A novel environmentally friendly method for
in situ
formation of CaCO
3
deep inside a wood's structure is presented. The method is based on vacuum-pressure impregnation using a one-component ...treatment medium - a water solution of calcium acetoacetate - and a single stage process to significantly improve the fire retardancy of the treated material.
In order to improve the fire retardancy of wood the eco-friendly method for
in situ
formation of CaCO
3
deep inside the wood's structure was proposed by the vacuum-pressure impregnation of only one component - water solution of calcium acetoacetate.
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•TiO2 encapsulated in mesoporous silica exhibits selective photocatalytic degradation of low-molecular-weight molecules.•Core@shell photocatalyst degrades rhodamine B in presence of ...fivefold mass concentration of starch, while pure TiO2 does not.•Potential use for removing water pollutants, while retaining non-harmful and beneficial macromolecules.
Photocatalytic TiO2 degrades organic matter unselectively. However, in certain applications, such as degradation of pollutants, selectivity towards pollutants is beneficial. We synthesized core@shell TiO2@SiO2 nanoparticles with photocatalytic activity featuring a significantly faster preferential degradation of model pollutant (rhodamine B) in presence of abundant concentration of natural organic matter compared to pure TiO2 (P25). The material’s photocatalytic activity was tested in aqueous medium. The selectivity of prepared effect of core@shell materials is explained based on transmission electron microscopy, nitrogen adsorption, X-ray powder diffraction and zeta potential measurements.
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Bronze surfaces, whether bare or patinated, tend to change when exposed to an outdoor atmosphere. Art made of bronze which is exposed to the outdoors is usually artificially patinated. This patina ...changes when exposed to rain, especially in polluted rain, where sulphuric, nitric or carbonic acids are present.
In order to gain optimal protection of different patinas and consequently reduce the patina changes over the time different protection systems were developed, tested and tailored. Three types of patina (brown, green sulphate, and green persulphate) were prepared, protected and subsequently studied. The protections were based on two coatings (i) fluoropolymer based coating (FA-MS) and (ii) newly developed fluoropolymer based coating with addition of mercaptopropyl groups, named as alternative fluoropolymer coating (FA-MS-SH). Both the pure patinas applied on bronze surfaces as well as the bare bronze were electrochemically tested, first unprotected and then following the application of two different types of protection. After the protection was applied to the patinas, the change in colour was defined. Different techniques were utilised in order to define the morphology and structure of the patinas, as well as the change in colour following application of the coating. It was shown that a fluoropolymer coating (FA-MS) provided the most efficient protection to bare bronze and the sulphate patina, while a newly proposed alternative fluoropolymer coating (FA-MS-SH) offered good protection to bare and brown patinated bronze. A mechanism for the protection of bare and patinated bronze was suggested.
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•Coatings for artificial patinas for outdoor application were developed.•Two fluoropolymer coatings FA-MS and FA-MS-SH were evaluated.•Brown sulphide, green sulphate and persulphate patinas were protected.•FA-MS coating efficiently protected bare and persulphate patinated bronze.•FA-MS-SH protection was efficient for brown and sulphate patina.
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GEOZS, IJS, IMTLJ, KILJ, KISLJ, NLZOH, NUK, OILJ, PNG, SAZU, SBCE, SBJE, UILJ, UL, UM, UPCLJ, UPUK, ZAGLJ, ZRSKP
In order to expand the use of titania indoor as well as to increase its overall performance, narrowing the band gap is one of the possibilities to achieve this. Modifying with rare earths (REs) has ...been relatively unexplored, especially the modification of rutile with rare earth cations. The aim of this study was to find the influence of the modification of TiO₂ with rare earths on its structural, optical, morphological, and photocatalytic properties. Titania was synthesized using TiOSO₄ as the source of titanium via hydrothermal synthesis procedure at low temperature (200 °C) and modified with selected rare earth elements, namely, Ce, La, and Gd. Structural properties of samples were determined by X-ray powder diffraction (XRD), and the phase ratio was calculated using the Rietveld method. Optical properties were analyzed by ultraviolet and visible light (UV-Vis) spectroscopy. Field emission scanning electron microscope (FE-SEM) was used to determine the morphological properties of samples and to estimate the size of primary crystals. X-ray photoelectron spectroscopy (XPS) was used to determine the chemical bonding properties of samples. Photocatalytic activity of the prepared photocatalysts as well as the titania available on the market (P25) was measured in three different setups, assessing volatile organic compound (VOC) degradation, NO
abatement, and water purification. It was found out that modification with rare earth elements slows down the transformation of anatase and brookite to rutile. Whereas the unmodified sample was composed of only rutile, La- and Gd-modified samples contained anatase and rutile, and Ce-modified samples consisted of anatase, brookite, and rutile. Modification with rare earth metals has turned out to be detrimental to photocatalytic activity. In all cases, pure TiO₂ outperformed the modified samples. Cerium-modified TiO₂ was the least active sample, despite having a light absorption tail up to 585 nm wavelength. La- and Gd-modified samples did not show a significant shift in light absorption when compared to the pure TiO₂ sample. The reason for the lower activity of modified samples was attributed to a greater Ti
/Ti
ratio and a large amount of hydroxyl oxygen found in pure TiO₂. All the modified samples had a smaller Ti
/Ti
ratio and less hydroxyl oxygen.
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•The mechanisms of calcium acetoacetate transformations into CaCO3 was proposed.•Strong influence of relative humidity on CaCO3 polymorph formation has been shown.•The formed crystal ...structure is found to be vaterite.•The amorphous CaCO3 appears to be very stable at lower values of relative humidity.
Calcium acetoacetate, Ca(OAcAc)2, was exposed 7, 30 and 365 days to different values of relative humidity (33%, 48%, 75% and 96%) at 40 °C in order to study its transformation to CaCO3. The resulting Ca(OAcAc)2 decomposition and the time dependence of the phase transformations were monitored and critically evaluated by Fourier transform infrared spectroscopy, field emission scanning electron microscopy and X-ray powder diffraction. The impact of relative humidity on CaCO3 polymorph formation was thoroughly assessed. In all of the conditions used and for all ageing periods, the formed crystal structure is found to be vaterite. At the lowest relative humidity (33%), the amorphous CaCO3 remains more or less almost untransformed even after one year of exposure. It is proposed that the reason for the stability of amorphous CaCO3 is due to the limited amount of physisorbed water on the surfaces of the particles, which is considered the driving force for its transformation. However, the carbonation process is faster in the case of the highest humidity (96%). The findings are not only important for better solutions in the field of cultural heritage, but also shed new light on the fundamental mechanism of CaCO3 crystallization.
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GEOZS, IJS, IMTLJ, KILJ, KISLJ, NLZOH, NUK, OILJ, PNG, SAZU, SBCE, SBJE, UILJ, UL, UM, UPCLJ, UPUK, ZAGLJ, ZRSKP
The development of non-biocidal and environmentally friendly systems to protect wood against biological decay has become a high priority in recent years. In the present study the impact of an ...innovative modification procedure, combining two environmentally friendly modification methods: thermal modification and mineralisation, using an aqueous solution of calcium acetoacetate as a precursor, on the fungal durability of wood was evaluated. European beechwood (Fagus sylvatica) and Norway sprucewood (Picea abies) were selected as model wood species. Wood samples were treated using either a single or combination of both methods and exposed to four different fungi: Gloeophyllum trabeum, Rhodonia placenta, Trametes versicolor and Pleurotus ostreatus. The effect of the different modifications on moisture content, dynamic vapour sorption, contact angle and pH value was also evaluated. Overall, the highest durability against Rhodonia placenta, Trametes versicolor and Pleurotus ostreatus was achieved through thermal modification in both wood species, while the combination of mineralisation and thermal modification has a synergistic effect against degradation by Gloeophyllum trabeum. In the case of beechwood the mass loss decreased from 41% for native to 6% for combined modified samples. We proved that the effectiveness of different treatment against fungal decay of wood were in strong dependence of their moisture content, dynamic vapour sorption, contact angle and pH values. The role of fungi on the morphology of the wood and on crystal structure of formed carbonate was investigated using SEM-EDS analysis.
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•Presented ecological modification of wood can be an alternative to biocides.•A significant improvement in the fungal durability of wood was achieved.•Thermal modification and mineralisation work synergistic against wood decay fungi.•The reasons for a synergistic effect of combining methods were proposed.•The mass loss decreased from 41% for native to 6% for combined modified beechwood.
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The photocatalytic properties of TiO2 are primarily determined by its crystallinity and crystalline phase ratios. To improve the photocatalytic properties of TiO2, greater control over the formation ...of crystalline and amorphous phases during synthesis is therefore required. In this study, we demonstrate how the addition of minute amounts of three organic compounds (isopropanol, acetone and acetic acid) during hydrothermal treatment affects the amorphous and crystalline phase ratios: the addition of isopropanol or acetone accelerates the phase transition from anatase and brookite to rutile, whereas the addition of acetic acid inhibits the transformation of anatase to rutile, increasing the content of amorphous phase compared to samples where no organic compound was added. We show that the combination of the organic compound added, along with the duration of the hydrothermal treatment, can be used to tailor the phase composition of TiO2, so as to obtain either: i) TiO2 with a high content of both rutile and amorphous phase, ii) TiO2 with a high rutile content and iii) TiO2 with different ratios of all four phases, when the duration of synthesis is short (2–4 h). The materials synthesized exhibited high photocatalytic activity (in most cases higher than P25), which is attributed to the beneficial phase composition and high specific surface area.
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GEOZS, IJS, IMTLJ, KILJ, KISLJ, NLZOH, NUK, OILJ, PNG, SAZU, SBCE, SBJE, UILJ, UL, UM, UPCLJ, UPUK, ZAGLJ, ZRSKP
Cellulose acetate is used in many applications, including for cigarette filters. Unfortunately, unlike cellulose, its (bio)degradability is under question, yet it often ends up uncontrolled in the ...natural environment. The main purpose of this study is to compare the effects of weathering on two types of cigarette filter (classic filters and newer filters that have more recently arrived on the market) following their use and disposal in nature. Microplastics were prepared from polymer parts of used (classic and heated tobacco products-HTP) cigarettes and artificially aged. TG/DTA, FTIR, and SEM analyses were performed both before and after the aging process. Newer tobacco products contain an additional film made of a poly(lactic acid) polymer which, like cellulose acetate, burdens the environment and poses a risk to the ecosystem. Numerous studies have been conducted on the disposal and recycling of cigarette butts and cigarette butt extracts, revealing alarming data that have also influenced the decisions of the EU, who addressed the disposal of tobacco products in the EU Directive (EU) 2019/904. Despite this, there is still no systematic analysis in the literature evaluating the impact of weathering (i.e., accelerated aging) on the degradation of cellulose acetate in classic cigarettes compared with that in newer tobacco products that have recently appeared on the market. This is of particular interest given that the latter have been promoted as being healthier and environmentally friendly. The results show that in cellulose acetate cigarette filters the particle size decreased after accelerated aging. Also, the thermal analysis revealed differences in the behavior of the aged samples, while the FTIR spectra showed no shifts in the position of the peaks. Organic substances break down under UV light, which can be seen by measuring the color change. The PLA film was found to be more stable than cellulose acetate under the influence of UV light.
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Waxes and wax emulsions are one of the most important solutions for non-biocidal wood protection. Wax treated wood is designed for outdoor use, therefore it is of considerable importance to elucidate ...the influence of weathering on the photodegradation processes. It is presumed, that wax treatment will reduce water uptake and thus reduce or slow down photodegradation processes. In order to test this hypothesis, three types of wax emulsions at two different concentrations were vacuum impregnated into Norway spruce wood specimens: an emulsion of montan wax (LGE), an emulsion of polyethylene (WE1) and an emulsion of oxidized polyethylene (WE6) wax. The samples were exposed to artificial accelerated weathering (AAW) for 500 cycles. Before and after AAW colour, the contact angle of water and moisture content were determined. Chemical and morphological changes at exposed surfaces were also investigated with FTIR spectroscopy and SEM. In parallel, the uptake of wax emulsions and water into the axial surfaces of samples was determined with a tensiometer. The moisture content measurements showed that the best hydrophobic effect was achieved with LGE treated wood, where the lowest colour and FTIR changes were observed as well. These results were supported by tensiometer measurements as well. Presented data clearly showed that high loadings of waxes reduce or at least slow down weathering. Among tested waxes, montan wax was found the most effective.
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GEOZS, IJS, IMTLJ, KILJ, KISLJ, NUK, OILJ, PNG, SAZU, SBCE, SBJE, UL, UM, UPCLJ, UPUK
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