Sorption of ionic liquids in soil enriched with polystyrene microplastic reveals independent behavior of cations and anions.

Recently, much attention has been focused on the application of the Ionic Liquids (ILs) with herbicidal activity in agriculture. It has been suggested that through the appropriate selection of cations and anions, one can adjust the properties of ILs, particularly the hydrophobicity, solubility, bioavailability, toxicity. In practical agricultural conditions, it will be beneficial to reduce the mobility of herbicidal anions, such as the commonly applied 2,4-dichlorophenoxyacetic acid [2,4-D] in the soil. Furthermore, microplastics are becoming increasingly prevalent in the soil, potentially stimulating herbicidal sorption. Therefore, we investigated whether cations in ILs influence the mobility of anions in OECD soil supplemented with polystyrene microplastic (PS). For this purpose, we used the 2,4-D based ILs consisting of: a hydrophilic choline cation [Chol][2,4-D] and a hydrophobic choline cation with a C12chain [C12Chol][2,4-D]. Characterization of selected micropolystyrene was carried out using the BET sorption-desorption isotherm, particle size distribution and changes in soil sorption parameters such as soil sorption capacity and cation exchange capacity. Based on the batch sorption experiment, the effect of microplastic on the sorption of individual cations and anions in soil contaminated with micropolystyrene was evaluated. The results obtained indicate that the introduction of a 1-10% (w/w) PS resulted in an 18-23% increase of the soil sorption capacity. However, the sorption of both ILs' cations increased only by 3-5%. No sorption of the [2,4-D] anion was noted. This suggests that cations and anions forming ILs, behave independently of each other in the environment. The results indicate the fact that ILs upon introduction into the environment are not a new type of emerging contaminant, but rather a typical mixture of ions. It is worth noting that when analyzing the behavior of ILs in the environment, it is necessary to follow the fate of both cations and anions.

The Accelerated Aging Impact on Mechanical and Thermal Properties of Polypropylene Composites with Sedimentary Rock Opoka-Hybrid Natural Filler.

This paper presents the impact of accelerated aging on selected mechanical and thermal properties of isotactic polypropylene (iPP) composites filled with sedimentary hybrid natural filler-Opoka rock. The filler was used in two forms: an industrial raw material originating as a subsieve fraction natural material, and a rock calcinated at 1000 °C for production of phosphorous sorbents. Fillers were incorporated with constant amount of 5 wt % of the resulting composite, and the material was subjected to accelerated weathering tests with different exposition times. The neat polypropylene and composites with calcium carbonate as a reference filler material were used for comparison. The aim of the research was to determine the possibility of using the Opoka rock as a new hybrid filler for polypropylene, which could be an alternative to the widely used calcium carbonate and silica. The thermal, mechanical, and structural properties were evaluated by means of differential scanning calorimetry (DSC), tensile tests, scanning electron microscopy (SEM), and Fourier-transform infrared spectroscopy with attenuated total reflectance (FTIR/ATR) prior to and after accelerated aging. As a result, it was found that the composites of polypropylene with Opoka were characterized by similar or higher functional properties and higher resistance to photodegradation compared to composites with conventional calcium carbonate. The results of measurements of mechanical properties, structural and surface changes, and the carbonyl index as a function of accelerated aging proved that Opoka was an effective ultraviolet (UV) stabilizer, significantly exceeding the reference calcium carbonate in this respect. The new hybrid filler of natural origin in the form of Opoka can therefore be used not only as a typical powder filler, but above all as a UV blocker/stabilizer, thus extending the life of polypropylene composites, especially for outdoor applications.

The Effect of Surface Treatment with Isocyanate and Aromatic Carbodiimide of Thermally Expanded Vermiculite Used as a Functional Filler for Polylactide-Based Composites.

In this work, thermally expanded vermiculite (TE-VMT) was surface modified and used as a filler for composites with a polylactide (PLA) matrix. Modification of vermiculite was realized by simultaneous ball milling with the presence of two PLA chain extenders, aromatic carbodiimide (KI), and 4,4'-methylenebis(phenyl isocyanate) (MDI). In addition to analyzing the particle size of the filler subjected to processing, the efficiency of mechanochemical modification was evaluated by Fourier transform infrared spectroscopy (FTIR) and scanning electron microscopy (SEM). The composites of PLA with three vermiculite types were prepared by melt mixing and subjected to mechanical, thermomechanical, thermal, and structural evaluation. The structure of composites containing a constant amount of the filler (20 wt%) was assessed using FTIR spectroscopy and SEM analysis supplemented by evaluating the final injection-molded samples' physicochemical properties. Mechanical behavior of the composites was assessed by static tensile test and impact strength hardness measurements. Heat deflection temperature (HDT) test and dynamic thermomechanical analysis (DMTA) were applied to evaluate the influence of the filler addition and its functionalization on thermomechanical properties of PLA-based composites. Thermal properties were assessed by differential scanning calorimetry (DSC), pyrolysis combustion flow calorimetry (PCFC), and thermogravimetric analysis (TGA). The use of filler-reactive chain extenders (CE) made it possible to change the vermiculite structure and obtain an improvement in interfacial adhesion and more favorable filler dispersions in the matrix. This translated into an improvement in impact strength and an increase in thermo-mechanical stability and heat release capacity of composites containing modified vermiculites.

The Influence of Sub-Zero Conditions on the Mechanical Properties of Polylactide-Based Composites.

Polylactide-based composites filled with waste fillers due to their sustainability are a subject of many current papers, in which their structural, mechanical, and thermal properties are evaluated. However, few studies focus on their behavior in low temperatures. In this paper, dynamic and quasi-static mechanical properties of polylactide-based composites filled with 10 wt% of linseed cake (a by-product of mechanical oil extraction from linseed) were evaluated at room temperature and at -40 °C by means of dynamic mechanical analysis (DMA), Charpy's impact strength test and uniaxial tensile test. It was found that the effect of plasticization provided by the oil contained in the filler at room temperature is significantly reduced in sub-zero conditions due to solidification of the oil around -18 °C, as it was shown by differential scanning calorimetry (DSC) and DMA, but the overall mechanical performance of the polylactide-based composites was sufficient to enable their use in low-temperature applications.

Improving the Toughness and Thermal Resistance of Polyoxymethylene/Poly(lactic acid) Blends: Evaluation of Structure-Properties Correlation for Reactive Processing.

The study focuses on the development of polyoxymethylene (POM)/poly(lactic acid) (PLA) blends with increased impact and thermal resistance. The study was conducted in two phases; in the first part, a series of unmodified blends with PLA content of 25, 50, and 75 wt.% was prepared, while the second part focused on the modification of the PLA/POM (50/50) blends. An ethylene/butyl acrylate/glycidyl methacrylate terpolymer (E/BA/GMA) elastomer (EBA) was used to improve the impact strength of the prepared blends, while reactive blending was used to improve interfacial interactions. We used a multifunctional epoxy chain extender (CE) as the compatibilizer. Static tensile tests and notched Izod measurement were used to evaluate the mechanical performance of the prepared samples. The thermomechanical properties were investigated using dynamic mechanical thermal analysis (DMTA) analysis and heat deflection temperature (HDT)/Vicat softening temperature (VST) methods. The crystallinity was measured using differential scanning calorimetry (DSC) and wide-angle X-ray diffraction (WAXS) measurements, while the rheology was evaluated using a rotational rheometer. The paper also includes a structure analysis performed using the SEM method. The structural tests show partial miscibility of the POM/PLA systems, resulting in the perfect compatibility of both phases. The impact properties of the final blends modified by the EBA/CE system were found to be similar to pure POM resin, while the E modulus was visibly improved. Favorable changes were also noticeable in the case of the thermomechanical properties. The results of most of the conducted measurements and microscopic observations confirm the high efficiency of the reaction for PLA as well as for the modified POM/PLA mixtures.

Accelerated Weathering of Polylactide-Based Composites Filled with Linseed Cake: The Influence of Time and Oil Content within the Filler.

This paper presents the effects of accelerated weathering on the properties of polylactide (PLA) composites filled with linseed cake. The particle-shaped waste filler with different linseed oil content (0.9-39.8 wt %) was incorporated with constant amount of 10 wt % to a polymeric matrix and subjected to accelerated weathering tests with different exposition times. The structure of the composites, their mechanical, thermal, and thermo-mechanical properties were evaluated by means of scanning electron microscopy, tensile test, dynamic mechanical thermal analysis, and differential scanning calorimetry prior to and after weathering. The results of the measurements were analyzed in reference to the amount of crude oil contained in the filler. The behavior of the multiphase composite during weathering was described. It was found that the oil-rich samples during the first stage of the process showed increased resistance to hydrolytic degradation due to their relatively high crystallinity. The presence of water and elevated temperatures caused swelling of the filler and cracking of the polymeric matrix. Those discontinuities enabled the plasticizing oil to be rinsed out of the composite and thus water penetrated into the samples. As a result, the PLA-based composites containing oil-rich linseed cake were found to be more vulnerable to hydrolytic degradation in a longer time.