Ultraviolet bonding of perfluoropolyethers to carbon surfaces investigated using quantum chemical methods

For improving the tribological performance of hard disk drives, nanometer-thick perfluoropolyether (PFPE) lubricant films are generally treated with ultraviolet (UV) irradiation to bond them to the carbon overcoats of the disks. By modeling UV irradiation as an electron emission and attachment process, we investigate the UV bonding of nonfunctional PFPE Z and functional PFPE Zdol to hydrogenated and nitrogenated carbon surfaces with quantum chemical methods. Our calculation results show that, upon electron attachment, Z dissociates at its main chain to two fragments terminated by CF₂CF₂ and CF₂O groups, whereas Zdol dissociates to a hydrogen fluoride and a fragment. The perfluoromethoxy oxygen in one of the Z fragments and the carbon radical and the hydrogen-truncated end group in the Zdol fragment interact strongly with sp² and oxidized sites on carbon surfaces. Imine moieties on the CNx surface also contribute considerably to the UV bonding of Zdol.     

Fabrication and morphological control of three-dimensional cage type mesoporous titanosilicate with extremely high Ti content

TiSBA-1 materials with extremely high Ti content, up to silicon to titanium ratio (n_Si/n_Ti) of 2.4, have been successfully prepared through direct synthesis method by controlling the molar ratio of hydrochloric acid to silicon (n_HCl/n_Si). It has been found that the amount of Ti content and the structure of the TiSBA-1 can easily be controlled by the simple adjustment of n_HCl/n_Si ratio. X-ray diffraction pattern (XRD) of the obtained materials revealed that the materials are highly ordered and possess cubic three-dimensional cage type structure with open windows. N₂ adsorption–desorption measurement confirmed the narrow pore size distribution, high specific surface area (1317–1491 m² g⁻¹), and large specific pore volume (0.68–0.75 cm³ g⁻¹) for all the samples. UV–vis DR spectra of the prepared materials confirmed that Ti atoms are exclusively incorporated within silica framework and occupy the tetrahedral position while the presence of isolated bulk titania could be negligible. Morphologies of the TiSBA-1 materials have been also controlled by simply adjusting the n_Si/n_Ti ratio. With the appropriate Ti content, TiSBA-1 materials can be obtained as regular fine spheres. Moreover, the detailed mechanism on the morphological and phase transition control, and the incorporation of high amount of Ti in the framework of TiSBA-1 materials has been also discussed in detail.     

A novel scheme to detect the best cloud service provider using logarithmic operational law in generalized spherical fuzzy environment

Knowledge and Information Systems - Generalized spherical fuzzy number (GSFN) is an extension of spherical fuzzy number (SFN) which deals the uncertainties involved in the real-life problems in...     

Optimum lipid production using agro-industrial wastewater treated microalgae as biofuel substrate

Abundant wastewater discharges from palm oil industries in tropical nations being a valuable resource of biodiesel need proper exploration. Research hinted that such wastewater as economical nutrient source or substrate can support the cultivation of microalgae. In this experiment, we have tested the growth and lipid production of five different microalgal strains in palm oil mill effluent (POME). POME as a biofuel substrate is demonstrated to be lucrative for microalgae-assisted lipids production. POME is rich in macro- and micronutrients can be used as a growth medium for algal growth in order to reduce the growth medium cost and environmental pollutions. Among the five microalgal strains tested, Chlorella sorokiniana revealed optimum biomass and lipid production. The productivity was evaluated in terms of chlorophyll content, growth rate, biomass, and lipid content, which discerned to be 0.099/day, 8.0 mg/L day and 2.68 mg/mg cell dry weight (CDW). Furthermore, in this study, an optimization study was carried out to enhance the microalgae to produce high lipid content using carbon-to-nitrogen ratio and different light/dark periods. The presence of nitrogen combined glucose (with a carbon-to-nitrogen ratio 100:7) as an alternative source to carbon displayed higher lipid production of 2.68 (mg/mg CDW) by C. sorokiniana. This study confirms that 8:16 h light/dark condition at C:TN ratio of 100:7 supported to produce high lipid content of 17 mg lipid/mg CDW. The above results revealed that POME could be a suitable growth media for the alga C. sorokiniana to improve the maximum lipid yield for biofuels production.     

Proton NMR studies of cytochrome c peroxidase mutant N82A: hyperfine resonance assignments, identification of two interconverting enzyme ofecies, quantitating the rate of interconversion, and determination of equilibrium constants

The cyanide-ligated form of the baker's yeast cytochrome c peroxidase mutant bearing the mutation Asn82-->Ala82 ([N82A]CcPCN) has been studied by proton NMR spectroscopy. This mutation alters an amino acid that forms a hydrogen bond to His52, the distal histidine residue that interacts in the heme pocket with heme-bound ligands. His52 is a residue critical to cytochrome c peroxidase's normal function. Proton hyperfine resonance assignments have been made for the cyanide-ligated form of the mutant by comparison with 1-D and NOESY spectra of the wild-type native enzyme. For [N82A]CcPCN, proton NMR spectra reveal two significant phenomena. First, similar to results published for the related mutant [N82D]CcPCN [Satterlee, J. D., et al. (1994) Eur. J. Biochem. 244, 81-87], for Ala82 mutation disrupts the hydrogen bond between His52 and the heme-ligated CN. Second, four of the 24 resolved hyperfine-shifted resonances are doubled in the mutant enzyme's proton spectrum, leading to the concept that the heme active site environment is dynamically microheterogeneous on a very localized scale. Two magnetically inequivalent enzyme forms are detected in a pure enzyme preparation. Varying temperature causes the two enzyme forms to interconvert. Magnetization transfer experiments further document this interconversion between enzyme forms and have been used to determine that the rate of interconversion is 250 (+/- 53) s-1. The equilibrium constant at 20 degrees C is 1.5. Equilibrium constants have been calculated at various temperatures between 5 and 29 degrees C leading to the following values: delta H = 60 kJ mol-1; delta S = 0.20 kJ K-1 mol-1.     

Studies of the positron lifetime and Doppler-broadened annihilation radiation of polypropylene-polystyrene alloys

Positron annihilation lifetime spectroscopy and Doppler-broadened annihilation radiation (DBAR) experiments were performed on polypropylene-polystyrene (PP-PS) alloys (0-100% styrene) prepared by in situ polymerisation of styrene in a PP host matrix. The mean size of free-volume holes estimated from the ortho-positronium lifetime τ₃ shows a continuous decrease from 0.119 nm³ in PP to 0.095 nm³ in PS. The intensity of the o-Ps component, I₃, the average positron lifetime τ_av, the curve-shape parameter S and the peak height H of the DBAR spectra increase linearly with the styrene concentration. This is attributed to a linear superposition of the Ps yields of PP and PS in the PP-PS alloys. The DBAR spectra were fitted by a sum of three Gaussians, the narrowest of them is attributed to self-annihilation of para-positronium confined within holes. After its subtraction, a ‘broad component’ is obtained which represents the momentum distribution of electrons bound to molecules. Its normalised peak height does not show any change with the composition which reflects the fact that both constituents of the PP-PS alloys contain only hydrogen and carbon atoms in their chemical units. Immersing of PP into styrene liquid leads to a very pronounced increases in the lifetime parameters which is attributed to the plasticisation of PP.     

Measuring the errors of form of industrial surfaces: prediction and optimization

To acquire maximum information on the geometrical errors of industrially made surfaces at a minimum cost, a method for estimating conditional probabilities of a random signal (Bayesian prediction) is applied to three-dimensional metrology. First, a surface is interpolated between data acquired on a coordinate measuring machine (CMM). Then, for a given probability, limit surfaces are computed that bind a region of space containing the known data and the most probable interpolation of the missing data of the surface. These bounds can be treated as the surface; their points can be considered as if they were actual CMM data when fitting a tolerance zone or a datum feature to the data. For Bayesian prediction, the basic hypotheses on the signal are stationarity, ergodicity, and gaussian density. Deviations from these hypotheses and their consequences on the prediction are taken into account and corrections are proposed.     

Health risk assessment of inorganic arsenic intake of Cambodia residents through groundwater drinking pathway

In order to compare the magnitudes and health impacts of arsenic and other toxic trace elements in well water, groundwater and hair samples were collected from three areas with different arsenic exposure scenarios in the Mekong River basin of Cambodia. Ampil commune in Kampong Cham province was selected as an uncontaminated area, Khsarch Andaet commune in Kratie province was selected as a moderately contaminated area, and Kampong Kong commune in Kandal Province was selected as an extremely contaminated area. Results of ICP-MS analyses of the groundwater samples revealed that As, Mn, Fe and Ba concentrations were significantly different among the three study areas (Kruskal-Wallis test, p < 0.0001). Out of 46 observed wells in the Kandal province study area, 100% detected As > 50 μg L⁻¹ and Fe > 300 μg L⁻¹; 52.17% had Mn > 400 μg L⁻¹ and 73.91% found Ba > 700 μg L⁻¹. In the Kratie province study area (n = 12), 25% of wells showed elevated arsenic levels above 10 μg L⁻¹ and 25% had Mn > 400 μg L⁻¹, whereas samples from Kampong Cham province study area (n = 18) were relatively clean, with As < 10 μg L⁻¹. A health risk assessment model derived from the USEPA was applied to calculate individual risks resulting from drinking groundwater. Computational results indicated that residents from Kandal Province study area (n = 297) confronted significantly higher non-carcinogenic and carcinogenic risks than those in Kratie (n = 89) and Kampong Cham (n = 184) province study areas (Kruskal-Wallis test, p < 0.0001). 98.65% of respondents from the Kandal province study area were at risk for the potential non-cancer effect and an average cancer risk index was found to be 5 in 1000 exposure. The calculations also indicated that, in the Kratie province study area, 13.48% of respondents were affected by non-cancer health risks and 33.71% were threatened by cancer, whereas none of respondents in the Kampong Cham province study area appeared to have non-carcinogenic effect. Positively significant correlations of the arsenic content in scalp hair (As_h) with both arsenic levels in groundwater (As_w) (r_s (304) = 0.757, p < 0.0001) and individual average daily doses (ADD) of arsenic (r_s (304) = 0.763, p < 0.0001) undoubtedly indicated that arsenic accumulation in the bodies of Cambodia residents in the Mekong River basin was mainly through a groundwater drinking pathway. To the best of our knowledge, this is the first comprehensive report comparing individual health risk assessments of arsenic exposure through a groundwater drinking pathway to enriched arsenic levels from groundwater in the Mekong River basin, Cambodia. This study indicates that elevated arsenic concentrations in groundwater may lead to thousands of cases of arsenicosis in the near future if mitigating actions are not taken.     

A polar-based guided multi-objective evolutionary algorithm to search for optimal solutions interested by decision-makers in a logistics network design problem

In practical multi-objective optimization problems, respective decision-makers might be interested in some optimal solutions that have objective values closer to their specified values. Guided multi-objective evolutionary algorithms (guided MOEAs) have been significantly used to guide their evolutionary search direction toward these optimal solutions using by decision makers. However, most guided MOEAs need to be iteratively and interactively evaluated and then guided by decision-makers through re-formulating or re-weighting objectives, and it might negatively affect the algorithms performance. In this paper, a novel guided MOEA that uses a dynamic polar-based region around a particular point in objective space is proposed. Based on the region, new selection operations are designed such that the algorithm can guide the evolutionary search toward optimal solutions that are close to the particular point in objective space without the iterative and interactive efforts. The proposed guided MOEA is tested on the multi-criteria decision-making problem of flexible logistics network design with different desired points. Experimental results show that the proposed guided MOEA outperforms two most effective guided and non-guided MOEAs, R-NSGA-II and NSGA-II.     

Numerical study on thermal impacts of different void patterns on performance of chip-scale packaged power device

Chip scale package (CSP) technology offers promising solutions to package power device due to its relatively good thermal performance among other factors. Solder thermal interface materials (STIMs) are often employed at the die bond layer of a chip-scale packaged power device to enhance heat transfer from the chip to the heat spreader. Nonetheless, the presence of voids in the solder die-attach layer impedes heat flow and could lead to an increase in the peak temperature of the chip. Such voids which form easily in the solder joint during reflow soldering process at manufacturing stage are primarily occasioned by out-gassing phenomenon and defective metallisation. Apparently, the thermal consequences of voids have been extensively studied, but not much information exist on precise effects of different patterns of solder die-attach voids on the thermal performance of chip-level packaged power device. In this study, three-dimensional finite element analysis (FEA) is employed to investigate such effects. Numerical studies were carried out to characterise the thermal impacts of various voids configurations, voids depth and voids location on package thermal resistance and chip junction temperature. The results show that for equivalent voiding percentage, thermal resistance increases more for large coalesced void type in comparison to the small distributed voids configuration. In addition, the study suggests that void extending through the entire thickness of solder layer and voids formed very close to the heat generating area of the chip can significantly increase package thermal resistance and chip junction temperature. The findings of this study indicate that void configurations, void depth and void location are vital parameters in evaluating the thermal effects of voids.