Sequential injection analysis (SIA) and response surface methodology: A versatile small volume approach for optimization of photo-Fenton processes

Optimization of photo-Fenton degradation of copper phthalocyanine blue was achieved by response surface methodology (RSM) constructed with the aid of a sequential injection analysis (SIA) system coupled to a homemade photo-reactor. Highest degradation percentage was obtained at the following conditions [H(2)O(2)]/[phthalocyanine] = 7, [H(2)O(2)]/[FeSO(4)] = 10, pH = 2.5, and stopped flow time in the photo reactor = 30 s. The SIA system was designed to prepare a monosegment containing the reagents and sample, to pump it toward the photo-reactor for the specified time and send the products to a flow-through spectrophotometer for monitoring the color reduction of the dye. Changes in parameters such as reagent molar ratios. residence time and pH were made by modifications in the software commanding the SI system, without the need for physical reconfiguration of reagents around the selection valve. The proposed procedure and system fed the statistical program with degradation data for fast construction of response surface plots. After optimization, 97% of the dye was degraded. (C) 2009 Elsevier B.V. All rights reserved.

Crosslinking of Poly(N-vinyl-2-pyrrolidone) in the Coating of Cotton Yarn

Coating of cotton yarn is employed in the textile industry to increase the mechanical resistance of the yarns and resistance to vibration, friction, impact, and elongation, which are some of the forces to which the yarn is subjected during the weaving process. The main objective of this study is to investigate the usage of a synthetic hydrophilic polymer, poly(N-vinyl-2-pyrrolidone) (PVP), to coat 100% cotton textile yarn, aiming to give the yarn a temporary mechanical resistance. For the improvement of the mechanical resistance of the yarn, the following crosslinking processes of PVP were investigated: UV-C (ultraviolet) radiation, the Fenton and photo-Fenton reactions, and sensitized UV-C radiation. The influence of each crosslinking process was determined through tensile testing of the coated yarns. The results indicated that the best crosslinking process employed was UV-C radiation; increasing the mechanical resistance of the yarn up to 44% if compared with the pure cotton yarn, that is, without polymeric coating and crosslinking. POLYM. ENG. SCI., 51:445-453, 2011. (C) 2010 Society of Plastics Engineers

Photo-assisted electrochemical degradation of the commercial herbicide atrazine

This paper presents a degradation study of the pesticide atrazine using photo-assisted electrochemical methods at a dimensionally stable anode (DSA (R)) of nominal composition Ti/Ru(0.3)Ti(0.7)O(2) in a prototype reactor. The effects of current density, electrolyte flow-rate, as well as the use of different atrazine concentrations are reported. The results indicate that the energy consumption is substantially reduced for the combined photochemical and electrochemical processes when compared to the isolated systems. It is observed that complete atrazine removal is achieved at low current densities when using the combined method, thus reducing the energy required to operate the electrochemical system. The results also include the investigation of the phytotoxicity of the treated solutions.

Strong quenching of chlorophyll fluorescence in the desiccated state in three poikilohydric and homoiochlorophyllous moss species indicates photo-oxidative protection on highly light-exposed rocks of a tropical inselberg

The three poikilophydric and homoiochlorophyllous moss species Campylopus savannarum (C. Muell.) Mitt., Racocarpus fontinaloides (C. Muell.) Par. and Ptychomitrium vaginatum Besch. grow on sun-exposed rocks of a tropical inselberg in Brazil subject to regular drying and wetting cycles. Effective photo-oxidative protection in the light-adapted desiccated state in all three species is achieved by a reduction of ground chlorophyll fluorescence, F, to almost zero. Upon rewatering, the kinetics of the recovery of F in air dry cushions to higher values is very fast in the first 5min, but more than 80min are needed until an equilibrium is reached gradually. The kinetics were not different between the three species. The three moss species, have a distinct niche occupation and form a characteristic zonation around soil vegetation islands on the rock outcrops, where C. savannarum and R. fontinaloides form an inner and outer belt, respectively, around vegetation islands and P vaginatum occurs as small isolated cushions on bare rock. However, they were not distinguished by the reduction of F in the dry state and the rewetting recovery kinetics and only slightly different in their photosynthetic capacity. Stable isotope ratios (delta C-13, delta N-15) indicate that liquid films of water limiting diffusion of CO2 are important in determining carbon acquisition and suggest that limitation of CO2 fixation by water films must be more pronounced over time in P vaginatum than in the latter species. This is determined by both the micro site occupied and the form of the moss cushions. (c) 2007 Elsevier GmbH. All rights reserved.

Photo-irradiation effects on the surface morphology of poly(p-phenylene vinylene) films

In this work, we have studied the surface morphology of photo-irradiated poly(p-phenylene vinylene) (PPV) thin films by using atomic force microscopy (AFM). We have analyzed the first-order statistical parameters, the height distribution and the distance between selected peaks. The second-order statistical analysis was introduced calculating the auto-covariance function to determine the correlation length between heights. We have observed that the photo-irradiation process produces a surface topology more homogeneous and isotropic such as a normal surface. In addition, the polymer surface irradiation can be used as a new methodology to obtain materials optically modified. (C) 2009 Elsevier B.V. All rights reserved.

Influence of different light sources and photo-activation methods on degree of conversion and polymerization shrinkage of a nanocomposite resin

The purpose of this study was to evaluate the influence of different light sources and photo-activation methods on degree of conversion (DC%) and polymerization shrinkage (PS) of a nanocomposite resin (Filtek (TM) Supreme XT, 3M/ESPE). Two light-curing units (LCUs), one halogen-lamp (QTH) and one light-emitting-diode (LED), and two different photo-activation methods (continuous and gradual) were investigated in this study. The specimens were divided in four groups: group 1-power density (PD) of 570 mW/cm(2) for 20 s (QTH); group 2-PD 0 at 570 mW/cm(2) for 10 s + 10 s at 570 mW/cm(2) (QTH); group 3-PD 860 mW/cm(2) for 20 s (LED), and group 4-PD 125 mW/cm(2) for 10 s + 10 s at 860 mW/cm(2) (LED). A testing machine EMIC with rectangular steel bases (6 x 1 x 2 mm) was used to record the polymerization shrinkage forces (MPa) for a period that started with the photo-activation and ended after two minutes of measurement. For each group, ten repetitions (n = 40) were performed. For DC% measurements, five specimens (n = 20) for each group were made in a metallic mold (2 mm thickness and 4 mm diameter, ISO 4049) and them pulverized, pressed with bromide potassium (KBr) and analyzed with FT-IR spectroscopy. The data of PS were analyzed by Analysis of Variance (ANOVA) with Welch`s correction and Tamhane`s test. The PS means (MPa) were: 0.60 (G1); 0.47 (G2); 0.52 (G3) and 0.45 (G4), showing significant differences between two photo-activation methods, regardless of the light source used. The continuous method provided the highest values for PS. The data of DC% were analyzed by Analysis of Variance (ANOVA) and shows significant differences for QTH LCUs, regardless of the photo-activation method used. The QTH provided the lowest values for DC%. The gradual method provides lower polymerization contraction, either with halogen lamp or LED. Degree of conversion (%) for continuous or gradual photo-activation method was influenced by the LCUs. Thus, the presented results suggest that gradual method photo-activation with LED LCU would suffice to ensure adequate degree of conversion and minimum polymerization shrinkage.

Continuous and gradual photo-activation methods: influence on degree of conversion and crosslink density of composite resins

Thermal properties and degree of conversion (DC%) of two composite resins (microhybrid and nanocomposite) and two photo-activation methods (continuous and gradual) displayed by the light-emitting diode (LED) light-curing units (LCUs) were investigated in this study. Differential scanning calorimetry (DSC) thermal analysis technique was used to investigate the glass transition temperature (T(g)) and degradation temperature. The DC% was determined by Fourier transform infrared spectroscopy (FT-IR). The results showed that the microhybrid composite resin presented the highest T(g) and degradation temperature values, i.e., the best thermal stability. Gradual photo-activation methods showed higher or similar T(g) and degradation temperature values when compared to continuous method. The Elipar Freelight 2 (TM) LCU showed the lowest T(g) values. With respect to the DC%, the photo-activation method did not influence the final conversion of composite resins. However, Elipar Freelight 2 (TM) LCU and microhybrid resin showed the lowest DC% values. Thus, the presented results suggest that gradual method photo-activation with LED LCUs provides adequate degree of conversion without promoting changes in the polymer chain of composite resins. However, the thermal properties and final conversion of composite resins can be influenced by the kind of composite resin and LCU.

Influence of light guide tip used in the photo-activation on degree of conversion and hardness of one nanofilled dental composite

The aim of this study was to evaluate the degree of conversion and hardness of a dental composite resin Filtek (TM) Z-350 (3M ESPE, Dental Products St. Paul, MN) photo-activated for 20 s of irradiation time with two different light guide tips, metal and polymer, coupled on blue LED Ultraled LCU (Dabi Atlante, SP, Brazil). With the metal light tip, power density was of 352 and with the polymer was of 456 mW/cm(2), respectively. Five samples (4 mm in diameter and 2mm in thickness-ISO 4049), were made for each Group evaluated. The measurements for DC (%) were made in a Nexus-470 FT-IR, Thermo Nicolet, E.U.A. Spectroscopy (FTIR). Spectra for both uncured and cured samples were analyzed using an accessory of reflectance diffuse. The measurements were recorded in absorbance operating under the following conditions: 32 scans, 4 cm(-1) resolution, 300-4000 cm(-1) wavelength. The percentage of unreacted carbon double bonds (% C=C) was determined from the ratio of absorbance intensities of aliphatic C=C (peak at 1637 cm(-1)) against internal standard before and after curing of the sample: aromatic C-C (peak at 1610 cm(-1)). The Vickers hardness measurements (top and bottom surfaces) were performed in a universal testing machine (Buehler MMT-3 digital microhardness tester Lake Bluff, Illinois USA). A 50 gf load was used and the indenter with a dwell time of 30 s. The data were submitted to the test t Student at significance level of 5%. The mean values of degree of conversion for the polymer and metal light guide tip no were statistically different (p = 0.8389). The hardness mean values were no statistically significant different among the light guide tips (p = 0.6244), however, there was difference between top and bottom surfaces (p < 0.001). The results show that so much the polymer light tip as the metal light tip can be used for the photo-activation, probably for the low quality of the light guide tip metal.

Surfactant degradation by a catechol-driven Fenton reaction

The addition of 0.5 mM catechol is shown to accelerate the degradation and mineralization of the anionic surfactant DOWFaX (TM) 2A1 (sodium dodecyldiphenyloxide disulfonate) under conventional Fenton reaction conditions (Fe(II) plus H(2)O(2) at pH 3). The catalytic effect causes a 3-fold increase in the initial rate (up to ca. 20 min) of conversion of the surfactant to oxidation products (apparent first-order rate constants of 0.021 and 0.061 min(-1) in the absence and presence of catechol, respectively). Although this catalytic rate increase persists for a certain amount of time after complete disappearance of catechol itself (ca. 8 min), the reaction rate begins to decline slowly after the initial 20 min towards that observed in the absence of added catechol. Total organic carbon (TOC) measurements of net mineralization and cyclic voltammetric and high performance liquid chromatographic (HPLC) measurements of the initial rate of reaction of catechol and the surfactant provide insight into the role of catechol in promoting the degradation of the surfactant and of degradation products as the eventual inhibitors of the Fenton reaction. (C) 2010 Elsevier B.V. All rights reserved.

PVP superabsorbent nanogels

Monomer free hydrogel nanoparticles (nanogels) were prepared by crosslinking preformed poly(N-vinyl-2-pyrrolidone) (PVP) entrapped in the aqueous pool of hexadecyltrimethylammonium bromide reverse micelles using the Fenton reaction. The PVP nanoparticles were spherical with a dry diameter of 27 nm. The diameter of the swollen particles was ten times higher, i.e., a swelling ratio, Q, above 900, characterizing this preparation as superabsorbent. PVP nanogel swelling was dependent on bound Fe(3+) and varied with pH and ionic strength. Nanogel deswelling by salt followed the anions lyotropic series, i.e., SCN(-) < HSO(3)(-) < NO(3)(-) < I(-) < Cl(-) < CH(3)COO(-) < CF(3)SO(3)(-). The value of Q reached 6,000 in iron-free PVP nanoparticles at low pH, making this nanogel one of the most efficient swelling systems so far described.

Applying sequential injection analysis (SIA) and response surface methodology for optimization of Fenton-based processes

This work presents the use of sequential injection analysis (SIA) and the response surface methodology as a tool for optimization of Fenton-based processes. Alizarin red S dye (C.I. 58005) was used as a model compound for the anthraquinones family. whose pigments have a large use in coatings industry. The following factors were considered: [H(2)O(2)]:[Alizarin] and [H(2)O(2)]:[FeSO(4)] ratios and pH. The SIA system was designed to add reagents to the reactor and to perform on-line sampling of the reaction medium, sending the samples to a flow-through spectrophotometer for monitoring the color reduction of the dye. The proposed system fed the statistical program with degradation data for fast construction of response surface plots. After optimization, 99.7% of the dye was degraded and the TOC content was reduced to 35% of the original value. Low reagents consumption and high sampling throughput were the remarkable features of the SIA system. (C) 2008 Published by Elsevier B.V.

Photocatalytic decomposition of methylene blue via Fenton mechanisms by silicon wafer doped with Au and Cu: a theoretical and experimental study

In this work, we studied the photocatalytic and the structural aspects of silicon wafers doped with Au and Cu submitted to thermal treatment. The materials were obtained by deposition of metals on Si using the sputtering method followed by fast heating method. The photocatalyst materials were characterized by synchrotron-grazing incidence X-ray fluorescence, ultraviolet-visible spectroscopy, X-ray diffraction, and assays of H(2)O(2) degradation. The doping process decreases the optical band gap of materials and the doping with Au causes structural changes. The best photocatalytic activity was found for thermally treated material doped with Au. Theoretical calculations at density functional theory level are in agreement with the experimental data.

Study of photo-assisted electrochemical degradation of carbaryl at dimensionally stable anodes (DSA (R))

This paper presents the results concerning the degradation of the pesticide carbaryl comparing two methods: electrochemical (EC) and photo-assisted electrochemical (PAEC). The experimental variables of applied current density, electrolyte flow-rate and initial carbaryl concentration were investigated. The results demonstrate that the electrochemical degradation of carbaryl was greatly enhanced when simultaneous UV light was applied. The greatest difference between the PAEC and EC method was apparent when lower current densities were applied. The extent of COD removal was much enhanced for the combined method, independent of the applied current density. It should be noted that the complete removal of carbaryl was achieved with out the need to add NaCl to the reaction mixture, avoiding the risk of chlorinated organic species formation. (C) 2009 Elsevier B.V. All rights reserved.

Photo-assisted electrochemical degradation of real textile wastewater

In the present study, photo-assisted electrochemical degradation of real textile wastewater was performed. Degradation assays were performed at constant current (40 mA cm(-2)) in a combined electro/photochemical flow-cell using a Ti/Ru(0.3)Ti(0.7)O(2) DSA(R) type electrode. The results show that the method is capable of removing color and chemical oxygen demand (COD) from the effluent. Additionally, the effect of initial pH and type of supporting electrolyte (Na(2)SO(4) or NaCl) was investigated. The principal figures of merit used in this study were COD removal and color removal (605 nm). The results show that up to 72% color and up to 59% COD removal in 120 min is possible under the operating conditions employed. Studies of the phytotoxicity of the wastewater before and after the photo-assisted degradation assays are also presented and the results demonstrate that the toxicity of the effluent is dependent on the length of electrolysis time and the treatment procedure employed.