Removal Mechanism Investigation of Ultraviolet Induced Nanoparticle Colloid Jet Machining.

Ultraviolet induced nanoparticle colloid jet machining is a new ultra-precision machining technology utilizing the reaction between nanoparticles and the surface of the workpiece to achieve sub-nanometer ultra-smooth surface manufacturing without damage. First-principles calculations based on the density functional theory (DFT) were carried out to study the atomic material removal mechanism of nanoparticle colloid jet machining and a series of impacting and polishing experiments were conducted to verify the mechanism. New chemical bonds of Ti-O-Si were generated through the chemical adsorption between the surface adsorbed hydroxyl groups of the TiO2 cluster and the Si surface with the adsorption energy of at least -4.360 eV. The two Si-Si back bonds were broken preferentially and the Si atom was removed in the separation process of TiO2 cluster from the Si surface realizing the atomic material removal. A layer of adsorbed TiO2 nanoparticles was detected on the Si surface after 3 min of fixed-point injection of an ultraviolet induced nanoparticle colloid jet. X-ray photoelectron spectroscopy results indicated that Ti-O-Si bonds were formed between TiO2 nanoparticles and Si surface corresponding to the calculation result. An ultra-smooth Si workpiece with a roughness of Rq 0.791 nm was obtained by ultraviolet induced nanoparticle colloid jet machining.

Investigation of Surfactant Type, Dosage and Ultrasonication Temperature Control on Dispersity of Metal-Coated Multi-Walled Carbon Nanotubes.

We studied the dispersity of multi-walled carbon nanotubes (MWNTs) combined with different metal- lic particles (Ni and Fe). An ultrasonic-assisted water-bath dispersion process was used to dis- perse the metal-coated MWNTs in different solutions and the dispersity was measured using an ultraviolet-visible spectrophotometer. The dispersity and morphology of the MWNTs were characterized using field-emission scanning electron microscopy (FE-SEM) together with digital image processing technology. Effects of dispersant type (sodium dodecyl benzene sulfonate (SDBS), oleic acid, and polymer (TNEDIS)) and surfactant dosage on the dispersity of the metal-coated MWNTs were investigated under controlled and uncontrolled temperatures and results were compared with those from the untreated MWNTs. The results showed that the negative effects of temperature on the ultrasonic dispersion process could be eliminated through a temperature-controlled system. Moreover, the TNEDIS, SDBS, and oleic acid were arranged in the descending order of the dispersion effect degree. The untreated MWNTs, Ni-coated MWNTs, and Fe-coated MWNTs were arranged in the descending degree of dispersity order. Since the metal coating makes the MWNTs harder and more fragile, the metal-coated MWNTs are more likely to fracture during the ultrasonic dispersion process.

Adsorption and Photocatalytic Degradation of Methylene Blue Using Potassium Polytitanate and Solar Simulator.

Solar photocatalytic degradation of organic water pollutants can be used to degrade toxic organic pollutants in water. In this study, potassium titanate nanofibres were synthesized by an aqueous peroxide route at high pH and examined as photocatalysts for photodegradation of methylene blue (MB) using a solar simulator. Initially, MB was adsorbed on the surface of potassium polytitanates to achieve adsorption equilibrium before the photocatalysts were illuminated using solar simulator. The results showed that potassium polytitanate nanofibres were effective adsorbents of MB and also facilitated its photocatalytic degradation. Sulphate ion evolution during photocatalysis confirmed that some mineralisation occurred and hence photo-oxidative degradation of MB took place. The optimum operational conditions for the photocatalytic degradation of MB were found at 0.05 g/L of photocatalyst load, 10 mg/L MB and pH 7. The stability and regeneration of the photocatalyst specimen was also studied for 3 degradation cycles using adsorption/photocatalysis model. Morphological structure analysis of potassium titanate showed nanocrystallines structure of longitudinally-oriented isolated fibre with a length up to several micrometres with diameters ranging from 10 to 20 nanometres.

Adsorption and photocatalytic degradation of malachite green by vanadium doped zinc oxide nanoparticles.

Herein the degradation of malachite green (MG) dye from aqueous medium by vanadium doped zinc oxide (ZnO:V3%) nanopowder was investigated. The specific surface area and pore volume of the nanopowder was characterized by nitrogen adsorption method. Batch experimental procedures were conducted to investigate the adsorption and photocatalytic degradation of MG dye. Adsorption kinetics investigations were performed by varying the amount of the catalyst and the initial dye concentrations. Adsorption and photocatalytic degradation data were modeled using the Lagergren pseudo-first-order and second-order kinetic equation. The results showed that the ZnO:V3% nanopowder was particularly effective for the removal of MG and data were found to comply with Lagergreen pseudo-first-order kinetic model.

Some observations on the development of superior photocatalytic systems for application to water purification by the "adsorb and shuttle" or the interphase charge transfer mechanisms.

Adsorb and shuttle (A/S) and interfacial charge transfer are the two major strategies for overcoming recombination in photocatalysis in this era of nanoparticle composites. Their relationships are considered here. A review of key literature is accompanied by a presentation of three new experiments within the overall aim of assessing the relation of these strategies. The cases presented include: A/S by a high silica zeolite/TiO2 composite, charge transfer (CT) between phases in a TiO2/WO3 composite and both A/S and CT by composites of TiO2 with powered activated carbon (AC) and single-walled carbon nanotubes (SWCNT). The opportunities presented by the two strategies for moving toward photocatalysts that could support applications for the removal of contaminants from drinking water or that lead to a practical adsorbent for organics that could be regenerated photocatalytically link this discussion to ongoing research here.

Transmittance enhancement of sapphires with antireflective subwavelength grating patterned UV polymer surface structures by soft lithography.

We report the total and diffuse transmission enhancement of sapphires with the ultraviolet curable SU8 polymer surface structures consisting of conical subwavelength gratings (SWGs) at one- and both-side surfaces for different periods. The SWGs patterns on the silicon templates were transferred into the SU8 polymer film surface on sapphires by a simple and cost-effective soft lithography technique. For the fabricated samples, the surface morphologies, wetting behaviors, and optical characteristics were investigated. For theoretical optical analysis, a rigorous coupled-wave analysis method was used. At a period of 350 nm, the sample with SWGs on SU8 film/sapphire exhibited a hydrophobic surface and higher total transmittance compared to the bare sapphire over a wide wavelength of 450-1000 nm. As the period of SWGs was increased, the low total transmittance region of < 85% was shifted towards the longer wavelengths and became broader while the diffuse transmittance was increased (i.e., larger haze ratio). For the samples with SWGs at both-side surfaces, the total and diffuse transmittance spectra were further enhanced compared to the samples with SWGs at one-side surface. The theoretical optical calculation results showed a similar trend to the experimentally measured data.

Effect of applied voltage on the structural properties of SnO2 nanostuctures grown on indium-tin-oxide coated glass substrates.

SnO2 nanostuctures were formed on indium-tin-oxide (ITO)-coated glass substrates by using an electrochemical deposition (ECD) method. X-ray photoelectron spectroscopy (XPS) spectra showed the existence of elemental Sn and O in the samples, indicative of the formation of SnO2 materials. An XPS spectrum showing the O 1s peak at a binding energy of 531.5 eV indicated that the oxygen atoms were bonded to the SnO2. Field-emission scanning electron microscopy (FE-SEM) images showed that the samples formed by using the ECD method had SnO2 nanostructures with a size between 280 and 350 nm. FE-SEM images showed that the size of the SnO2 nanostructures formed at 65 degrees C for 30 min increased with decreasing applied voltage. X-ray diffraction (XRD) patterns showed that the SnO2 nanostrucures had tetragonal structures with cell parameters of a = 4.738 A and c = 3.187 A. XRD results showed that the peak intensity of the (110) plane increased with decreasing applied voltage, indicative of a preferencial orientation of the (110) plane.

Integrated electrokinetics-adsorption remediation of saline-sodic soils: effects of voltage gradient and contaminant concentration on soil electrical conductivity.

In this study, an integrated in situ remediation technique which couples electrokinetics with adsorption, using locally produced granular activated carbon from date palm pits in the treatment zones that are installed directly to bracket the contaminated soils at bench-scale, is investigated. Natural saline-sodic clay soil, spiked with contaminant mixture (kerosene, phenol, Cr, Cd, Cu, Zn, Pb, and Hg), was used in this study to investigate the effects of voltage gradient, initial contaminant concentration, and polarity reversal rate on the soil electrical conductivity. Box-Behnken Design (BBD) was used for the experimental design and response surface methodology (RSM) was employed to model, optimize, and interpret the results obtained using Design-Expert version 8 platform. The total number of experiments conducted was 15 with voltage gradient, polarity reversal rate, and initial contaminant concentration as variables. The main target response discussed in this paper is the soil electrical conductivity due to its importance in electrokinetic remediation process. Responses obtained were fitted to quadratic models whose R (2) ranges from 84.66% to 99.19% with insignificant lack of fit in each case. Among the investigated factors, voltage gradient and initial contaminant concentration were found to be the most significant influential factors.

Effects of pH value of the electrolyte and glycine additive on formation and properties of electrodeposited Zn-Fe coatings.

Environmentally friendly and cyanide-free sulfate bath under continuous current and the corrosion behavior of electrodeposits of zinc-iron alloys were studied by means of electrochemical tests in a solution of 3.5% NaCl in presence and absence of glycine. The effects of pH on the quality of Zn-Fe coatings were investigated in order to improve uniformity and corrosion protection performance of the coating films. The deposit morphology was analyzed using scanning electron microscopy (SEM), and X-ray diffraction (XRD) was used to determine the preferred crystallographic orientations of the deposits. It was found that the uniformity and corrosion resistance of Zn-Fe coating films were strongly associated with pH of the coating electrolyte. To obtain the effect of pH on the film quality and corrosion performances of the films, the corrosion test was performed with potentiodynamic anodic polarization method. It was also observed that uniformity and corrosion resistivity of the coating films were decreased towards pH = 5 and then improved with increasing pH value of the electrolyte. The presence of glycine in the plating bath decreases the corrosion resistance of Zn-Fe coatings.

Coupled electrokinetics-adsorption technique for simultaneous removal of heavy metals and organics from saline-sodic soil.

In situ remediation technologies for contaminated soils are faced with significant technical challenges when the contaminated soil has low permeability. Popular traditional technologies are rendered ineffective due to the difficulty encountered in accessing the contaminants as well as when employed in settings where the soil contains mixed contaminants such as petroleum hydrocarbons, heavy metals, and polar organics. In this study, an integrated in situ remediation technique that couples electrokinetics with adsorption, using locally produced granular activated carbon from date palm pits in the treatment zones that are installed directly to bracket the contaminated soils at bench-scale, is investigated. Natural saline-sodic soil, spiked with contaminant mixture (kerosene, phenol, Cr, Cd, Cu, Zn, Pb, and Hg), was used in this study to investigate the efficiency of contaminant removal. For the 21-day period of continuous electrokinetics-adsorption experimental run, efficiency for the removal of Zn, Pb, Cu, Cd, Cr, Hg, phenol, and kerosene was found to reach 26.8, 55.8, 41.0, 34.4, 75.9, 92.49, 100.0, and 49.8%, respectively. The results obtained suggest that integrating adsorption into electrokinetic technology is a promising solution for removal of contaminant mixture from saline-sodic soils.

Micelle-assisted synthesis of Al2O3·CaO nanocatalyst: optical properties and their applications in photodegradation of 2,4,6-trinitrophenol.

Calcium oxide (CaO) nanoparticles are known to exhibit unique property due to their high adsorption capacity and good catalytic activity. In this work the CaO nanocatalysts were prepared by hydrothermal method using anionic surfactant, sodium dodecyl sulphate (SDS), as a templating agent. The as-synthesized nanocatalysts were further used as substrate for the synthesis of alumina doped calcium oxide (Al2O3·CaO) nanocatalysts via deposition-precipitation method at the isoelectric point of CaO. The Al2O3·CaO nanocatalysts were characterized by FTIR, XRD, TGA, TEM, and FESEM techniques. The catalytic efficiencies of these nanocatalysts were studied for the photodegradation of 2,4,6-trinitrophenol (2,4,6-TNP), which is an industrial pollutant, spectrophotometrically. The effect of surfactant and temperature on size of nanocatalysts was also studied. The smallest particle size and highest percentage of degradation were observed at critical micelle concentration of the surfactant. The direct optical band gap of the Al2O3·CaO nanocatalyst was found as 3.3 eV.

Voltage-induced adsorbate damping of single gold nanorod plasmons in aqueous solution.

Unbiased gold nanoparticles are negatively charged in aqueous solution but not hydrated. Optical spectroscopy of voltage-clamped single gold nanoparticles reveals evidence that anion adsorption starts at positive potentials above the point of zero charge, causing severe but reversible plasmon damping in combination with a spectral red shift exceeding the linear double layer charging effect. Plasmon damping by adsorbate is relevant for the use of nanoparticles in catalysis, in biodiagnostics, and in surface enhanced Raman scattering.

Bacteria-directed construction of hollow TiO2 micro/nanostructures with enhanced photocatalytic hydrogen evolution activity.

A general method has been developed for the synthesis of various hollow TiO2 micro/nanostructures with bacteria as templates to further study the structural effect on photocatalytic hydrogen evolution properties. TiO2 hollow spheres and hollow tubes, served as prototypes, are obtained via a surface sol-gel process using cocci and bacillus as biotemplates, respectively. The formation mechanisms are based on absorption of metal-alkoxide molecules from solution onto functional cell wall surfaces and subsequent hydrolysis to give nanometer-thick oxide layers. The UV-Vis absorption spectrum shows that the porous TiO2 hollow spheres have enhanced light harvesting property compared with the corresponding solid counterpart. This could be attributed to their unique hollow porous micro/nanostructures with microsized hollow cavities and nanovoids which could bring about multiple scattering and rayleigh scattering of light, respectively. The hollow TiO2 structures exhibit superior photocatalytic hydrogen evolution activities under UV and visible light irradiation in the presence of sacrificial reagents. The hydrogen evolution rate of hollow structures is about 3.6 times higher than the solid counterpart and 1.5 times higher than P25-TiO2. This work demonstrates the structural effect on enhancing the photocatalytic hydrogen evolution performance which would pave a new pathway to tailor and improve catalytic properties over a broad range.

Efficient photocatalytic decomposition of perfluorooctanoic acid by indium oxide and its mechanism.

Perfluorooctanoic acid (C(7)F(15)COOH, PFOA) has increasingly attracted worldwide concerns due to its global occurrence and resistance to most conventional treatment processes. Though TiO(2)-based photocatalysis is strong enough to decompose most organics, it is not effective for PFOA decomposition. We first find that indium oxide (In(2)O(3)) possesses significant activity for PFOA decomposition under UV irradiation, with the rate constant about 8.4 times higher than that by TiO(2). The major intermediates of PFOA were C(2)-C(7) shorter-chain perfluorocarboxylic acids, implying that the reaction proceeded in a stepwise manner. By using diffuse reflectance infrared Fourier transform spectroscopy, (19)F magic angle spinning nuclear magnetic resonance, and electron spin resonance, we demonstrate that the terminal carboxylate group of PFOA molecule tightly coordinates to the In(2)O(3) surface in a bidentate or bridging configuration, which is beneficial for PFOA to be directly decomposed by photogenerated holes of In(2)O(3) under UV irradiation, while PFOA coordinates to TiO(2) in a monodentate mode, and photogenerated holes of TiO(2) preferentially transform to hydroxyl radicals, which are inert to react with PFOA. PFOA decomposition in wastewater was inhibited by bicarbonate and other organic matters; however, their adverse impacts can be mostly avoided via pH adjustment and ozone addition.

Enhancing oil-sorption performance of polypropylene fiber by surface modification via UV-induced graft polymerization of butyl acrylate.

In order to improve oil sorption performances, polypropylene (PP) fiber was modified through graft polymerization with butyl acrylate (BA) initiated by ultraviolet (UV) radiation in isopropanol/water mixture solution. Fourier transform infrared (FT-IR) spectra, scanning electron microscopy (SEM) and specific surface area were used to characterize the chemical and morphological changes of the PP fiber surface. Static contact angle (CA) measurements showed that the hydrophilicity of original PP fiber was enhanced after graft polymerization. The grafted fiber exhibited an excellent oil-sorption, oil-retention performance, fast saturation-sorption rate and superior reusability of oil. When the grafting degree was 15.55%, the maximum oil-sorption capacity reached 18.35 g/g, while the oil-sorption capacity of original PP fiber was only 11.54 g/g. After the tenth cycle of reuse, the grafted fiber sorbent assembly only lost 30% of its virgin sorption capacity.

Light harvesting, energy transfer and electron cycling of a native photosynthetic membrane adsorbed onto a gold surface.

Photosynthetic membranes comprise a network of light harvesting and reaction center pigment-protein complexes responsible for the primary photoconversion reactions: light absorption, energy transfer and electron cycling. The structural organization of membranes of the purple bacterial species Rb. sphaeroides has been elucidated in most detail by means of polarized light spectroscopy and atomic force microscopy. Here we report a functional characterization of native and untreated membranes of the same species adsorbed onto a gold surface. Employing fluorescence confocal spectroscopy and light-induced electrochemistry we show that adsorbed membranes maintain their energy and electron transferring functionality. Gold-adsorbed membranes are shown to generate a steady high photocurrent of 10 microA/cm(2) for several minutes and to maintain activity for up to three days while continuously illuminated. The surface-adsorbed membranes exhibit a remarkable functionality under aerobic conditions, even when exposed to light intensities well above that of direct solar irradiation. The component at the interface of light harvesting and electron cycling, the LH1 complex, displays exceptional stability, likely contributing to the robustness of the membranes. Peripheral light harvesting LH2 complexes show a light intensity dependent decoupling from photoconversion. LH2 can act as a reversible switch at low-light, an increased emitter at medium light and photobleaches at high light.

Improving protein transfer efficiency and selectivity in affinity contact printing by using UV-modified surfaces.

Affinity contact printing (αCP) is a technique that allows the selective capture of a target protein from solutions to a polymeric stamp decorated with an antibody, and then the target protein is printed onto a solid surface. The success of αCP critically relies on the precise control of protein-surface interactions. Here, we report a study on the effect of UV on the protein-surface interactions between protein and polydimethylsiloxane stamps and between protein and glass slides decorated with N,N-dimethyl-n-octadecyl-3-aminopropyltrimethoxysilyl chloride (DMOAP). Our results show that UV-modified surfaces can be used to improve the transfer efficiency and selectivity of proteins during αCP. For example, the protein transfer efficiency of human IgG onto a DMOAP-coated slide increases from 7.2% to 45.1% after the UV treatment. On the basis of these results, UV-modified surfaces were employed to develop a αCP system for protein detection. The detection limit of anti-IgG in this system is around 10 ng/mL, and the dynamic range is 4 orders of magnitude.

2,4,5-Trichlorophenol degradation using a novel TiO2-coated biofilm carrier: roles of adsorption, photocatalysis, and biodegradation.

Intimate coupling of photocatalysis and biodegradation (ICPB) offers potential for degrading biorecalcitrant and toxic organic compounds. This study reports on a novel sponge-type, TiO(2)-coated biofilm carrier that showed significant adherence of TiO(2) and ability to accumulate biomass in its interior. This carrier was tested for ICPB in a continuous-flow photocatalytic circulating-bed biofilm reactor (PCBBR) to mineralize 2,4,5-trichlorophenol (TCP), which is biorecalcitrant. Four mechanisms possibly acting in ICPB were tested separately: TCP adsorption to the carrier, UV photolysis, UV photocatalysis, and biodegradation by biofilm inside the carrier. The carrier exhibited strong TCP adsorption that followed a Freundlich isotherm with an exponent near 2. Whereas UV photolysis was negligible, photocatalysis produced TCP-degradation products that could be mineralized, and the strong adsorption of TCP to the carrier enhanced biodegradation by relieving toxicity. Validating the ICPB concept, biofilm was protected inside the carriers, although biomass originally on the outer surface of the carriers was eliminated. ICPB significantly lowered the diversity of the bacterial community, but five genera known to biodegrade chlorinated phenols (Ralstonia, Bradyrhizobium, Methylobacterium, Cupriavidus, and Pandoraea) were markedly enriched.

The ratio of transmitted near-infrared radiation to photosynthetically active radiation (PAR) increases in proportion to the adsorbed PAR in the canopy.

The daily total photosynthetically active radiation (400-700 nm, PAR) and near-infrared radiation (700-1000 nm, NIR) were measured in the understory beneath the canopy (PARt and NIRt) and above the canopy (PARi and NIRi) of a Japanese cool-temperate deciduous broad-leaved forest during the snow-free period (May to November). The integration of spectral radiation for NIR and that for PAR, and the daily integrations of instantaneous NIR and PAR, reduced the noises from the optical difference in spectrum and from canopy structure heterogeneity, sky condition and solar elevation. PARi/PARt was linearly related to NIRt/PARt (R² = 0.96). The effect of cloudiness was negligible, because the fluctuation of NIRi/PARi was quite small regardless of season and weather conditions compared with the range of NIRt/PARt in the forest. The ratio of NIRt/PARt beneath the canopy was log-linearly related to the in situ leaf area index (LAI) with a wide range from 0 to 5.25 (R² = 0.97). We conclude that seasonal changes in fAPAR (= 1 - PARt/PARi) and LAI of a canopy can be estimated with high accuracy by transmitted NIRt and PARt beneath the canopy.

Dynamic control over cell adhesive properties using molecular-based surface engineering strategies.

In complex organisms, cells are often dependent on their extracellular matrix (ECM) for structural integrity, the mechanical properties of tissues, and for signaled regulation of cellular processes including adhesion, migration, growth, secretion, gene expression and apoptosis. Achieving dynamic control, i.e. by using an external stimulus, over the interactions between cells and artificial interfaces holds considerable promise in tissue engineering, medicine, cell biology and immunology. For example, improved spatial control over cell-surface interaction is potentially useful in the design of cell-based screening devices. Dynamic control over SAMs for cell adhesion provides an additional handle to direct and study the attachment of cells to surfaces, e.g., in studying cell spreading from a predetermined pattern in order to screen the cytotoxicity of drug candidates. However, 'reversible' control of cell adhesion onto substrates is an area that is still in its infancy. In this critical review recent developments in cell adhesion of mammalian cells to SAM-modified surfaces, the physical properties of which can be controlled by an external stimulus, e.g. by light, electrochemistry, etc., are discussed (118 references).