UV curing and matting of acrylate nanocomposite coatings by 172 nm excimer irradiation

For UV-curable acrylate coatings reinforced by silica nanoparticles, the effect of 172 nm excimer irradiation on the surface roughness has been studied. A dual UV lamp set-up consisting of a 172 nm excimer lamp and a mercury arc lamp allowed obtaining gloss levels down to 0.5 units (at 60°) depending on the acrylate formulation and curing conditions. Moreover, UV matt-finished sample showed enhanced surface hardness and increased chemical resistance. It is assumed that 172 nm excimer irradiation resulted in a higher network density via additional cross-linking reactions.To study the depth profile of acrylate conversion for coatings cured by the combination of a 172 nm excimer lamp (accountable for surface curing) and a mercury arc lamp (responsible for through curing), FTIR microscopy as well as (Ge)ATR-FTIR having an IR penetration depth of less than 0.5 μm have been applied. Providing the presence of a photoinitiator as well as the absence of oxygen inhibition, similar degrees of double bond conversion of about 90% were observed on the entire area of the cross-section of the coating, i.e. the wavelength of UV irradiation was found to have no significant impact on acrylate conversion.     

A novel thin film photoreactor

A novel thin film photoreactor is described and characterised. The photoreactor was based on a nozzle of special design which generated an unsupported thin liquid film commonly referred to as a liquid ‘bell’. The arrangement described permitted liquids to be irradiated without making contact with either the UV sources or any solid walls in the vicinity of the sources. High speed ciné photography of air bubbles entrained by the liquid films enabled estimates of film velocities and thicknesses to be made. The films accelerated under the influence of gravity with velocities in excess of 2·8 × 10² cm s⁻¹ being obtained near the bottom edge of the bells. Film thicknesses decreased correspondingly, measuring approximately 0·3 cm at the top of the bell and only 1·0 × 10⁻² cm near the bottom. From the film thicknesses, internal and external bell surface areas and volume could be determined: these were respectively 2697·1 cm², 2705·0 cm² and 80·4 cm³. A bioassay based on the bacterium Escherichia coli was used to determine the UV dose accumulated by the bell. The doses obtained ranged from 2·03 mW-s cm⁻² for irradiation by a single source, to 4·84 mW-s cm⁻² for irradiation by all five sources. The properties of the bell photoreactor make the unit potentially applicable to areas of photo-technology in addition to UV sterilisation of liquids.     

PHOTOCATALYSIS BY IRON-RICH MONTMORILLONITE FOR THE TREATMENT OF DYEING WASTEWATER

This study investigates the photocatalytic degradation of dyeing wastewater by iron-rich montmorillonite (MMt) under a 25 W low-pressure mercury lamp (λ = 254 nm, I = 48.4 μW/cm²). Exposing MMt to UV irradiation worked to catalyze the photobleaching of wastewater used in the dyeing process. COD removal efficiencies of 65.0% and 74.0% were achieved in 1 g/L MMt suspensions at a pH of 3 in the absence and presence of 30 min of UV irradiation, respectively. A decolorization efficiency of 71.4% was reached with 1 g/L MMt suspensions at a pH of 3 after 30 min of UV irradiation, while only 4.9% decolorization was attained in darkness. These results indicate that iron-rich MMt is a good photocatalyst for decolorization and COD removal in wastewater from dyeing processes. A low pH value is beneficial to the decolorization of dyeing wastewater. A preliminary photocatalytic mechanism is proposed: the iron in the MMt is responsible for the decolorization of the wastewater because it produces a highly oxidative species of hydroxyl radicals (^?OH).     

Enhancement of UV disinfection efficiency by arraying inclined lamps

A computational study on UV disinfection efficiency has been developed based on the Lambert-Beer law. Comparing a UV lamp arranged vertically to the flow of one arranged on an incline led to the conclusion that UV doses could be increased. The study of the inclination effect was divided into four stages in order to evaluate the increase in the UV dose at each stage. The slope of the inclined UV lamp ranged between 1‡ and 89‡ (0‡<θ<90‡) with other parameters such as diameter of the UV lamp, distance from the surface of the UV lamp, and velocity also recorded. The increase of UV dosage was largely affected by the diameter and velocity of the UV lamp, especially on a lesser slope. To obtain a greater UV dose, it was necessary to assemble UV lamps with lesser slopes. By arranging lamps on an incline, UV disinfection could be enhanced.     

The Basic Principles of UV–Disinfection of Water

The disadvantage of chlorination of drinking water is the possible synthesis of toxic chlorinated fragments. In different cases UV can be an alternative to chlorination. The germicidal effectiveness of UV–radiation is in the 180–320 nm region with an optimum at 265 nm. Approximately 95% of the energy radiated by a low–pressure mercury arc is at the 253.7 nm line, so this source is the most effective one for germicidal applications. The germicidal effectiveness of a broadband source can be calculated. UV alone cannot decrease the concentrations of organic contaminants of the treated water. Quite promising are the systems where UV–radiation acts as a catalyst in oxidation reactions in order to decrease the organic contaminants.     

Effect of pigment colour on the printing performance of synthetic leather using a ultraviolet‐curable water‐borne polyurethane acrylate binder

The effect of pigment colours, cyan (C), magenta (M) and yellow (Y), and a blend of these (CMY blend) on the printing performance of synthetic leather using a ultraviolet (UV)‐curable water‐borne polyurethane acrylate binder and two types of photoinitiators was investigated. The curing process was carried out at different radiation doses using gallium and mercury UV lamps in combination. The performance of the prints was evaluated with abrasion resistance, crock fastness, gloss and hardness values and K/S. Chemical changes in the cured film structures due to UV curing were analysed by Fourier Transform–infrared spectroscopy measurements. The highest hardness values for clear and pigmented cured films were obtained with a gallium and mercury lamp combination at the highest energy density (1529 mJ/cm²). The highest K/S was obtained for the sample printed with the formulation including the C pigment and cured under a gallium and mercury lamp combination at low energy density (398 mJ/cm²). The M‐pigmented film displayed the highest hardness and abrasion resistance, whereas lower values were obtained with films pigmented with Y and C, and CMY blend, successively. The highest dry and wet crock values were obtained with the formulation including the M pigment. CMY‐pigmented film showed the highest gloss values at all energy densities. The pigment colour affected the curing degree of printed films due to the different absorption/transmission intervals of each colour in the UV spectrum.     

Preliminary Data on the Fate of Bromate Ion in Simulated Gastric Juices

Ozone is a drinking water disinfectant that quickly and efficiently kills many types of pathogens. However, the ozonation of bromide ion containing waters can form the disinfection byproduct, bromate ion. Bromate ion is a possible human carcinogen that is regulated by the US EPA at a Maximum Contaminant Level (MCL) of 10 micrograms per liter (μg/L). The lifetime risk at the MCL was calculated from studies where laboratory animals received large doses of bromate ion that would produce effects in their lifetimes. The data from these large doses was fitted to a low-dose linear extrapolation (also called a linearized dose-response) model. The model assumes there is a finite, albeit small, risk at any dose above zero of a genotoxic carcinogen. The validity of the linearized dose-response model projection at low doses is being questioned (i.e., the actual shape and slope of the dose/response as the dose approaches zero). The test system is bromate ion in synthetic and real gastric juices. The results reported here show that the bromate ion half-life, in the presence of typical H⁺, Cl^?, and H₂S concentrations found in the stomach, is 1.5–2 minutes. Thus, as much as 99% of the ingested bromate ion should be decomposed, while it is retained in the stomach. The results of these experiments will be used in the development of a more scientifically rigorous methodology for determining low level effects of bromate ion.     

Optimization of holographic polymer dispersed liquid crystal for ternary monomers

Polarized optical micrography (POM) images of gratings and UV–visible spectra of holographic polymer dispersed liquid crystals (HPDLC) are reported for a ternary monomer system composed of dipentaerythritol hydroxypentaacrylate/trimethylolpropanetriacrylate/N‐vinylpyrrolidone (DPHPA/TMPTA/NVP) = 7/2/1 by weight. Gratings were written by irradiation with an argon ion laser (λ = 488 nm) at various intensities (20–200 mW cm⁻²) on monomer/liquid crystal (LC) composite films of various compositions (75/25, 70/30, 65/35, 62/38, 60/40). Reflection efficiency–irradiation intensity–film composition relationships are obtained in three dimensional plots which show that maximum reflection moves from high LC content (38%) at low irradiation intensity (20 mW cm⁻²) to low LC content (25 wt%) at high irradiation intensity (200 mW cm⁻²). © 1999 Society of Chemical Industry     

紫外光与合成材料的光老化

系统分析了太阳近紫外能量累积值与紫外能谱实测结果及实测阳光碳弧、紫外碳弧、氙灯等人工光源紫外能谱分布图;阐明了应以太阳紫外能谱(290nm~400nm)为依据,重点考察了人工光源紫外能谱的模拟性和紫外能量。以此评价合成材料老化与防老化行为、状态会更趋真实性、科学性与可比性;由我们试验分析的结果可知,氙灯的确是一种理想的人工光源。     

Bromate Ion Analysis By Ion Chromatography

Bromate ion occurs during ozonation of bromide-containing waters. The current WHO guideline for bromate ion is 25 μg/L. Bromate analysis in drinking waters can be performed by various techniques. However, given the commonly low concentrations of bromate ion found in drinking waters, the classical methods do not fit for bromate analysis in most cases.

A specific conductimetric method with anion suppression which enhances analyte detection by lowering the eluent conductivity is described in this paper for low bromate level analysis. Three eluents have been tested in order to have the best signal to noise ratio. Some other parameters likely to interfere in bromate ion detection (nitrate and sulfate in particular) are also investigated. Taking into account the results of three interlaboratory trials between six European laboratories, a 2 μg/L detection level for bromate can be established.     

UV treatment of synthetic styrene-butadiene-styrene rubber

The effectiveness of the treatment with ultraviolet light (UV) on several polymeric surfaces has previously been established. In this study, a low pressure mercury vapour lamp was used as a source of UV radiation for the surface treatment of a difficult-to-bond block styrenebutadiene-styrene rubber (S6), the treatment time ranging from 10 s to 30 min. The UV-treated S6 rubber surfaces were characterized by contact angle measurements (ethylene glycol, 25°C), ATR-IR spectroscopy, XPS, Scanning Electron Microscopy (SEM), and Atomic Force Microscopy (AFM). T-peel tests on UV-treated S6 rubber/polyurethane (PU) adhesive/ leather joints (before and after ageing) were carried out to quantify adhesion strengths. The UV treatment of S6 rubber produced improved wettability, the formation of C—O, C=O and COO^- moieties, and ablation (removal of a thin rubber layer from the surface). The extent of these modifications increased with increasing treatment time. The extended UV treatment produced greater surface modifications, as well as the incorporation of nitrogen moieties at the surface. Furthermore, noticeable ablation of S6 rubber surface occurred. Peel strength values increased with increased treatment time of UV treatment of S6 rubber. Also, with increasing treatment time, the adhesive joints showed different loci of failure: adhesional failure for the as-received and 2 min-UV treated S6 rubber/polyurethane adhesive/leather joints changed to mixed failure (cohesive in the treated S6 rubber + adhesional failure) for the 30 min-UV treated S6 rubber/polyurethane adhesive/leather joint.     

Colour removal of three reactive dyes by UV light exposure after electrochemical treatment

This study applies UV light irradiation after a low current density electrochemical treatment to degrade reactive dyes to remove wastewater colour. The combination of these two techniques improves the quality of the treated effluent with respect to only an electrochemical treatment. Synthetic dyeing effluents containing a reactive dye (C.I. Reactive Orange 4, C.I. Reactive Black 5 or Procion Navy H-EXL) and Na₂SO₄ were studied. Ti/Pt oxides electrodes and UV irradiation lamp (6 W, 254 nm maximum emission) were used. Kinetic constants of the UV irradiation step were calculated. The influence of chloride ion at 3 and 6 mA/cm² was evaluated. Results showed that, with a very small Cl^? concentration (in the order of the net water content) the combined techniques provided full decolourization. The possible presence of 25 organic halogenated compounds was studied by gas chromatography–mass spectrophotometry (GCMS). Only four of them were detected after the electrochemical treatment at low intensity, mainly chloroform. Its concentration was found to be highly dependent of the Cl^? concentration, being much lower when reducing the amount of chloride ion. In all cases, the chloroform concentration was dramatically reduced by further UV irradiation which destroyed it up to a 75%.     

Compromise Between Bromate Ion Formation and Pesticides Degradation and/or Manganese Removal

Ozonation is a widely used technology within the water industry. Bromate ion formed by oxidation of water containing bromide ion was studied with the Gas Ozone Test and Pilot Scale Ozonation. Bromate ion formation was investigated along with the removal of triazines and/or manganese. Under identical conditions of ozonation, BrO₃ ^? formation is specific for each water and depends on parameters such as Total Organic Carbon, UV absorbance at 254 nm, applied ozone and ozone residual. Pesticides degradation by ozonation alone cannot be achieved without the formation of BrO₃ ^? at a high concentration. Hydrogen peroxide, at a constant ozone dose, reduces the BrO₃ ^? formation. However, even with the use of hydrogen peroxide, the concentration of BrO₃ ^? can remain in excess of the provisional Maximum Contaminant Level (10 μg/L). For certain types of water, pesticide degradation is difficult to achieve if the MCL for BrO₃ ^? has to be met. Manganese oxidation by ozone appears to be achieved without high bromate formation; indeed the presence of manganese hinders BrO₃ ^? formation.     

F–Specific Bacteriophages as Indicators of the Disinfection Efficiency of Secondary Effluent with Ultraviolet Radiation

Secondary effluent was irradiated with UV in a shallow bed reactor at flow rates between 10 and 30 m³. h^-1 using 1–3 high pressure mercury lamps. UV doses were calculated to range between 2.5 and 25 mJ.cm^?2 and inactivation of four groups of microorganisms was measured: E. noli, fecal streptococci, somatic coliphagesi and F–specific bacteriophages. Their relative UV resistance (in this order) was 1.0 : 1.5 : 1.1 : 2.3. Inactivation of F–specific (coliphages with 3 log₁₀ units required a dose of approx. 36 mJ.cm^?2. Dose–response curves were linear with correlation coefficients of ca. 0.90, except for somatic coliphages, which seem to include a relatively UV–sensitive and a more resistant fraction. This study clearly demonstrated that F–specific bacteriophages are better indicator organisms with regard to viral inactivation by UV than classical parameters like E. coli. fecal streptococcior coliphages.     

Ozone Generation with Narrow–Band UV Radiation

Ozone formation in oxygen at atmospheric pressure following the photodissociation of O₂ molecules in the vacuum UV range is tudied. A new VUV source based on incoherent xenon excimer radiation from a dielectric–barrier discharge provided narrow–band UV radiation at 172 nm with a half–width of 14 nm. The formation of ozone from the initial photodissociation fragments O(³P) and O(¹D) is treated theoretically and compared to measurements.     

Spatial and temporal evolution of the photoinitiation rate for thick polymer systems illuminated by polychromatic light: selection of efficient photoinitiators for LED or mercury lamps

BACKGROUND: Four common free radical photoinitiators were evaluated for use in thick photopolymerizations illuminated with a medium‐pressure 200 W mercury–xenon arc lamp and a high‐intensity 400 nm light‐emitting diode (LED) lamp. For each photoinitiator/lamp combination, the spatial and temporal evolution of the photoinitiation rate profile was analyzed by solving the set of differential equations that govern the light intensity gradient and initiator concentration gradient for polychromatic illumination. RESULTS: The simulation results revealed that two of the four photoinitiators evaluated were ineffective for photoinitiating thick polymer systems. The photoinitiator bis(2,4,6‐trimethylbenzoyl)‐phenylphosphine oxide, in combination with the 400 nm LED lamp, was shown to be the most efficient photoinitiator/light source combination for photoinitiation of thick systems. CONCLUSION: The results show that some photoinitiators commonly used for photopolymerization of thin coatings are ineffective for curing thick systems. LED light sources provide advantages over traditional mercury lamps, and may have tremendous potential in the effective photoinitiation of thick polymer systems. Copyright © 2008 Society of Chemical Industry     

Pilot Plant Results with Three Different Types of UV Lamps for Advanced Oxidation

Three different types of ultraviolet lamps were tested for the advanced oxidation process application on pre-treated surface water in a pilot plant. The pilot setup consisted of three parallel reactors with either medium pressure, low pressure or dielectric barrier discharge UV lamps. Four model compounds (atrazine, bromacil, ibuprofen and N-nitroso-dimethylamine (NDMA)) and 0, 5 or 10 ppm hydrogen peroxide were dosed. Low pressure lamps were shown to have the lowest energy demand, calculated as electrical energy per order, followed by dielectric barrier discharge lamps and then medium pressure lamps. Medium pressure lamps gave the highest formation of genotoxic activity and nitrite formation, whereas no formation of genotoxic activity was observed for either of the other lamp types.     

UV/H2O2 Treatment: A Practical Solution for Organic Contaminant Control and Primary Disinfection

PWN's water treatment plant Andijk was commissioned almost 40 years ago. It services water from the IJssel Lake by conventional surface water treatment. In view of taste and odor problems the plant was retrofitted with GAC filtration 25 years ago. The finished water quality still complies with all E.C. and Dutch drinking water standards. Nevertheless an upgrade is desired to avoid the use of chlorine and to extend the barriers against pathogenic micro-organisms and a broad range of organic micropollutants such as pesticides, rocket fuel by-products (NDMA), fuel oxygenates (MTBE), solvents (dioxane), endocrine disruptors, algae toxins, pharmaceuticals, etc. UV/H₂O₂ treatment was selected for both primary disinfection and organic contaminant control. The disinfection requirements were based on a 10^?4 health risk. The required 3 log inactivation for Giardia and Cryptosporidium was achieved by an UV dose lower than 20 mJ/cm². The highest UV dose, 105 mJ/cm², was needed for the inactivation of spores of Sulphite Reducing Clostridia. Reactivation of protozoa was established for UV doses up to 25 mJ/cm², for doses higher than 45 mJ/cm² no reactivation was observed. In view of the raw water concentrations the required organic contaminant degradation was set at 80%. Collimated beam and pilot-plant work showed that the required degradation can be achieved by the proper combination of electric energy and H₂O₂. In a UV reactor optimized for organic contaminant control, UV dose of 540 mJ/cm² (about 0.5 kWh/m³) and 6 mg/L H₂O₂ were needed. Under those conditions pesticides (atrazine), NDMA, MTBE, dioxane, endocrine disruptors (bisphenol A), microcystine and pharmaceuticals (diclofenac, ibuprofen) could be removed up to the required 80%. Bromate formation was absent while formation of primary metabolites was insignificant. The UV dose for organic contaminant control is about five times higher than the dose needed for disinfection. The UV/H₂O₂ process was implemented into the existing treatment train between the sand and GAC filters. In the GAC filters excess H₂O₂ is degraded, nitrite is converted into nitrate and biodegradable reaction products are consumed by bacteria. The full-scale installation with 3 streets of 4 Trojan Swift 16L30 reactors has been in operation since October 2004. Disinfection and organic contaminant control are as expected.     

Degradation of Carbamazepine by Photo-assisted Ozonation: Influence of Wavelength and Intensity of Radiation

This article presents the results of an investigation into the function of UV in a photo-assisted ozonation process for treatment of carbamazepine (CBZ) in treated domestic wastewaters. Experiments were conducted on synthetic spiked water and secondary treated municipal wastewater. Degradation of CBZ was studied for various combination of O₃ dosage ranging from 4.8 to 14.4 mg/h and UV intensities with varying intensity and wavelength (UVC: λ = 254 nm and UVA: 352 nm). In synthetic spiked water, CBZ was degraded to below detectable limits within 0.5 min for ozone dose of 14.4 mg/h. The rate of degradation of CBZ increased exponentially with increase in ozone dose following a zero-order rate at each dose level. The degradation rate of CBZ in wastewater was slower compared to deionized water (DI) water by 40–75% for various doses of ozone, presumably due to the presence of organic matter remaining in treated wastewater. Optimal UV intensities for UVA and UVC were obtained as 0.62 and 0.82 mW/cm² for all doses of ozone in synthetic spiked water samples and UV intensities beyond this resulted in lower rates of degradation of CBZ. For photo-assisted ozonation with ozone doses of 9.6 and 14.4 mg/L, rate constants were two times higher for UVA irradiations as compared to UVC irradiation. Contrary to observations in DI water, experiments in wastewater showed increase in rate of degradation with higher UV intensities. Overall, photo-assisted ozonation was found to be appropriate for both water and wastewater treatment by exploiting the benefit of direct attack of ozone and of produced ^?OH radicals to yield a greater extent of mineralization of CBZ.