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 CaCO3 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 CaCO3 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 CaCO3 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.

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.

Combination of organoclay sorption with manganese(IV) oxide (MnO2) 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 MnO2. 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 MnO2 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 MnO2-catalyzed oxidation for the diffusion control of toxic agrochemicals.

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 (R2 = 0.993) and Langmuir (R2 = 0.988). This study proved that organoclay can be used as a promising adsorbent for dye removal with low cost and high removal efficiency.

TiO2/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 TiO2 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 N2 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 TiO2 nanoparticles. As a result, the TiO2/Na-Mt series displayed superior textural properties, with specific surface area up to 256 m2g-1 and pore volume up to 0.247 cm3g-1 compared with 208 m2g-1 and 0.231 cm3g-1, respectively, for the TiO2/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.

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 CS1, CS2, and CS3 nanocomposite films were found as 0.305, 0.297, and 0.297 mg/dm2, respectively. The inhibition zone of CS1, CS2, and CS3 nanocomposite films were found as 1547, 386, and 1884 mm2 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.

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.

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 m2/g and a large pore volume of 0.763 cm3/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.