Compatibility of Sustainable Mater-Bi/poly(ε-caprolactone)/cellulose Biocomposites as a Function of Filler Modification.

Despite their popularity and multiplicity of applications, wood-polymer composites (WPCs) still have to overcome particular issues related to their processing and properties. The main aspect is the compatibility with plant-based materials which affects the overall performance of the material. It can be enhanced by strengthening the interfacial adhesion resulting from physical and/or chemical interactions between the matrix and filler, which requires introducing a compatibilizer or a proper modification of one or both phases. Herein, the impact of cellulose filler modifications with varying contents (1-10 wt%) of hexamethylene diisocyanate (HDI) on the compatibility of Mater-Bi/poly(ε-caprolactone) (PCL)-based biocomposites was evaluated. An analysis of surface wettability revealed that the filler modification reduced the hydrophilicity gap between phases, suggesting compatibility enhancement. It was later confirmed via microscopic observation (scanning electron microscopy (SEM) and atomic force microscopy (AFM)), which pointed to the finer dispersion of modified particles and enhanced quality of the interface. The rheological analysis confirmed increased system homogeneity by the reduction in complex viscosity. In contrast, thermogravimetric analysis (TGA) indicated the efficient modification of filler and the presence of the chemical interactions at the interface by the shift of thermal decomposition onset and the changes in the degradation course.

Effect of Shear Stress during Processing on Structure, Morphology, and Properties of Isotactic Polypropylene Nucleated with Silsesquioxane-Based ß-Nucleating Agent.

The study aimed to determine the influence of shear stress during real-life industrial processes such as compression molding and injection molding to different cavities on the crystallization of the isotactic polypropylene nucleated with a novel silsesquioxane-based ß-nucleating agent. Octakis(N2,N6-dicyclohexyl-4-(3-(dimethylsiloxy)propyl)naphthalene-2,6-dicarboxamido)octasilsesquioxane (SF-B01) is a highly effective nucleating agent (NA) based on the hybrid organic-inorganic silsesquioxane cage. The samples containing various amounts of the silsesquioxane-based and commercial iPP ß-nucleants (0.01-0.5 wt%) were prepared by compression molding and injection molding, including forming in the cavities with different thicknesses. The study of the thermal properties, morphology, and mechanical properties of iPP samples allows for obtaining comprehensive information about the efficiency of silsesquioxane-based NA in shearing conditions during the forming. As a reference sample, iPP nucleated by commercial ß-NA (namely N2,N6-dicyclohexylnaphthalene-2,6-dicarboxamide, NU-100) was used. The static tensile test assessed the mechanical properties of pure and nucleated iPP samples formed in different shearing conditions. Variations of the ß-nucleation efficiency of the silsesquioxane-based and commercial nucleating agents caused by shear forces accompanying the crystallization process during forming were evaluated by differential scanning calorimetry (DSC) and wide-angle X-ray scattering (WAXS). The investigations of changes in the mechanism of interactions between silsesquioxane and commercial nucleating agents were supplemented by rheological analysis of crystallization. It was found that despite the differences in the chemical structure and solubility of the two nucleating agents, they influence the formation of the hexagonal iPP phase in a similar way, taking into consideration the shearing and cooling conditions.

The impact of thermomechanical and chemical treatment of waste Brewers' spent grain and soil biodegradation of sustainable Mater-Bi-Based biocomposites.

Due to the massive plastic pollution, development of sustainable and biodegradable polymer materials is crucial to reduce environmental burdens and support climate neutrality. Application of lignocellulosic wastes as fillers for polymer composites was broadly reported, but analysis of biodegradation behavior of resulting biocomposites was rarely examined. Herein, sustainable Mater-Bi-based biocomposites filled with thermomechanically- and chemically-modified brewers' spent grain (BSG) were prepared and subjected to 12-week soil burial test simulating their biodegradation in natural environment. BSG stabilizing effect on polymer matrix affected by the content of melanoidins and antioxidant phytochemicals, along with the impact of diisocyanate applied to strengthen the interfacial adhesion. Biocomposites showed 25-35 wt% mass loss over 12 weeks resulting from swelling of BSG filler and sample microcracking, which increased surface roughness by 247-448 %. The degree of decomposition was partially reduced by BSG modifications pointing to the stabilizing effect of melanoidins and phytochemicals, and enhanced interfacial adhesion. Soil burial-induced structural changes enhanced biocomposites' thermal stability determined by thermogravimetric analysis shifting decomposition onset by 14.4-32.0 °C due to the biodegradation of lower molecular weight starch macromolecules confirmed by differential scanning calorimetry. For unfilled Mater-Bi, it caused an average 32 % reduction in complex viscosity and storage modulus captured by oscillatory rheological measurements. Nonetheless, the inverse effect was noted for biocomposites where modulus increased even by one order of magnitude due to the swelling of BSG particles and amorphous phase decomposition. Presented results indicate that BSG promotes soil degradation of Mater-Bi and its rate can be engineered by biofiller treatment elaboration.

Mater-Bi/Brewers' Spent Grain Biocomposites-Novel Approach to Plant-Based Waste Filler Treatment by Highly Efficient Thermomechanical and Chemical Methods.

Thermoplastic starch (TPS) is a homogenous material prepared from native starch and water or other plasticizers subjected to mixing at a temperature exceeding starch gelatinization temperature. It shows major drawbacks like high moisture sensitivity, poor mechanical properties, and thermal stability. To overcome these drawbacks without significant cost increase, TPS could be blended with bio-based or biodegradable polymers and filled with plant-based fillers, beneficially waste-based, like brewers' spent grain (BSG), the main brewing by-product. Filler modifications are often required to enhance the compatibility of such composites. Herein, we investigated the impact of BSG thermomechanical and chemical treatments on the structure, physical, thermal, and rheological performance of Mater-Bi-based composites. Thermomechanical modifications enhanced matrix thermal stability under oxidative conditions delaying degradation onset by 33 °C. Moreover, BSG enhanced the crystallization of the polybutylene adipate terephthalate (PBAT) fraction of Mater-Bi, potentially improving mechanical properties and shortening processing time. BSG chemical treatment with isophorone diisocyanate improved the processing properties of the composites, expressed by a 33% rise in melt flow index. Depending on the waste filler's selected treatment, processing, and rheological performance, thermal stability or interfacial adhesion of composites could be enhanced. Moreover, the appearance of the final materials could be adjusted by filler selection.

Evaluation of the Oil-Rich Waste Fillers' Influence on the Tribological Properties of Polylactide-Based Composites.

In recent years, natural-based polymeric composites have gained the attention of researchers and the industry due to their low environmental impact and good applicational properties. A promising example of these materials is polylactide-based composites filled with linseed cake. Even though they can be characterized by reduced brittleness and enhanced crystallization rate, their applicational potential cannot be fully evaluated without knowing their tribological properties. This paper is aimed to analyze the influence of the oil contained by the filler on the mechanical and frictional properties of polylactide-based composites. Specimens of unfilled polylactide and its composites containing 10 wt % of linseed cake with different oil content were prepared by injection molding. Their microhardness was measured by the Vickers method. The softening temperature was determined by the Vicat method. The scratch resistance of the samples was tested with the loading of 10, 20 and 40 N. The coefficient of friction was evaluated by the pin-on-plate method, using CoCrMo alloy as the counter surface. It was found that the oil content in the filler does not directly influence the mechanical and tribological properties, but the composite samples present comparable hardness and lower coefficient of friction than the unfilled polymer, so they can be a good eco-friendly alternative to the unfilled polylactide when the frictional properties are an important factor.

Polyethylene/Polyamide Blends Made of Waste with Compatibilizer: Processing, Morphology, Rheological and Thermo-Mechanical Behavior.

The aim of this study was to develop a polyethylene/polyamide (R-PE/R-PA) regranulated product made from post-consumer wastes grafted with polyethylene-graft-maleic anhydride (PE-g-MAH) by reactive extrusion in a twin-screw extruder equipped with an external mixing zone. The compatibility effect of PE-g-MAH used as a modifier in R-PE/R-PA blends was evaluated by means of differential scanning calorimetry (DSC) and dynamic mechanical thermal analysis (DMTA), while the analysis of the chemical structure of this blend was carried out by Fourier transform infrared spectroscopy (FT-IR). The thermal properties, complex viscosity, and selected usage properties of R-PE/R-PA blends compatibilized with PE-g-MAH, i.e., density and water absorption, were evaluated. The morphology of the blends with and without the compatibilizer was observed by scanning electron microscopy. The R-PE/R-PA/MAH blend shows heterogenic structure, which is a result of the chemical reaction in reactive extrusion between functional groups of PE-g-MAH used as modifier and the end groups of R-PA6. The results show that the R-PE/R-PA blend with increased PE-g-MAH content showed increased hardness, stiffness, and ultimate tensile strength due to the increased degree of crystallinity. The increase in crystallinity is proportional to the improvement of the mechanical properties. Moreover, it is shown that 1 wt.% PE-g-MAH added to the R-PE/R-PA waste blend increases the interfacial interactions and compatibility between R-PE and R-PA, resulting in decreased polyamide particle size. Finally, the results show that it is possible to produce good quality regranulated products with advantageous properties and structure from immiscible polymer waste for industrial 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.

Effect of Basalt Powder Surface Treatments on Mechanical and Processing Properties of Polylactide-Based Composites.

Legislative restrictions and the needs of consumers have created a demand for sustainable materials. Polylactide (PLA) is a biodegradable polyester with advantageous mechanical properties, however, due to its low crystallization rate, it also has low thermomechanical stability. Its range of application temperatures can be widened using nucleating agents and fillers including basalt powder (BP), a waste product from the mining industry. This study analyzed the possibility of enhancing the properties of a PLA-BP composite by chemically treating the filler. Basalt powder was subjected to silanization with 3-aminopropyltriethoxysilane or γ-glycidoxypropyltrimethoxysilane and mixed with PLA at 5-20 wt%. The nucleating effect of a potassium salt of 3,5-bis(methoxycarbonyl) (LAK-301) in the silanized composite was also evaluated. The properties of the materials with silanized BP were compared with the unmodified basalt powder. The miscibility of the filler and the polymer was assessed by oscillatory rheometry. The structure of the composites was studied using scanning electron microscopy and their thermomechanical properties were analyzed using dynamic mechanical thermal analysis. Mechanical properties such as tensile strength, hardness and impact strength, and heat deflection temperature of the materials were also determined. It was concluded that BP-filled nucleated PLA composites presented satisfactory thermomechanical stability without silanization, but chemical treatment could improve the matrix-filler interactions.

Correlation between Processing Parameters and Degradation of Different Polylactide Grades during Twin-Screw Extrusion.

This article presents the effect of twin-screw extrusion processing parameters, including temperature and rotational speed of screws, on the structure and properties of four grades of polylactide (PLA). To evaluate the critical processing parameters for PLA and the possibilities for oxidative and thermomechanical degradation, Fourier-transform infrared spectroscopy (FT-IR), oscillatory rheological analysis, and differential scanning calorimetry (DSC) measurements were used. The influence of degradation induced by processing temperature and high shearing conditions on the quality of the biodegradable polyesters with different melt flow indexes (MFIs)was investigated by color analysis within the CIELab scale. The presented results indicate that considering the high-temperature processing of PLA, the high mass flow index and low viscosity of the polymer reduce its time of residence in the plastifying unit and therefore limit discoloration and reduction of molecular weight due to the degradation process during melt mixing, whereas the initial molecular weight of the polymer is not an essential factor.

Mechanical, Thermal and Rheological Properties of Polyethylene-Based Composites Filled with Micrometric Aluminum Powder.

Investigations related to polymer/metal composites are often limited to the analysis of the electrical and thermal conductivity of the materials. The presented study aims to analyze the impact of aluminum (Al) filler content (from 1 to 20 wt%) on the rarely investigated properties of composites based on the high-density polyethylene (HDPE) matrix. The crystalline structure, rheological (melt flow index and oscillatory rheometry), thermal (differential scanning calorimetry), as well as static (tensile tests, hardness, rebound resilience) and dynamic (dynamical mechanical analysis) mechanical properties of composites were investigated. The incorporation of 1 and 2 wt% of aluminum filler resulted in small enhancements of mechanical properties, while loadings of 5 and 10 wt% provided materials with a similar performance to neat HDPE. Such results were supported by the lack of disturbances in the rheological behavior of composites. The presented results indicate that a significant content of aluminum filler may be introduced into the HDPE matrix without additional pre-treatment and does not cause the deterioration of composites' performance, which should be considered beneficial when engineering PE/metal composites.

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.