energy: Anisotropic surface broken bonds consideration

The population of surface broken bonds of some typical sulfide, oxide and salt-type minerals which may belong to cubic, tetragonal, hexagonal, or orthorhombic system, were calculated. In terms of the calculation results, the cleavage natures of these minerals were analyzed, and the relationship between surface broken bonds density and surface energy was also established. The results show that the surface broken bonds properties could be used to predict the cleavage nature of most of minerals, and the predicted cleavage planes agree well with those reported in previous literature. Moreover, this work explored a rule that, surface broken bonds density is directly related to surface energy with determination coefficient（R2） of over 0.8, indicating that the former is a dominant factor to determine the latter. Therefore, anisotropic surface broken bonds density can be used to predict the stability of mineral surface and the reactivity of surface atoms.

Effect of Surface Dangling Bonds and Molecular Passivation on Doped GaAs Nanowires

We have investigated the effect of surface dangling bonds and molecular passivation on the doping of GaAs nanowires by first-principles calculations. Results show that the positively charged surface dangling bond on Ga atom is the most stable defect for both ultrathin and large size GaAs nanowires. It can form the trap centers of holes and then prefer to capture the holes from p-type doping. Thus it could obviously reduce the efficiency of the p-type doping. We also found that the NO2 molecule is electronegative enough to capture the unpaired electrons of surface dangling bonds, which is an ideal passivation material for the Zn-doped GaAs nanowires.

Covalent electron density analysis and surface energy calculation of gold with the empirical electron surface model

Based on the empirical electron surface model （EESM）,the covalent electron density of dangling bonds （CEDDB） was calculated for various crystal planes of gold,and the surface energy was calculated further.Calculation results show that CEDDB has a great influence on the surface energy of various index surfaces and the anisotropy of the surface.The calculated surface energy is in agreement with experimental and other theoretical values.The calculated surface energy of the close-packed （111） surface has the lowest surface energy,which agrees with the theoretical prediction.Also,it is found that the spatial distribution of covalent bonds has a great influence on the surface energy of various index surfaces.Therefore,CEDDB should be a suitable parameter to describe and quantify the dangling bonds and surface energy of various crystal surfaces.

Electron beam surface heating-diffusion bonding:An effective joining method for aluminum alloy metal-matrix composite with high SiC volume

As a novel method to reduce the temperature during electron beam welding,and to subsequently inhibit interfacial reaction between SiC and Al matrix,the electron beam surface heating-diffusion bonding is proposed for joining SiC particle reinforced aluminum alloy metal-matrix composite of 45 vol.%SiC/2024 Al.The defocused electron beam was used to heat the base metal surface,and the simultaneous pressure was applied to the butt surface to achieve bonding.The base metals were successfully joined by diffusion.The maximum temperature of the whole joint was effectively decreased to less than 650°C.The Gibbs free energy change of interfacial reaction was calculated,meaning a positive value reaching 218 kJ/mol and a consequently prominent inhibitory effect on the formation of brittle Al_(4)C_(3)that was proved by microstructural observation.The tensile strength for the bonded joint was increased by 35%compared to that for ordinary welded joint.When the TC4 layer was added,TiC strengthening particles were formed with the deficiency of Al_(4)C_(3),corresponding to the significantly increased tensile strength of 63%of base metal(154 MPa).

Extraction Difficulty of Lithium Ions from Various Crystal Planes of Lithium Titanate

To study the extraction difficulty of lithium ions from various crystal planes of Li2 TiO3, according to the first principle, four representative crystal surfaces of Li2TiO3（precursor）,（-133）,（-206）,（002） and（-131）, were selected to establish a model and to calculate the surface energy, bond length and population using Materials Studio 5.5（MS 5.5）. The results demonstrate that there is no direct relationship between the surface energy and the order of disappearance of the four diffraction peaks when lithium titanate is treated with hydrochloric acid, instead, the difficulty of Li~＋ extraction from various crystal faces corresponds to the Li-O bond strength. Lithium ion is easy to remove from（-133） and（-206） due to the relatively weak Li-O bond strength. In contrast, Li＋ extraction requires a longer time for（002） and（-131）.

Electronic states and shapes of silicon quantum dots

A curviform surface breaks the symmetrical shape of silicon quantum dots on which some bonds can produce localized electronic states in the bandgap. The calculation results show that the bonding energy and electronic states of silicon quantum dots are different on various curved surfaces, for example, a Si-O-Si bridge bond on curved surface provides localized levels in bandgap and its bonding energy is shallower than that on the facet. The red-shifting ofthe photoluminescence spectrum on smaller silicon quantum dots can be explained by the curved surface effect. Experiments demonstrate that silicon quantum dots are activated for emission due to the localized levels provided by the curved surface effect.

PL Emission and Shape of Silicon Quantum Dots

The calculation results show that the bonding energy and electronic states of silicon quantum dots are different on various curved surfaces, for example, a Si-O-Si bridge bond on curved surface provides the localized levels in band gap and its bonding energy is shallower than that on facet. The red-shifting of PL spectra on smaller silicon quantum dots can be explained by curved surface effect. Experiments demonstrate that silicon quantum dots are activated for emission due to the localized levels provided in curved surface effect.

Metals Supported Water Monomers:the Bonding Nature Revisited

A single water monomer is known as a hard-to-observe molecule even in the presence of metal surfaces as supporting matrix. This review highlights effort in experimental characterizations and theoretical modeling of transition metals supported water monomers with attention given to its structure and bonding, together with the insights that we have provided into the bonding nature of the water-interactions by the newly employed projected PDOS （partial density of states） difference analysis, which is proved to be an effective tool to be elucidate such bonding nature. The general s-d hybridization and d-shell effect are summarized, and how these effects can be tuned by tailoring local surface configurations is discussed.

Exploring electronic-level principles how size reduction enhances nanomaterial surface reactivity through experimental probing and mathematical modeling

Size reduction can generally enhance the surface reactivity of inorganic nanomaterials.The origin of this nano-effect has been ascribed to ultrasmall size,large specific surface area,or abundant defects,but the most intrinsic electronic-level principles are still not fully understood yet.By combining experimental explorations and mathematical modeling,herein we propose an electronic-level model to reveal the physicochemical nature of size-dependent nanomaterial surface reactivity.Experimentally,we reveal that competitive redistribution of surface atomic orbitals from extended energy band states into localized surface chemical bonds is the critical electronic process of surface chemical interactions,using H_(2)O_(2)-TiO_(2)chemisorption as a model reaction.Theoretically,we define a concept,orbital potential(G),to describe the electronic feature determining the tendency of orbital redistribution,and deduce a mathematical model to reveal how size modulates surface reactivity.We expose the dual roles of size reduction in enhancing nanomaterial surface reactivity-inversely correlating to orbital potential and amplifying the effects of other structural factors on surface reactivity.