Cable Aging Monitoring with Differential Scanning Calorimetry (DSC) in Nuclear Power Plants

As a requirement for plant life extension for more than 40 years, additional Cable Aging Management Program (CAMP) has to be implemented in Nuclear Power Plant Krško. Samples of cables are selected based on nuclear safety and electrical equipment criticality for inspection and testing, to check functionality and prevent unexpected failure during normal operation. Different onsite testing equipment and methods are implemented to find harsh environment due to temperature, radiation, humidity and chemical effects that could affect insulation lifetime. Infrared thermography is used for determining and evaluating temperature hot spots. The article presents a development of laboratory testing of cable insulation using Differential Scanning Calorimetry (DSC). Thirty-six samples of different nuclear qualified cables made of most frequently used materials, ethylene propylene rubber (EPR) and cross linked polyethylene (XLPE) – all with chlorosulfonated polyethylene (CSPE) jacket, were tested. Samples were 35 years old and additionally temperature aged in several steps with an intention to get acceptance criteria. Similar tests were conducted in two testing laboratories. The results showed an evident decrease in oxidation stability of the inner EPR insulation; the onset temperature of oxidation processes has been shifted from 238 °C (unaged samples) to 175 °C (most aged samples). A decrease in oxidation stability was also observed for XPLE insulation; the onset oxidation temperature decreased from 266 °C for unaged samples to 213 °C (most aged samples). For the jacket material CSPE used as the insulation protection nearly no changes were observed

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Approximately, 15% of the total textile colorant production is estimated to be lost during dyeing and processing of textile fibres. If left untreated, these wastewaters can represent a serious environmental threat. In the present paper a combination of photocatalytic and biological degradation of prepared textile wastewaters (simulation of real textile effluent) is presented. Samples have been monitored through the course of photocatalytic experiments: change in UV-VIS absorbance spectra and complete decolouration were achieved for all three tested dyed wastewaters; however, only partial COD removal was achieved with photocatalytic oxidation (PCOx) and photocatalytic ozonation (PCOz). Toxicity test (Vibrio fischeri) of untreated and pretreated (constructed wetland, CW) samples showed a decrease in toxicity values only for the red-dyed wastewater. Comparison of efficiency of PCOx and PCOz for decolouration and mineralization of three structurally different dyes (anthraquinone and two azo dyes) has been done. CW pretreatment caused faster decolouration and substantial COD removal in PCOx (up to 45%). Pretreatment also accelerated decolouration during PCOz, but it accelerated COD removal only in the case of red-dyed wastewater due to short irradiation times applied

The role of fluorine in F-La/TiO2 photocatalysts on photocatalytic decomposition of methanol-water solution

F-La/TiO2 photocatalysts were studied in photocatalytic decomposition water-methanol solution. The structural, textural, optical, and electronic properties of F-La/TiO2 photocatalysts were studied by combination of X-ray powder diffraction (XRD), nitrogen physisorption, Ultraviolet-visible diffuse reflectance spectroscopy (UV-Vis DRS), Electrochemical impedance spectroscopy (EIS), and X-ray fluorescence (XPS). The production of hydrogen in the presence of 2.8F-La/TiO2 was nearly up to 3 times higher than in the presence of pure TiO2. The photocatalytic performance of F-La/TiO2 increased with increasing photocurrent response and conductivity originating from the higher amount of fluorine presented in the lattice of TiO2.Web of Science1218art. no. 286

Optimization Method of the Solvothermal Parameters Using Box–Behnken Experimental Design—The Case Study of ZnO Structural and Catalytic Tailoring

ZnO photocatalysts were synthesized via solvothermal method and a reduced experimental design (Box–Behnken) was applied to investigate the influence of four parameters (temperature, duration, composition of the reaction mixture) upon the photocatalytic activity and the crystal structure of ZnO. The four parameters were correlated with photocatalytic degradation of methyl orange and the ratio of two crystallographic facets ((002) and (100)) using a quadratic model. The quadratic model shows good fit for both responses. The optimization experimental results validated the models. The ratio of the crystal facets shows similar variation as the photocatalytic activity of the samples. The water content of the solvent is the primary factor, which predominantly influence both responses. An explanation was proposed for the effect of the parameters and how the ratio of (002) and (100) crystal facets is influenced and its relation to the photocatalytic activity. The present research laconically describes a case study for an original experimental work, in order to serve as guideline to deal with such complicated subjects as quantifying influence of synthesis parameters upon the catalytic activity of the obtained ZnO

One-Pot Synthesis of Sulfur-Doped TiO2/Reduced Graphene Oxide Composite (S-TiO2/rGO) with Improved Photocatalytic Activity for the Removal of Diclofenac from Water

Sulfur-doped TiO2 (S-TiO2) composites with reduced graphene oxide (rGO), wt. % of rGO equal to 0.5%, 2.75%, and 5.0%, were prepared by a one-pot solvothermal procedure. The aim was to improve photocatalytic performance in comparison to TiO2 under simulated solar irradiation for the treatment of diclofenac (DCF) in aqueous medium. The obtained composites were characterized for physical- chemical properties using thermogravimetric analysis (TGA), X-ray diffractograms (XRD), Raman, scanning electron microscopy (SEM)/energy dispersive X-ray (EDX), Brauner Emmett Teller (BET), and photoluminescence (PL) analyses, indicating successful sulfur doping and inclusion of rGO. Sulfur doping and rGO have successfully led to a decrease in photogenerated charge recombination. However, both antagonistic and synergistic effects toward DCF treatment were observed, with the latter being brought forward by higher wt.% rGO. The composite with 5.0 wt.% rGO has shown the highest DCF conversion at pH 4 compared to that obtained by pristine TiO2, despite lower DCF adsorption during the initial dark period. The expected positive effects of both sulfur doping and rGO on charge recombination were found to be limited because of the subpar interphase contact with the composite and incomplete reduction of the GO precursor. Consequent unfavorable interactions between rGO and DCF negatively influenced the activity of the studied S-TiO2/rGO photocatalyst under simulated solar irradiation

Self-cleaning and photoactive TiO2 – ZrO2 – SiO2 films on thermosensitive and glass substrates

Nanosized TiO2 is well-known for its photocatalytic property. From the combination of photocatalysis and photoinduced hydrophilicity properties, thin films of this material have also anti-fogging, self-cleaning and antimicrobial properties. There are numerous deposition techniques e.g. spin-coating, dip-coating, spraying, the most suitable one is chosen based on substrate or solution characteristics. Thin films are often required to be transparent for visible light, especially if we use them on transparent substrates, or they should not affect the color of the substrate. Radicals that are produced during photosensitizing process are able to destroy structure of a substrate and substrate can lose mechanical stability [1,2]. Some studies show that adding a SiO2 protective layer can prevent the damage of the substrate [3–5]. Ti-Zr containing sols were prepared with sol-gel process, where titanium(IV) isopropoxide, zirconium(IV) butoxide and ethanol were hydrolyzed with aqueous solution of perchloric acid. Solution was then refluxed for 48 hours. During that time crystallization and deaggregation took place and that resulted in a stable final solution [6]. To prepare suitable solution for production of durable films silica binder was added. On glass and plastic substrates, thin films were deposited with the dip-coating method and dried with a heat-gun. Thin films were characterized by measurements of photocatalytic activity with terephthalic acid as model organic pollutant subjected to oxidation via fluorescent degradation product, photoinduced superhydrophilicity phenomena, UV-Vis and ATR-FTIR spectroscopy, SEM images, as well as mechanical properties measurements. References [1] H. Schmidt, M. Naumann, T.S. Müller, M. Akarsu, Thin Solid Films (2006) 502, 132– 137. [2] W. A. Daoud, J.H. Xin, Y.H. Zhang, Surf. Sci. (2005) 599, 69–75. [3] Ž. Senić, S. Bauk, M. Vitorović-Todorović, N. Pajić, A. Samolov, D. Rajić, Sci. Tech. Rev. (2011) 61, 63–72. [4] T. Yuranova, R. Mosteo, J. Bandara, D. Laub, J. Kiwi, J. Mol. Catal. A: Chem. (2006) 244, 160–167. [5] T. Yuranova, D. Laub, J. Kiwi, Catal. Today (2007) 122, 109–117. [6] N. Vodišek, K. Ramanujachary, V. Brezová, U. Lavrenčič Štangar, Catal. Today (2017) 287, 142–147

Efficient mineralization of aqueous organic pollutants by photocatalytic ozonation

Photocatalytic ozonation process using TiO2 photocatalyst (O3/TiO2/UV – PH-OZ) conducted in acidic water environment often leads to synergistic effect in terms of decomposition and mineralization of aqueous organic contaminants, which makes the process suitable for waste water treatment or pretreatment of drinking water. [1,2] The synergism is among other factors (pH, O3 dose, T,…) greatly influenced by photocatalyst physicochemical properties and pollutant type. In the first part of the study, five different commercial TiO2 photocatalysts (P25, PC500, PC100, PC10 and JRC-TiO-6) were used in O2/TiO2/UV, O3/TiO2 and O3/TiO2/UV advanced oxidation systems for degradation of two pollutants (dichloroacetic acid - DCAA and thiacloprid – neonicotinoid pesticide), simultaneously present in water solution. [3] Results of PH-OZ (O3/TiO2/UV) experiments showed that in contrast to DCAA which adsorbs on TiO2 surface, synergistic effect is much more expressed in the case of thiacloprid which doesn’t adsorb. The influence of BET surface area of the photocatalyst and its dispersivity will be discussed. In the second part of this study, selected catalysts were immobilized on a proper support to avoid post-filtration step in the process of greywater treatment. A good adhesion of a catalyst on various supports was successfully achieved by immobilization of commercial TiO2 powders (P25, P90, PC500) with the help of a sol-gel silica-titania binder [4]. For the purpose of simulated greywater treatment, special compact reactor was designed and developed, utilizing Al2O3 porous reticulated monolith foams as TiO2 carriers and UVA-lamps inside (Fig. 1). [5] With degradation of LAS+PBIS and Reactive blue 19 (RB 19) as representatives of surfactants and textile dyes respectively, commonly found in household greywater, and phenol as trace contaminant, an evaluation of PH-OZ and photocatalytic oxidation has been performed (an example in Fig. 2). Synergistic effect of PH-OZ was generally much more expressed in mineralization reactions, showing TOC half lives of less than one hour for the mixture of pollutants in compact reactor. [5] Due to its superior cleaning capacity, PH-OZ process employing efficient photocatalysts is suitable for treating wastewaters also with higher loading of organic pollutants. 1. U. Černigoj, U.Lavrenčič Štangar, J. Jirkovsky, J. Hazard. Mater. (2010) 177:399–406. 2. U. Černigoj, U.Lavrenčič Štangar, P. Trebše, Appl. Catal. B Environ. (2007) 75:229–238. 3. M. Kete, U. Černigoj, U. Lavrenčič Štangar: Photocatalytic ozonation – study of reaction parameters and mechanism, article under submission 4. M. Kete, E. Pavlica, F. Fresno, G. Bratina, U. Lavrenčič Štangar, Environ. Sci. Pollut. Res. (2014) 21:11238–11249. 5. M. Kete: Towards efficient removal of contaminants in water from household appliances by TiO2-photocatalysis: design, optimization and performance studies of the photoreactor with immobilized catalysts, Doctoral dissertation (2015), University of Nova Gorica, Nova Gorica