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Organically modified clays (organoclays) have been considered effective adsorbents for the treatment of per- and polyfluoroalkyl substances (PFAS). However, the stability of organoclays prepared through the conventional cation exchange approach has been a major concern for their practical application. In this study, we reported the development of a new organically functionalized clay by grafting pillared clay substrate with an organosilane through covalent bonding. The performance of the silylated clay (QAG-ZrMT) was systematically compared with an organoclay prepared from ion exchange (HDTMA-ZrMT) for the adsorption of two legacy perfluoroalkyl acids: perfluorooctanoic acid (PFOA) and perfluorooctanesulfonic acid (PFOS), and two precursor compounds 5:3 fluorotelomer carboxylic acid (5:3FTCA) and 6:2 fluorotelomer sulfonic acid (6:2FTS). Compared to HDTMA-ZrMT, QAG-ZrMT showed substantially improved performance for adsorption of less hydrophobic PFAS (e.g., 5:3FTCA), which could be related to the stronger electrostatic interactions between PFAS and QAG-ZrMT than HDTMA-ZrMT. More importantly, QAG-ZrMT could be conveniently regenerated and reused for multiple cycles with robust performance. In contrast, HDTMA-ZrMT almost completely lost its capacity for PFAS removal after regeneration, due to the loss of organic functional groups during solvent regeneration. Results can shed light on the design of efficient and regenerable organoclay adsorbents for remediation of PFAS-contaminated water matrices., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

This study focuses on polyamide 6/organo-modified montmorillonite (PA6/OMMT) nanocomposites as potential liner materials, given the growing interest in enhancing the performance of type IV composite overwrapped hydrogen storage pressure vessels. The mechanical properties of PA6/OMMT composites with varying filler concentrations were investigated across a temperature range relevant to hydrogen storage conditions (-40 °C to +85 °C). Liner collapse, a critical issue caused by rapid gas discharge, was analyzed using an Ishikawa diagram to identify external and internal factors. Mechanical testing revealed that higher OMMT content generally increased stiffness, especially at elevated temperatures. The Young's modulus and first yield strength exhibited non-linear temperature dependencies, with 1 wt. per cent OMMT content enhancing yield strength at all tested temperatures. Dynamic mechanical analysis (DMA) indicated that OMMT improves the storage modulus, suggesting effective filler dispersion, but it also reduces the toughness and heat resistance, as evidenced by lower glass transition temperatures. This study underscores the importance of optimizing OMMT content to balance mechanical performance and thermal stability for the practical application of PA6/OMMT nanocomposites in hydrogen storage pressure vessels.

Biochars and organoclays have been proposed as efficient adsorbents to reduce the mobility of agrochemicals in soils. However, following their application to soils, these adsorbents undergo changes in their physicochemical properties over time due to their interaction with soil components. In this study, the adsorption capacity of a commercial biochar and a commercial organoclay for the antibiotic sulfamethoxazole (SFMX) and the pesticide ethofumesate (ETFM) was evaluated over aging periods of 3 months in the laboratory and 1 year in the field, subsequent to their application to a Mediterranean soil. The results showed that the adsorption of SFMX and ETFM in the soil amended with the adsorbents was greater than in the unamended soil, but for both chemicals, adsorption decreased with aging of the adsorbents in the soil. Characterization of the adsorbents before and after aging revealed physical blocking of adsorption sites by soil components. The loss of adsorption capacity of the adsorbents upon aging led to higher leaching of SFMX and ETFM in the soil containing field-aged adsorbents, although leaching remained lower than in unamended soil. Our findings reveal that, under the Mediterranean environment studied, the efficacy of the studied materials as adsorbents is maintained to a considerable extent for at least one year after their field application, which would have positive implications in their use for attenuating the dispersion of agricultural contaminants in the environment., Competing Interests: Declaration of competing interest The authors declare the following financial interests/personal relationships which may be considered as potential competing interests: Rafael Celis & Lucia Cox reports financial support was provided by Spain Ministry of Science and Innovation. Rafael Celis reports financial support was provided by Government of Andalusia. If there are other authors, they declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Authors. Published by Elsevier B.V. All rights reserved.)

Combination of organoclay sorption with manganese(IV) oxide (MnO 2 ) catalyzed catechol oxidation was studied for the removal of a dicarboximide fungicide, iprodione, from water. Iprodion in water was sorbed on didodecyldimethylammonium bromide (DDAB)-modified montmorillonite (MT) organoclay and converted into the degraded product, 3,5-dichloroaniline (DCA). The degree of sorption increased by the modification with DDAB, because of the formation of a hydrophobic region for the incorporation of iprodione and negligibly interfered by coexisting MnO 2 . The half-life for the degradation of irodione in water at 25 °C was 7 days, whreas it reduced to 15 min in the organoclay. The activation energy, 65.4 ± 4.8 kJ mol -1 , for the first-order reaction in the aqueous solution (pH 7.0) decreased to 43.9 ± 1.8 kJ mol -1 in the organoclay, indicating the catalytic activity of the organoclay that accelerates the hydrolysis reaction of iprodione. In the coexistence of appropriate amounts of MnO 2 and catechol, the degraded product, DCA, reacted with oxidized products of catechol to form a water-insoluble precipitate and was successfully eliminated from water. The results obtained in the present study strongly suggest the applicability of the combined method of organoclay sorption method and MnO 2 -catalyzed oxidation for the diffusion control of toxic agrochemicals., (© 2024. The Author(s), under exclusive licence to The Japan Society for Analytical Chemistry.)

Pultruded fiber reinforced polymer composites used in civil, power, and offshore/marine applications use fillers as resin extenders and for process efficiency. Although the primary use of fillers is in the form of an extender and processing aid, the appropriate selection of filler can result in enhancing mechanical performance characteristics, durability, and multifunctionality. This is of special interest in structural and high voltage applications where the previous use of specific fillers has been at levels that are too low to provide these enhancements. This study investigates the use of montmorillonite organoclay fillers of three different particle sizes as substitutes for conventional CaCO 3 fillers with the intent of enhancing mechanical performance and hygrothermal durability. The study investigates moisture uptake and kinetics and reveals that uptake is well described by a two-stage process that incorporates both a diffusion dominated initial phase and a second slower phase representing relaxation and deterioration. The incorporation of the organoclay particles substantially decreases uptake levels in comparison to the use of CaCO 3 fillers while also enhancing stage I, diffusion, dominated stability, with the use of the 1.5 mm organoclay fillers showing as much as a 41.5% reduction in peak uptake as compared to the CaCO 3 fillers at the same 20% loading level (by weight of resin). The mechanical performance was characterized using tension, flexure, and short beam shear tests. The organoclay fillers showed a significant improvement in each, albeit with differences due to particle size. Overall, the best performance after exposure to four different temperatures of immersion in deionized water was shown by the 4.8 mm organoclay filler-based E-glass/vinylester composite system, which was the only one to have less than a 50% deterioration over all characteristics after immersion for a year in deionized water at the highest temperature investigated (70 °C). The fillers not only enhance resistance to uptake but also increase tortuosity in the path, thereby decreasing the overall effect of uptake. The observations demonstrate that the use of the exfoliated organoclay particles with intercalation, which have been previously used in very low amounts, and which are known to be beneficial in relation to enhanced thermal stability, flame retardancy, and decreased flammability, provide enhanced mechanical characteristics, decreased moisture uptake, and increased hygrothermal durability when used at particle loading levels comparable to those of conventional fillers, suggesting that these novel systems could be considered for critical structural applications.

The aim of this work was to synthesize and study the functional properties of polymer-clay nanocomposite (PCNCs) based on poly(sodium 4-styrene sulfonate) (NaPSS) and two types of clay in the dispersed phase: bentonite and kaolinite, in order to advance in the development of new geomimetic materials for agricultural and environmental applications. In this study, the effect of adding high concentrations of clay (10-20 wt. %) on the structural and functional properties of a polymer-clay nanocomposite was evaluated. The characterization by infrared spectroscopy made it possible to show that the PCNCs had a hybrid nature structure through the identification of typical vibration bands of the clay matrix and NaPSS. In addition, scanning electron microscopy allowed us to verify its hybrid composition and an amorphous particle-like morphology. The thermal characterization showed degradation temperatures higher than ~300 °C with Tg values higher than 100 °C and variables depending on the clay contents. In addition, the PCNCs showed a high water-retention capacity (>2900%) and cation exchange capacity (>112 meq/100 g). Finally, the results demonstrated the ability of geomimetic conditioners to mimic the structure and functional properties of soils, suggesting their potential application in improving soil quality for plant growth.

Polymer clay nanocomposites, which can exhibit many superior properties compared to virgin polymers, have gained increasing interest and importance in recent years. This study aimed to prepare composites of two organoclays with unusual ratios and different degrees of lyophilicity with low-density polyethylene and compare their textural structures and thermal and mechanical properties with those of virgin polymer. For this purpose, firstly, organoclays, hydrophobic and superhydrophobic organoclays (OC and SOC), were prepared by solution intercalation method using cetyltrimethylammonium bromide with and without addition of a hydrocarbon substance. Then, using both organoclays, polyethylene organoclay composites were prepared and characterized using X-ray powder diffraction (XRD), high-resolution transmission electron microscopy (HRTEM) and Fourier transform infrared spectroscopy (FTIR) techniques. Additionally, tensile and hardness tests were performed to determine the mechanical properties of the composites, and differential scanning calorimetry (DSC) thermograms were taken to examine their thermal behavior. XRD patterns and HRTEM images of hydrophobic and superhydrophobic organoclays and the composites show that the characteristic smectite peak of the clay shifts to the left and expands, that is, the interlayer space widens and, in the composites, it deforms immediately at low clay ratios. HRTEM images of the composites prepared especially with low clay ratios indicate that a heterogeneous dispersion of clay platelets occurs, indicating that nanocomposite formation has been achieved. On the contrary, in the composites prepared with high clay ratios, this dispersion behavior partially turns into aggregation. In the composites prepared using up to 20% by weight of superhydrophobic organoclay, extremely stable and continuous improvements in all mechanical properties were observed compared to those of the composites prepared using hydrophobic organoclay. This indicates that by using superhydrophobic organoclay, a ductile nanocomposite of polyethylene containing inorganic components in much higher than usual proportions can be prepared.

There is an urgent need for developing eco-friendly adsorbents for dye wastewater treatment with high efficiency and low cost. Meanwhile, organoclay has received an increasing attention as a natural adsorbent for dye removal. However, no comprehensive investigation has been conducted to evaluate the feasibility of this approach in terms of operation cost and removal efficiency. In this research, we intend to answer this question: could organoclay be used as an efficient and cost-effective approach for dye wastewater treatment? In line with that, after characterization of the Na-bentonite and modified clay by using SEM, EDX, FTIR and XRD, the performance of the organoclay was optimized in terms of AO7 dye removal efficiency and adsorption cost using response surface methods (RSM). Then, the organoclay performance was compared with other typical adsorbents activated carbon and chitosan. The characterization results proved that Na-bentonite was successfully modified by CTAB. According to RSM results, the maximum dye removal of 95% and the minimum adsorption cost of 0.009 $/g were achieved under optimum conditions of: pH: 5, AO7 concentration: 56 mg/L, contact time: 53 min and organoclay dosage: 0.8 g/L. While, in the case of other adsorbents of Na-bentonite, chitosan and activated carbon the maximum removal of 11%, 84% and 92% were achieved with 0.0136, 0.0324 and 0.1011 $/g, respectively. The adsorption kinetics and isotherms analyses revealed that the experimental data fitted well with the pseudo-second-order (R 2  = 0.993) and Langmuir (R 2  = 0.988). This study proved that organoclay can be used as a promising adsorbent for dye removal with low cost and high removal efficiency., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Ltd. All rights reserved.)

Herein, a highly porous bimetal-organic framework (bi-MOF) based on cobalt and nickel was successfully in situ grown on organoclay (OC) clusters by solvothermal method. Accordingly, the hierarchical porous CoNi-MOF/OC composite with a superior specific surface area of 2046 m 2 /g and a large pore volume of 0.763 cm 3 /g was obtained, which facilitated the adsorption of organic dyes. A morphological study using scanning electron microscopy indicated the formation of uniform bi-MOF crystals on the OC plates. Furthermore, the single- and multi-dye adsorption assays were implemented to precisely evaluate the adsorption capacity and selectivity of CoNi-MOF/OC composite to anionic and cationic dyes. The results revealed a high adsorption capacity of 58.61 mg/g at an adsorbent content of 15 mg, initial dye concentration of 20 ppm, and contact time of 25 min for MB, which is superior to several existing clay-based adsorbents. The adsorption kinetics study showed that the adsorption of cationic and anionic dyes onto the CoNi-MOF/OC composite followed the pseudo-second-order kinetic model. Interestingly, the regeneration study showed appropriate reusability and stability of the CoNi-MOF/OC composite for the removal of organic dyes with an almost unchanged structure after four regeneration cycles. The results of this study provide new insights for the rational design and fabrication of next-generation clay-based adsorbent by combining the synergistic advantages of bi-MOF with superior specific surface area and pore volume with organoclay composition and structure., (© 2023. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

TiO 2 /montmorillonite composites were synthesized using inverse micellar route for the preparation of titania nanoparticles (4-6 nm diameter) in 1-hexanol and for the dispersion of one of the clay components. Two series of composites were obtained: one derived from cetyltrimethylammonium organomontmorillonite (CTA-Mt), exfoliated in 1-hexanol, and the other from sodium form of montmorillonite (Na-Mt) dispersed by formation of an inverse microemulsion in 1-hexanol. The TiO 2 content ranged from 16 to 64 wt.%. The composites were characterized with X-ray diffraction, scanning/transmission electron microscopy/energy dispersive X-ray spectroscopy, thermal analysis, and N 2 adsorption-desorption isotherms. The Na-Mt-derived component was shown to undergo transformation to CTA-Mt, as indicated by basal spacing of 17.5 nm, due to the interaction with the CTABr surfactant in inverse microemulsion. It was also better dispersed and intermixed with TiO 2 nanoparticles. As a result, the TiO 2 /Na-Mt series displayed superior textural properties, with specific surface area up to 256 m 2 g -1 and pore volume up to 0.247 cm 3 g -1 compared with 208 m 2 g -1 and 0.231 cm 3 g -1 , respectively, for the TiO 2 /CTA-Mt counterpart. Members of both series were uniformly mesoporous, with the dominant pore size around 5 nm, i.e., comparable with the dimensions of titania nanoparticles. The advantage of the adopted synthesis method is discussed in the context of other preparative procedures used for manufacturing of titania-clay composites.

The paper provides an overview of biocosmetics, which has tremendous potential for growth and is attracting huge business opportunities. It emphasizes the immediate need to replace conventional fossil-based ingredients in cosmetics with natural, safe, and effective ingredients. It assembles recent technologies viable in the production/extraction of the bioactive ingredient, product development, and formulation processes, its rapid and smooth delivery to the target site, and fosters bio-based cosmetic packaging. It further explores industries that can be a trailblazer in supplying raw material for extraction of bio-based ingredients for cosmetics, creating biodegradable packaging, or weaving innovation in fashion clothing. Lastly, the paper discusses what it takes to become the first generation of a circular economy and supports the implementation of strict regulatory guidelines for any cosmetic sold globally., (© 2021. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

In this original research, biodegradable corn starch (CS) and wheat gluten (wg)-based silver nanofilms were synthesized and analyzed by using goji berry extract taurine (ta), garlic extract (GC), whey powder (wh), and montmorillonite clay nanoparticles. Antibacterial-corn-starch-based nano films were analyzed by using the methods of high-performance liquid chromatography (HPLC), Fourier Transform infrared spectroscopy (FTIR-ATR), X-ray diffraction (XRD), dynamic and mechanical (DMA) analysis, and scanning electron microscopy (SEM). In addition, the antibacterial resistances of the corn starch nano films against the bacteria Salmonella and Staphylococcus aureus ( S. aureus ) and Listeria monocytogenes were examined and the migration assays were carried out. The migration analysis results of CS 1 , CS 2 , and CS 3 nanocomposite films were found as 0.305, 0.297, and 0.297 mg/dm 2 , respectively. The inhibition zone of CS 1 , CS 2 , and CS 3 nanocomposite films were found as 1547, 386, and 1884 mm 2 against Salmonella bacteria. The results show that silver nanofilms are suitable as packaging films for the production of packaging in milk and dairy products, liquid foods, and acidic foods.

Water pollution by toxic organic dyes is one of the most critical health and environmental problems worldwide. By means of molecular dynamics method, the present work aims to evaluate the applicability of montmorillonite (Mt) modified by hexadecyltrimethylammonium cations (HDTMA + ) compared to unmodified Na-Mt for the adsorption of cationic methylene blue (MB) dye. The results showed that the adsorption energy of MB on both HDTMA-Mt and Na-Mt absorbent ranged from - 100 to - 250 kJ/mol, indicating the effectiveness of two types of adsorbents in dye water treatment. The highest adsorption energy was found at w = 50% in each adsorbent system. Adsorption mechanisms of MB depend on molecular orientations, which is influenced by the surfactant and water content. The adsorption mechanism of MB is chemisorption dominated by strong electrostatic interaction between CH 3 groups of MB and oxygen atoms of Mt surfaces. Besides, physisorption also plays a minor role in MB orientations. It is found that the existence of cationic surfactants can slightly improve the adsorption capacity of MB only at higher water content through enlarging the interlayer space of Mt and reducing mobility of MB. However, there will be a negative impact on the reduction of adsorption sites for dyes especially at low water content. Our results provide a possible application for swelling clay minerals being a promising adsorbent for dyes-surfactants co-existing wastewater treatment., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 Elsevier B.V. All rights reserved.)

This paper presents the influence of the presence of a modified organoclay, Cloisite ® 20A (MMTA) on the structural and drug release properties of ureasil organic-inorganic hybrid. Sol-gel process was used to prepare the hybrid nanocomposites containing sodium diclofenac (DCF) at 5% wt. The effect of the amount of MMTA incorporated into the ureasil hybrid matrix was evaluated and characterized in depth by different techniques such as X-ray diffraction (XRD), small angle X-ray scattering (SAXS), differential scanning calorimetry (DSC), and swelling properties. The influence of MMTA on ureasil nanocomposites release profile was evaluated by in situ UV-vis. The diffraction patterns of the UPEO-MMTA nanocomposites showed a synergistic contribution effect that led to an intensity increase and narrowed the diffraction peaks, evidencing a crystallite PEO growth as a function of the modified nanoclay content. The interactions between polyether chains and the hydrogenated tallow of MMTA led to an easy intercalation process, as observed in UPEO-MMTA nanocomposites containing low (1% wt) or high (20% wt) nanoclay content. The waterway (channels) created in UPEO-MMTA nanocomposites contributed to a free volume increase in the swollen network compared to UPEO without MMTA. The hypothesis of the channels created after intercalation of the PEO phase in the interlayer of MMTA containing organoammonium ions corroborates with the XRD results, swelling studies by SAXS, and release assays. Furthermore, when these clay particles were dispersed in the polymeric matrix by an intercalation process, water uptake improvement was observed, with an increased amount of DCF release. The design of ureasil-MMTA nanocomposites containing modified nanoclay endows them with tunable properties; for example, swelling degree followed by amount of controlled drug release, opening the way for more versatile biomedical applications.

Linseed oil-based composite films were prepared with cinnamaldehyde (Cin) using a modified clay (organoclay) through in situ polymerization, which is the result of the interaction between Cin and organoclay. The incorporation of organoclay reduces the polymer chain's mobility and, therefore, increases the thermal stability of the composite films. In some experimental conditions, the clay is located both inside and on the surface of the film, thus, affecting the mechanical and thermal properties as well as the surface properties of the composite films. The incorporation of organoclay decreases the water contact angle of the composite film by more than 15%, whatever the amount of cinnamaldehyde. However, the incorporation of cinnamaldehyde has the opposite effect on film surface properties. Indeed, for the water vapor permeability (WVP), the effect of cinnamaldehyde on the film barrier properties is much higher in the presence of organoclay. The incorporation of hydrophobic compounds into the polymer films reduces the water content, which acts as a plasticizer and, therefore, decreases the WVP by more than 17%. Linseed oil has a natural antioxidant activity (~97%) due to the higher content of unsaturated fatty acids, and this activity increased with the amount of organoclay and cinnamaldehyde.

This article proposes a foaming method using supercritical carbon dioxide (scCO 2 ) to obtain compostable bionanocomposite foams based on PLA and organoclay (C30B) where this bionanocomposite was fabricated by a previous hot melt extrusion step. Neat PLA films and PLA/C30B films (1, 2, and 3 wt.%) were obtained by using a melt extrusion process followed by a film forming process obtaining films with thicknesses between 500 and 600 μm. Films were further processed into foams in a high-pressure cell with scCO 2 under constant conditions of pressure (25 MPa) and temperature (130 °C) for 30 min. Bionanocomposite PLA foams evidenced a closed cell and uniform cell structure; however, neat PLA presented a poor cell structure and thick cell walls. The thermal stability was significantly enhanced in the bionanocomposite foam samples by the good dispersion of nanoclays due to scCO 2 , as demonstrated by X-ray diffraction analysis. The bionanocomposite foams showed improved overall mechanical performance due to well-dispersed nanoclays promoting increased interfacial adhesion with the polymeric matrix. The water uptake behavior of bionanocomposite foams showed that they practically did not absorb water during the first week of immersion in water. Finally, PLA foams were disintegrated under standard composting conditions at higher rates than PLA films, showing their sustainable character. Thus, PLA bionanocomposite foams obtained by batch supercritical foaming seem to be a sustainable option to replace non-biodegradable expanded polystyrene, and they represent a promising alternative to be considered in applications such as food packaging and other products.

Cefazolin (CFZ) is a ubiquitous antibiotic in hospital settings and has been recognized as an emerging contaminant due to its ecotoxicity. Despite the growing concern around this compound, the literature addressing feasible advanced techniques for CFZ uptake from aqueous matrices is still scarce. Thus, the objective of this work was to evaluate the adsorption of cefazolin on Spectrogel® organoclay in a batch system as an efficient remediation method. The optimization of experimental conditions was determined by a central composite rotational design. A pH study, as well as equilibrium, kinetic, and thermodynamic assays, was performed to assess the adsorption of CFZ on Spectrogel®. The kinetic and equilibrium models that best described the system were the external mass transfer resistance and Sips models, respectively. A removal efficiency above 80% was achieved, and the maximum adsorption capacity at 25 °C was 398.6 mg g -1 . The post-process contaminated organoclay was thermally regenerated. The outcomes of this work indicate that Spectrogel® is an environmentally friendly adsorbent for the removal of cefazolin from wastewater., (© 2022. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

Polymer/layered silicate composites have gained huge attention in terms of research and industrial applications. Traditional nanocomposites contain particles regularly dispersed in a polymer matrix. In this work, a strategy for the formation of a composite thin film on the surface of a polycaprolactone (PCL) matrix was developed. In addition to the polymer, the composite layer was composed of the particles of saponite (Sap) modified with alkylammonium cations and functionalized with methylene blue. The connection between the phases of modified Sap and polymer was achieved by fusing the chains of molten polymer into the Sap film. The thickness of the film of several μm was confirmed using electron microscopy and X-ray tomography. Surfaces of precursors and composite materials were analyzed in terms of structure, composition, and surface properties. The penetration of polymer chains into the silicate, thus joining the phases, was confirmed by chemometric analysis of spectral data and changes in some properties upon PCL melting. Ultimately, this study was devoted to the spectral properties and photoactivity of methylene blue present in the ternary composite films. The results provide directions for future research aimed at the development of composite materials with photosensitizing, photodisinfection, and antimicrobial surfaces.

Cefazolin (CFZ) is an antibiotic widely used in veterinary and human medicine that has been detected in high residual levels in the environment and is therefore considered an emerging contaminant. This work evaluated the adsorption of this contaminant by Spectrogel® type C organoclay, in continuous mode using a fixed-bed column. The fluid dynamics and the effect of the CFZ concentration were evaluated. In addition, prior and post-process organoclay were characterized. The continuous system under the conditions of C 0  = 0.3 mmol/L and Q = 0.1 mL/min presented lower values of mass transfer zone (5.88 cm), whereas the system with C 0  = 0.5 mmol/L and Q = 0.1 mL/min achieved higher CFZ adsorption capacity (20 µmol/g). Phenomenological and mass-transfer models were applied to the experimental data. The dual-site diffusion (DualSD) model better described the breakthrough (BTC) data. Furthermore, density functional theory (DFT) calculation was performed at the molecular level to provide a better comprehension of CFZ adsorption., (© 2022. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

In this study, the effects of NBR polarity and organoclay addition on the curing, rheological, mechanical, and thermal properties of an NBR/phenolic resin blend were investigated. The samples were prepared using a two-roll mill. The results showed that rheological and tensile properties improved due to the good distribution of nanoparticles, as well as the good compatibility of nitrile butadiene rubber with phenolic resin. The addition of 1.5 phr of nanoparticles to blends containing 33% and 45% acrylonitrile increased the curing torque difference by approximately 12% and 28%, respectively. In addition, the scorch time and curing time decreased in nanocomposites. Adding nanoparticles also increased the viscosity. The addition of phenolic resins and nanoparticles has a similar trend in modulus changes, and both of these factors increase the stiffness and, consequently, the elastic and viscous modulus of the specimens. Adding 1.5 phr of organoclay increased the tensile strength of the blends by around 8% and 13% in the samples with low and high content of acrylonitrile, respectively. Increasing the temperature of the tensile test led to a reduction in the tensile properties of the samples. Tensile strength, elongation at break, modulus, and hardness of the samples increased with increasing organoclay content. In addition, with increasing nanoparticle concentration, the samples underwent lower deterioration in tensile strength and Young's modulus at different temperatures compared to the blends. In the samples containing 1.5 phr of organoclay, the thermal decomposition temperatures were enhanced by around 24 and 27 °C for low and high acrylonitrile content.

Illite is a clay mineral that shows antioxidant and antibacterial activities because of the abundance of important clay elements in its structure. However, illite has low bioactivity due to its low solubility and electron-donating ability in aqueous solutions. Therefore, we aimed to develop polyvinylpyrrolidone (PVP)-stabilized illite microparticles (P-lite MPs) via polymer adsorption on illite surfaces. An increasing amount of PVP was used to coat a fixed amount of illite to prepare P-lite MPs of different hydrodynamic diameters in the range of 4-9 μm. These sizes were maintained for 2 weeks during storage in a biological buffer without any noticeable changes. The stabilization of illite microparticles using a hydrophilic PVP polymer improved their aqueous dispersity and free radical-scavenging activity. Since the large surface area of microparticles provides several sites for interactions, the smallest P-lite MP exhibited the highest antioxidant and antibacterial activities. More importantly, the MPs showed effective free radical-scavenging activity in vitro without any cytotoxicity. Therefore, P-lite MPs with improved bioavailability may represent a suitable bioactive material for various industrial and biomedical applications.

The dispersion mechanisms in a clay-based polymer nanocomposite (CPNC) during twin-screw extrusion are studied by in-situ rheo-optical techniques, which relate the CPNC morphology with its viscosity. This methodology avoids the problems associated with post extrusion structural rearrangement. The polydimethylsiloxane (PDMS) matrix, which can be processed at ambient and low temperatures, is used to bypass any issues associated with thermal degradation. Local heating in the first part of the extruder allows testing of the usefulness of low matrix viscosity to enhance polymer intercalation before applying larger stresses for clay dispersion. The comparison of clay particle sizes measured in line with models for the kinetics of particle dispersion indicates that larger screw speeds promote the break-up of clay particles, whereas smaller screw speeds favor the erosion of the clay tactoids. Thus, different levels of clay dispersion are generated, which do not simply relate to a progressively better PDMS intercalation and higher clay exfoliation as screw speed is increased. Reducing the PDMS viscosity in the first mixing zone of the screw facilitates dispersion at lower screw speeds, but a complex interplay between stresses and residence times at larger screw speeds is observed. More importantly, the results underline that the use of larger stresses is inefficient per se in dispersing clay if sufficient time is not given for PDMS to intercalate the clay galleries and thus facilitate tactoid disruption or erosion.

The performance of sunscreen products depends on their ultraviolet (UV) absorption ability through the film formed on the skin surface upon their application. Therefore, it is important that a uniform film is formed on the uneven skin surface for effective sunscreen performance. Because most UV filters are oil soluble, we hypothesized in this study that increasing the viscosity of the oil phase of a sunscreen product can improve the performance of the sunscreen. We first examined the association between the concentration of the oil thickener and the UV absorption ability of the sunscreen product using a skin-mimicking substrate (SMS). Among all thickeners examined (petrolatum, dextrin palmitate, silica silylate, and organoclay), organoclay and silica silylate significantly increased the UV absorbance of sunscreen on the SMS in a concentration-dependent manner. Thereafter, we examined film uniformity to elucidate the mechanism underlying the observed increase in UV absorption. The uniformity of film thickness on the SMS increased with increasing organoclay content, based on decreased standard deviations of film thickness. Our results showed that increasing the viscosity of the oil phase with organoclay resulted in the formation of a uniform film by preventing the sunscreen from flowing into the grooves when applied on the SMS, thereby increasing UV absorbance by more than two-fold that of sunscreen without organoclay. Thus, the use of thickeners, such as organoclay, increases the viscosity of the oil phase at a low shear rate after the high shear of application. This is an effective strategy for improving the overall quality and performance of sunscreen products.

The three-parameter ( K , b , and n ) Song isotherm model was slightly modified to make it possible to obtain analytical integration of the spreading pressure integral. The modified Song model (MSM) allows more efficient and accurate calculation of the ideal adsorbed solution theory (IAST). The MSM also satisfies the Henry's law and the Freundlich model at low and high concentrations, respectively, and reverts to the Langmuir and the linear models when n equals zero and one, respectively. Approximate values of each parameter could be estimated from a plot of log ( q/c ) versus log c ; the partition coefficient in the Henry's law region ( K ) and the Freundlich index ( n ) can be estimated from the ordinate value of the low-concentration asymptote and the slope of the high-concentration asymptote, respectively, and the parameter ( b ) can be estimated from the solution-phase concentration of the intersection point of the two asymptotes. The MSM was fitted to the single-solute sorption of 2-chloro-, 3-cyano-, and 4-nitrophenol onto montmorillonites modified with either HDTMA cation or TMA/HDTMA dual cations. The ideal adsorbed solution theory (IAST) combined with either dual-mode model, Khan model or MSM as a single-solute isotherm model was used to predict three bisolute and one trisolute sorption to organoclays. The Sheindorf-Rebhun-Sheintuch (SRS) and Murali-Aylmore (M-A) were also used to predict bisolute sorption to organoclays. The IAST predictions were generally in good agreement with the multisolute sorption data. The advantages of MSM over other three-parameter models were fully discussed.

An amperometric sensor based on an inkjet-printed graphene electrode (IPGE) modified with amine-functionalized montmorillonite (Mt-NH 2 ) for the electroanalysis and quantification of gentisic acid (GA) has been developed. The organoclay used as IPGE modifier was prepared and characterized by infrared spectroscopy, X-ray diffraction, scanning electron microscopy, CHN elemental analysis, and thermogravimetry. The electrochemical features of the Mt-NH 2 /IPGE sensor were investigated by cyclic voltammetry and electrochemical impedance spectroscopy. The sensor exhibited charge selectivity ability which was exploited for the electrochemical oxidation of GA. The GA amperometric response was high in acidic medium (Brinton-Robinson buffer, pH 2) due to favorable interactions between the protonated amine groups and the negatively charged GA. Kinetic studies were also performed by cyclic voltammetry, and the obtained electron transfer rate constant of 11.3 s -1 indicated a fast direct electron transfer rate of GA to the electrode. An approach using differential pulse voltammetry was then developed for the determination of GA (at + 0.233 V vs. a pseudo Ag/Ag + reference electrode), and under optimized conditions, the sensor showed high sensitivity, a wide working linear range from 1 to 21 μM (R 2  = 0.999), and a low detection limit of 0.33 μM (0.051 ± 0.01 mg L -1 ). The proposed sensor was applied to quantify GA in a commercial red wine sample. The simple and rapid method developed using a cheap clay material could be employed for the determination of various phenolic acids.

A Na + exchanged montmorillonite clay (Na-Mt) and its organoclay derivatives prepared with benzyldimethyltetradecylammonium (BDTA) cationic and polyoxyethylene (20)oleyl-ether (Brij-O20) non-ionic surfactants were used for first time at our knowledge as adsorbents the removal diverse pharmaceuticals (PPs) from samples collected in a rural wastewater facility (town of Josnes in France). The selected facility showed a poor efficiency for the elimination of PPs that were permanently release to the environment. Although involving different interactional mechanisms, the whole adsorbents Na-Mt, nonionic Brij-Mt and cationic BDTA-Mt organoclays, could remove the entire PPs of various chemical nature in a low concentration regime (ng L -1 ), where electrostatic interactions mainly controlled the adsorption. Thus, the organic PPs cations were preferentially adsorbed onto Na-Mt and Brij 0.4 -Mt (with its dual hydrophilic-hydrophobic nature) while anionic PPs showed a bold affinity to BDTA-Mt. The hydrophobic environment generated by the intercalation of surfactants within the interlayer space of organoclays conferred a versatility for the adsorption of numerous PPs through weak molecular forces (Van der Waals and/or pi-pi interactions). The study confirmed the proper efficiency of the studied layered materials including organoclays and emphasized about their promising interests in water remediation strategy., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

Green nanocomposites from rosin-limonene (Ros-Lim) copolymers based on Algerian organophilic-clay named Maghnite-CTA + (Mag-CTA + ) were prepared by in-situ polymerization using different amounts (1, 5 and 10% by weight) of Mag-CTA + and azobisisobutyronitrile as a catalyst. The Mag-CTA + is an organophilic montmorillonite silicate clay prepared through a direct exchange process; the clay was modified by ultrasonic-assisted method using cetyltrimethylammonuim bromide in which it used as green nano-filler.The preparation method of nanocomposites was studied in order to determine and improve structural, morphological, mechanical and thermal properties ofsin.The structure and morphology of the obtained nanocomposites(Ros-Lim/Mag-CTA + ) were determined using Fourier transform infrared spectroscopy, X-ray diffraction, scanning electronic microscopy and transmission electronic microscopy. The analyses confirmed the chemical modification of clay layers and the intercalation of rosin-limonene copolymer within the organophilic-clay sheets. An exfoliated structure was obtained for the lower amount of clay (1% wt of Mag-CTA + ), while intercalated structures were detected for high amounts of clay (5 and 10% wt of Mag-CTA + ). The thermal properties of the nanocomposites were studied by thermogravimetric analysis (TGA) and show a significant improvement inthe thermal stability of the obtained nanocomposites compared to the purerosin-limonene copolymer (a degradation temperature up to 280 °C).

We investigated the effect of modified aluminosilicates, including bentonite from Armenia (BA) modified with quaternary ammonium salts (BAQAS) and phosphonium salts (BAQPS), on the mechanical properties and morphology of Kevlar/epoxy composites. The Kevlar/epoxy composites containing 1.0 or 3.0 wt.% modified bentonites were fabricated using the hand lay-up technique. The mechanical properties, including the tensile, flexural, and in-plane shear strength, were tested. Based on the obtained results, we found that the mechanical properties increased with modified bentonite loading. The best results were obtained for composites containing 3 wt.% BAQAS, as most of the mechanical properties were significantly improved (tensile strength 302.9 MPa (+30%), Young's modulus 16.3 GPa (+17%), flexural modulus 23.4 GPa (+12.5%), in-plane shear strength 22.8 MPa (+24.5%), and in-plane shear modulus 677.2 MPa (+42%)). The obtained improvements in the mechanical properties are attributed to the uniform dispersion of the filler, which was confirmed by the highest increase in the intergallery spacing, from 28.3 Å for BAQAS to 45.1 Å for the composite with 3 wt.% BAQAS. Scanning electron microscopy (SEM) analysis of the brittle fracture surface indicated that the addition of modified bentonite to the epoxy matrix changed the morphology of the Kevlar/epoxy/organoclay composites and improved the fiber-matrix interfacial adhesion.

In this study, biodegradable starch-based nano films were developed by turmeric extract curcuma longa (CC), octaphenyl-polyhedral oligomeric silsesquioxane (POSS), garlic extract with antibacterial properties (GC) and clay nanoparticles. Ag + -Mt-POSS-CC-CS, Mt-CC-CS and Mt-GC-CS nanofilms were synthesized as the final products. The antibacterial and surface-active corn starch-based nanofilms that were synthesized were analyzed by using the methods of X-ray diffraction (XRD), Fourier Transform Infrared Spectroscopy (FTIR) and scanning electron microscopy (SEM). After this, the antibacterial resistances of the corn starch nanofilms against the bacteria Salmonella and Staphylococcus aureus (S. aureus) and their surface-active properties against the bacteria S. aureus, E. coli, Listeria monocytogenes and Salmonella were examined. The synthesized nano films were subjected to migration analyses, which are an important criterion for food packaging films, and their results were compared.According to the results of the analysis, while the starch nanofilms containing garlic showed antibacterial resistance against salmonella and S. aureus bacteria, the starch nano films containing curcumin and octaphenyl-POSS did not form an inhibition zone. Comparing surface activity properties, curcumin and octaphenyl-POSS-containing nano films showed surface activity, while the garlic-containing nanofilms did not show surface activity. This result shows that the mechanical properties of nanofilm containing garlic have given stronger results. Migration analysis results show that the synthesized nanofilm has found to suitable for use in the packaging of all food products such as milk products, fatty foods, liquid, acidic and dry foods according to the results of all migration analyses.

The objective of this review is to evaluate materials for use as a barrier or other deployed technology to treat technetium-99 (Tc) in the subsurface. To achieve this, Tc interactions with different materials are considered within the context of remediation strategies. Several naturally occurring materials are considered for Tc immobilization, including iron oxides and low solubility sulfide phases. Synthetic materials are also considered, and include tin-based materials, sorbents (resins, activated carbon, modified clays), layered double hydroxides, metal organic frameworks, cationic polymeric networks and aerogels. All of the materials were evaluated for their potential in-situ and ex-situ performance with respect to long-term Tc uptake and immobilization, environmental impacts and deployability. Other factors such as the technology maturity, cost and availability were also considered. Given the difficulty of evaluating materials under different experimental conditions (e.g., solution chemistry, redox conditions, solution to solid ratio, Tc concentration etc.), a subset of these materials will be selected, on the basis of this review, for subsequent standardized batch loading tests., (Copyright © 2020 Elsevier B.V. All rights reserved.)

Patch tests are highly recommended in eczema patients with eyelid involvement. Sunscreen constitutes a potential cause of eyelid or facial allergic contact dermatitis, and should be considered in patients with refractory eczema on these locations. We report a patient sensitized to several emerging allergens such as bis-ethylhexyloxyphenol methoxyphenyl triazine (Tinosorb S), Scutellaria baicalensis extract, and propylene glycol with an eyelid dermatitis. Patch tests to the combined ingredients propylene carbonate, cyclopentasiloxane, and disteardimonium hectorite; and talc, Cl 77 491, and dimethicone/methicone copolymer were also positive. We highlight the importance of systematically patch testing with the cosmetics brought in by our patients, as well as with the individual ingredients whenever positive. The identification of emerging allergies to new compounds in cosmetics mainly depends on this practice., (© 2020 John Wiley & Sons A/S. Published by John Wiley & Sons Ltd.)

Poly (amic acid) s (PAAs) were synthesized using 4,4'-(hexafluoroisopropyl-idene) diphthalic anhydride (6FDA) and two types of diamines-bis(3-aminophenyl) sulfone (BAS) and bis(3-amino-4-hydroxyphenyl) sulfone (BAS-OH). Two series of transparent polyimide (PI) hybrid films were synthesized by solution intercalation polymerization and thermal imidization using various concentrations (from 0 to 1 wt%) of organically modified clay Cloisite 30B in PAA solution. The thermo-mechanical properties, morphology, and optical transparency of the hybrid films were observed. The transmission electronic microscopy (TEM) results showed that some of the clays were agglomerated, but most of them showed dispersed nanoscale clay. The effects of -OH groups on the properties of the two PI hybrids synthesized using BAS and BAS-OH monomers were compared. The BAS PI hybrids were superior to the BAS-OH PI hybrids in terms of thermal stability and optical transparency, but the BAS-OH PI hybrids exhibited higher glass transition temperatures ( T g ) and mechanical properties. Analysis of the thermal properties and tensile strength showed that the highest critical concentration of organoclay was 0.50 wt%.

In this work, the optimum filler loading to prepare epoxy/organoclay nanocomposites by the in-situ polymerization method was studied. Bi-functionalized montmorillonite at different filler loading (0.5, 1.0, 2.0, 4.0 wt %) was dispersed in epoxy resin by using a high shear speed homogenizer. The effect on morphology, thermal, dynamic mechanical, and tensile properties of the epoxy/organoclay nanocomposites were studied in this work. Wide-angle X-ray scattering (WAXS) and field emission scanning electron microscope (FESEM) studies revealed that possible intercalated structures were obtained in epoxy/organoclay nanocomposites. Thermogravimetric analysis (TGA) shows that epoxy/organoclay nanocomposites exhibit higher thermal stability at the maximum and final decomposition temperature, as well as higher char content, compared to pristine epoxy. The dynamic mechanical analysis (DMA) indicate that storage modulus (E'), loss modulus (E″), cross-link density and glass transition temperature ( T ) of the nanocomposites were improved with organoclay loading up to 1 wt %. Beyond this loading limit, the deterioration of properties was observed. A similar trend was also observed on tensile strength and modulus. We concluded from this study that organoclay loading up to 1 wt % is suitable for further study to fabricate hybrid nanocomposites for various applications.g ) of the nanocomposites were improved with organoclay loading up to 1 wt %. Beyond this loading limit, the deterioration of properties was observed. A similar trend was also observed on tensile strength and modulus. We concluded from this study that organoclay loading up to 1 wt % is suitable for further study to fabricate hybrid nanocomposites for various applications.

Novel biomedical composites, based on organically modified vermiculite and montmorillonite with deposited Ca-deficient hydroxyapatite (CDH), were prepared. The monoionic sodium forms of vermiculite and montmorillonite were intercalated with chlorhexidine diacetate (CA). The surfaces of organoclays were used for the precipitation of Ca-deficient hydroxyapatite. The composites with Ca-deficient hydroxyapatite showed very good antibacterial effects, similar to the antimicrobial activity of pure organoclay samples. Better antibacterial activity was shown in the organically modified montmorillonite sample with Ca-deficient hydroxyapatite compared with the vermiculite composite, but, in the case of Staphylococcus aureus , both composites showed the same minimum inhibitory concentration (MIC) value. The antimicrobial effect of composites against bacteria and fungi increased with the time of exposure. The structural characterization of all the prepared materials, performed using X-ray diffraction and FT infrared spectroscopy analysis, detected no changes in the original clay or CDH during the intercalation or precipitation process, therefore we expect the strength of the compounds to be in the original power.

A series of linear aromatic copolyimides (Co-PIs) were synthesized by reacting 4,4'-biphthalic anhydride (BPA) with various molar contents of 2,2'-bis(trifluoromethyl)benzidine (TFB) and p -xylylenediamine ( p -XDA) in N , N '-dimethylacetamide (DMAc). Co-PI films were fabricated by solution casting and thermal imidization with poly(amic acid) (PAA) on glass plates. The thermo-optical properties and gas permeabilities of Co-PI films composed of various molar ratios of p -XDA (0.2⁻1.0 relative to BPA) were investigated. Thermal properties were observed to deteriorate with increasing p -XDA concentration. However, oxygen-transmission rates (O₂TRs) and optical transparencies improved with increasing p -XDA concentration. Co-PI hybrids with a 1:0.2:0.8 molar ratio of BPA:TFB: p -XDA and organically modified hectorite (STN) were prepared by the in situ intercalation method. The morphologies and the thermo-optical and gas permeation properties of the hybrids were examined as functions of STN loading (5⁻50 wt %). XRD and TEM revealed substantial increases in clay particle agglomeration in the Co-PI hybrid films as the clay loading was increased from 5 to 50 wt %. The coefficient of thermal expansion (CTE) and the O₂TR of a Co-PI hybrid film were observed to improve with increasing STN concentration; however, its optical transparency decreased gradually with increasing STN concentration.

A variety of quaternary ammonium salts with different carbon chain lengths were used to modify and convert montmorillonite clay to organoclays. The surface modification attributing to the wettability was investigated using various techniques. The zeta-potential values of all clays showed pH dependency. The prepared organoclays were utilized for phenol (protic) and nitrobenzene (aprotic) adsorption in a batch system, with pH and contact time as variables. The optimized removal for phenol and nitrobenzene within 30 min of equilibrium observed at pH 9.0 and 5.0, respectively. Observed equilibrium data followed the Langmuir monolayer adsorption kinetics with two adsorption sites (outer-layer and interlayer) for purified clay, and third additional sites for organoclays. Kinetic studies revealed that the adsorption of phenol was in the order of mono- > tetra- > di- > benzyl-substituted organoclays, which is similar to the hydrophilicity order. However, the exact opposite trend of adsorption was observed for nitrobenzene. From the performed quantitative study, it is inferred that -OH functional phenol and -NO 2 functional nitrobenzene have an affinity towards the hydrophilic clay surface and hydrophobic surfaces of quaternary ammonium salts as its first preference, respectively. This study brings promising observations and implications to the vital structural-property relationship for selective adsorption of pollutants from aqueous solutions., (Copyright © 2018 Elsevier Inc. All rights reserved.)

Composites of Laponite and Cu⁻Mn hopcalite-related mixed oxides, prepared from hydrotalcite-like (Htlc) precursors obtained in inverse microemulsions, were synthesized and characterized with XRF, XRD, SEM, TEM, H₂ temperature-programmed reduction (TPR), and N₂ adsorption/desorption at -196 °C. The Htlc precursors were precipitated either with NaOH or tetrabutylammonium hydroxide (TBAOH). Al was used as an element facilitating Htlc structure formation, and Ce and/or Zr were added as promoters. The composites calcined at 600 °C are mesoporous structures with similar textural characteristics. The copper⁻manganite spinel phases formed from the TBAOH-precipitated precursors are less crystalline and more susceptible to reduction than the counterparts obtained from the precursors synthesized with NaOH. The Cu⁻Mn-based composites are active in the combustion of toluene, and their performance improves further upon the addition of promoters in the following order: Ce < Zr < Zr + Ce. The composites whose active phases are prepared with TBAOH are more active than their counterparts obtained with the use of the precursors precipitated with NaOH, due to the better reducibility of the less crystalline mixed oxide active phase., Competing Interests: The authors declare no conflict of interest. The founding sponsors had no role in the design of the study; in the collection, analyses, or interpretation of data; in the writing of the manuscript; or in the decision to publish the results.

Synthesized organobentonite (SOB), montmorillonite (MMT), and commercial organobentonite (COB) were used as adsorbents for paraffin oil, a model pollutant in land-based oil spills and oil pipeline rupture. The characterization of clays was carried out with scanning electron microscopy (SEM), thermogravimetric analysis (TG), Fourier transform infrared spectroscopy (FTIR), and X-ray diffraction (XRD). After adsorption, oil was separated from adsorbents with a carbon dioxide responsive solvent N,N-dimethylcyclohexylamine (DMCHA), and DMCHA was subsequently separated from paraffin oil upon CO 2 bubbling instead of distillation with high energy cost. The adsorption capacity of oil to SOB, MMT, and COB was 0.686, 1.124, and 1.239 g/g, respectively. It was found that the adsorption capacity and rinsed amount of the adsorbents depended on the d-spacing, which is related to surfactant content. Electrical conductivity and pH measurements suggested that the separation process occurred via two steps. Firstly, during the initial 35 min, carbonate ions coexisted with bicarbonate ions. Then, only bicarbonate ions existed after the introduction of CO 2 gas for 120 min. Thus, organobentonites were feasible for hydrocarbon adsorption and could be simply reused by an amine-based responsive solvent. This work provided a cost-effective and sustainable method of recycling of organobentonites and the responsive solvent, which can be used to deal with leaked oil and oil spills.

In this study, the stabilization of tannery sludge, which produced during the physico-chemical treatment of tannery wastewaters, was examined by the addition of ladle furnace slag. Moreover, the simultaneous addition of organoclay and ladle furnace slag for the stabilization of tannery sludge was also examined. Chromium and dissolved organic carbon in the leachate of raw tannery sludge, using the EN 12457-2 standard leaching test, were found to exceed the limit values for disposal in non-hazardous and even in hazardous waste landfills, according to the EU Decision 2003/33/EC. Tannery waste (air-dried sludge) was mixed with ladle furnace slag and water or ladle furnace slag, organoclay and water at different ratios, in order to study the stabilization of chromium and organic compounds. The mixtures were left for one week aging and then they were subjected to the standard leaching test EN 12457-2. The leachate of tannery waste stabilized with ladle furnace slag showed Cr concentrations below the respective regulation limit value for disposal in non-hazardous waste landfills; however, the dissolved organic carbon cannot meet the respective limit value. On the other hand, the leachate of tannery waste stabilized with a mixture of ladle furnace slag and organoclay, using 30:50:20 mass ratio, presented both Cr and dissolved organic carbon concentrations below the regulation limit values for disposal in non-hazardous waste landfills. Moreover, this leachate was further subjected to ecotoxicity test, using the Vibrio fischeri photo-bacterium. The leachate of stabilized tannery waste showed reduced ecotoxicity, in comparison with the toxicity effect of the leachate of the untreated tannery waste., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

The potential of layered silicates as drug carrier is overviewed. Due to their large surface area and expandable interlayer space to accommodate drug molecules, layered silicates have a potential as carrier of various molecules. In addition to the electrostatic interactions between negatively charged layered silicates and positively charged drug molecules, the organic modification of the surface of layered silicates has been applied to accommodate a variety of drug molecules not only cationic ones. The in vitro release experiment of the accommodated drug molecules has been reported under the acidic conditions. In order to discuss the future direction of layered silicates as drug carrier, materials' variation of layered silicates and their modification, and the reported stimuli-responsive hybrids based on layered silicates were introduced., (© 2018 Elsevier Inc. All rights reserved.)

A novel design of combustion catalysts is proposed, in which clay/TiO₂/MnAl-mixed oxide composites are formed by intermixing exfoliated organo-montmorillonite with oxide precursors (hydrotalcite-like in the case of Mn-Al oxide) obtained by an inverse microemulsion method. In order to assess the catalysts' thermal stability, two calcination temperatures were employed: 450 and 600 °C. The composites were characterized with XRF (X-ray fluorescence), XRD (X-ray diffraction), HR SEM (high resolution scanning electron microscopy, N₂ adsorption/desorption at -196 °C, and H₂ TPR (temperature programmed reduction). Profound differences in structural, textural and redox properties of the materials were observed, depending on the presence of the TiO₂ component, the type of neutralization agent used in the titania nanoparticles preparation (NaOH or NH₃ (aq)), and the temperature of calcination. Catalytic tests of toluene combustion revealed that the clay/TiO₂/MnAl-mixed oxide composites prepared with the use of ammonia showed excellent activity, the composites obtained from MnAl hydrotalcite nanoparticles trapped between the organoclay layers were less active, but displayed spectacular thermal stability, while the clay/TiO₂/MnAl-mixed oxide materials obtained with the aid of NaOH were least active. The observed patterns of catalytic activity bear a direct relation to the materials' composition and their structural, textural, and redox properties., Competing Interests: The authors declare no conflict of interest. The founding sponsors had no role in the design of the study; in the collection, analyses, or interpretation of data; in the writing of the manuscript, and in the decision to publish the results.

This work presents the fabrication and characterization of novel colloidal multifunctional polymer nanofiber composites (NFCs) from water dispersion blends of intercalated silicate layered nanocomposites of poly (2-vinyl-N-pyrrolidone)/octadecyl amine-montmorillonite (ODA-MMT) and dextran/ODA-MMT as matrix and partner polymer intercalated nanocomposites in the presence of NaOH and folic acid (FA) as doping agents by green reactive electrospinning. Chemical and physical structures, surface morphology and electrical properties were investigated. Effects of matrix/partner polymer ratios, doping agents, absorption time of NaOH, and temperature on electrical parameters of NFCs were evaluated. The presence of FA and increasing dextran fraction in NFCs resulted in reducing fiber diameter and improving diameter distribution. High complexing behaviors of matrix/partner polymer chains, organoclay, FA, and NaOH significantly improved conductivity parameters, especially 5-min of absorption time (≈10 -2 -10 - 3 Sm -1 ). The conductivity of the samples decreased with increasing temperature. NFCs fabricated for the first time are promising candidates for various biomedical, electrochemical and electronic applications as electro-active platforms., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

Stimuli-responsive colloidal nanocomposite hydrogels are prepared by exploiting non-covalent interactions between anionic cellulose nanocrystals and polycationic delaminated sheets of aminopropyl-functionalized magnesium phyllosilicate clays.

Among pharmaceutical products (PPs) recalcitrant to water treatments, diclofenac shows a high toxicity and remains at high concentration in natural aquatic environments. The aim of this study concerns the understanding of the adsorption mechanism of this anionic PP onto two organoclays prepared with two long-alkyl chains cationic surfactants showing different chemical nature for various experimental pH and temperature conditions. The experimental data obtained by a set of complementary techniques (X-ray diffraction, elemental analyses, gas chromatography coupled with mass spectrometry, and Fourier transform infrared spectroscopy) and the use of Langmuir, Freundlich and Dubinin-Radushkevish equation models, reveal that organoclays show a good affinity to diclofenac which is enhanced as the temperature is under 35°C and for pH above 4.5 (i.e. >pKa of diclofenac) while the chemical nature of surfactant appears to play a minor role. The thermodynamic parameters derived from the fitting procedure point out the strong electrostatic interaction with organic cations adsorbed within the interlayer space in the organoclays for the adsorption of diclofenac. This study stress out the application of organoclays for the adsorption of a recalcitrant PPs in numerous aquatic compartments that can be used as a complement with activated carbon for waste water treatment., (Copyright © 2016 Elsevier B.V. All rights reserved.)

This work presents the synthesis and characterisation of intercalated nanocomposites (NCs) from dispersed water solution blends of octadecyl amine-montmorillonite (ODA-MMT) (NC-0), folic acid (FA) conjugated ODA-MMT (NC-1) and Ag-MMT clay as a stable silver carrying agent (NC-2). The composition, chemical/physical and morphology of NCs with in situ intercalating nanostructures were investigated. Effect of organoclay, FA and Ag-MMT on L929 fibroblast (control), human colon carcinoma (DLD-1) cell lines, and the cytotoxicity, apoptosis and necrosis degree were estimated via WST-1/hemocytometric, double staining (as a ribonuclease A enzyme based method) and fluorescence microscopy methods in a dose-dependent manner. The mentioned cell lines integrated with NCs resulted in remarkable change in both morphology and nuclei of DLD-1 and fibroblast cells by apoptosis analysis. The number of necrotic cells were remarkably increased, as the toxic effects of nanocomposite nanoparticles were applied to both cell lines. Finally, the molecular mechanism of anticancer action of functionalised organoclays was elucidated.

This article surveys the decade of progress accomplished in the application of isoconversional methods to thermally stimulated processes in polymers. The processes of interest include: crystallization and melting of polymers, gelation of polymer solutions and gel melting, denaturation (unfolding) of proteins, glass transition, polymerization and crosslinking (curing), and thermal and thermo-oxidative degradation. Special attention is paid to the kinetics of polymeric nanomaterials. The article discusses basic principles for understanding the variations in the activation energy and emphasizes the possibility of using models for linking such variations to the parameters of individual kinetic steps. It is stressed that many kinetic effects are not linked to a change in the activation energy alone and may arise from changes in the preexponential factor and reaction model. Also noted is that some isoconversional methods are inapplicable to processes taking place on cooling and cannot be used to study such processes as the melt crystallization., (© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The immobilization of Candida antarctica lipase B (CALB) was performed by physical adsorption on both neat and organo-modified forms of sepiolite and montmorillonite. The influence of different parameters, e.g., solvent, enzyme loading, cross-linking, and type of clay support, on immobilization efficiency and catalyst hydrolytic activity has been investigated. The highest hydrolytic activities were obtained for CALB immobilized on organo-modified clay minerals, highlighting the beneficial effect of organo-modification. The esterification activity of these CALB/organoclay catalysts was also tested in the ring-opening polymerization of ε-caprolactone. The polymerization kinetics observed for clay-immobilized catalysts confirmed that CALB adsorbed on organo-modified montmorillonite (CALB/MMTMOD) was the highest-performing catalytic system.

β-Lactam antibiotics including penicillin G, nafcillin, cefazolin, cefotaxime, and oxacilline in water were rapidly removed and degraded by using didodecyldimethylammonium bromide (DDAB)-montmorillonite (MT) organoclay. Removal of antibiotics increased with increasing the amount of organoclay added and the amount of DDAB sorbed on MT. Extents of organoclay sorption of antibiotics were represented by the binding constants to DDAB molecules and correlated to the aqueous-octanol distribution coefficients. The degradation rate of β-lactam antibiotics was found to significantly increase by the organoclay sorption. Even under the mild conditions (25°C and pH 7), penicillin G (m/z=335) nearly completely (>98%) degraded into penicilloic acid (m/z=353) missing β-lactam ring within 2h. The first-order reaction rate of the primary degradation increased with increasing in temperature. The activation energy estimated from the Arrhenius plot was 49kJmol(-1) and lower than the value (83.5kJmol(-1)) in water, strongly suggesting catalytic activity of DDAB-MT organoclay. The applicability to wastewater treatment was demonstrated by using secondary effluents of municipal sewage treatment plants and synthesized hospital wastewaters., (Copyright © 2016 Elsevier B.V. All rights reserved.)

Chitosan-montmorillonite composites can provide hydrophobicity and amino groups to enhance the performances of montmorillonite in wastewater treatment. In this paper, low molar mass chitosan (LC) and medium molar mass chitosan (MC) were selected to intercalate a sodium montmorillonite (Mt). The adsorption isotherm of LC and MC on the Mt and the pH dependency were measured. Thermo X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FTIR) were used to characterize the chitosan-Mt composites. Results showed that with hydrochloric acid as the solvent of chitosans, increasing pH from 3 to 5.5 enhanced the adsorption of both LC and MC on the Mt, and when the equilibrium concentration of chitosans approached 300mg/L at pH 5.5, the amount of adsorbed chitosan reached the highest level of 0.203mg/mg for LC and 0.190mg/mg for MC, respectively. When the Mt was saturated with the chitosan, the amino groups on the chitosan were bonded with the Mt through electrostatic interaction and there was monolayer of the chitosan in the interlayer space of Mt, which were confirmed by FTIR spectra and XRD patterns, respectively., (Copyright © 2016. Published by Elsevier B.V.)

Background: Imazamox is an ionisable herbicide, weakly retained and with high soil vertical mobility, that is used for the control of the root-parasitic plants Orobanche spp. A natural smectite (SW) modified with the biopolymer chitosan (Ch) or with Fe(3+) cation was assayed as adsorbent or carrier for imazamox controlled-release formulations (CRFs)., Results: The greatest adsorption (74%) was observed for SWFe at high initial concentration (500 µM) and low pH (4.3). The interaction mechanism of imazamox on SWFe implies interlayer polar adsorption, followed by protonation of the imidazolinone ring, whereas ionic, polar and hydrophobic interactions seemed to occur in imazamox adsorption on SWCh. The herbicide release into water was inversely related to the strength of the imazamox-clay interactions and ranged in the first 10 min for imazamox-SWFe and imazamox-SWCh complexes from 27 to 75%, whereas commercial imazamox released 86%. The imazamox-SWCh weak complex (SWCh6 WC) showed similar herbicidal activity to the commercial formulation but produced a reduction of 15% in the total soil leaching losses and a reduction of 40% in the peak maximum concentration in soil column leachates., Conclusion: The imazamox-clay weak complex (WC) of SWFe and SWCh and the strong complex (SC) with SWCh showed appropriate behaviour as nanopesticides or smart delivery systems to be incorporated in CRFs. © 2015 Society of Chemical Industry., (© 2015 Society of Chemical Industry.)