More than just a beer - Brewers' spent grain, spent hops, and spent yeast as potential functional fillers for polymer composites.

Beer is among the most popular beverages in the world, with the production distributed uniformly between the biggest continents, so the utilization of brewing by-products is essential on a global scale. Among their potential recipients, the plastics industry offers extensive range of potential products. Herein, the presented study investigated the application of currently underutilized solid brewing by-products (brewers' spent grain, spent hops, spent yeast) as fillers for highly-filled poly(ε-caprolactone)-based composites, providing the first direct connection between spent hops or spent yeast and the polymer composites. Comprehensive by-product characterization revealed differences in chemical composition. The elemental C:O ratio, protein content, and Trolox equivalent antioxidant capacity varied from 1.40 to 1.89, 12.9 to 32.4 wt%, and 2.41 to 10.24 mg/g, respectively, which was mirrored in the composites' structure and performance. Morphological analysis pointed to the composition-driven hydrophilicity gap limiting interfacial adhesion for high shares of brewers' spent grain and spent hops, due to high hydrophilicity induced by carbohydrate content. Phytochemicals and other components of applied by-products stimulated composites' oxidative resistance, shifting oxidation onset temperature from 261 °C for matrix over 360 °C for high spent yeast shares. Simultaneously, spent yeast also provided compatibilizing effects for poly(ε-caprolactone)-based composites, reducing complex viscosity compared to other fillers and indicating its highest affinity to poly(ε-caprolactone)due to the lowest hydrophilicity gap. The presented results indicate that the proper selection of brewing by-products and adjustment of their shares creates an exciting possibility of engineering composites' structure and performance, which can be transferred to other polymers differing with hydrophilicity.

Uniaxial Rotational Molding of Bio-Based Low-Density Polyethylene Filled with Black Tea Waste.

In this paper, the possibility of obtaining uniaxially rotomolded composite parts was discussed. The used matrix was bio-based low-density polyethylene (bioLDPE) filled with black tea waste (BTW) to prevent the thermooxidation of samples during processing. In rotational molding technology, the material is held at an elevated temperature in a molten state for a relatively long time, which can result in polymer oxidation. The Fourier transform infrared spectroscopy (FTIR) shows that adding 10 wt% of black tea waste has not led to the formation of carbonyl compounds in polyethylene, and adding 5 wt% and above prevents the appearance of the C-O stretching band connected with degradation of LDPE. The rheological analysis proved the stabilizing effect of black tea waste on the polyethylene matrix. The same temperature conditions of rotational molding did not change the chemical composition of black tea but slightly influenced the antioxidant activity of methanolic extracts; the detected changes suggest degradation is a color change, and the total color change parameter (ΔE) is 25. The oxidation level of unstabilized polyethylene measured using the carbonyl index exceeds 1.5 and gradually decreases with the addition of BTW. The BTW filler did not influence the melting properties of bioLDPE; the melting and crystallization temperature remained stable. The addition of BTW deteriorates the composite mechanical performance, including Young modulus and tensile strength, compared to the neat bioLDPE.

Comprehensive Analysis of the Influence of Expanded Vermiculite on the Foaming Process and Selected Properties of Composite Rigid Polyurethane Foams.

This article presents the results of research on obtaining new polyurethane (PUR) foams modified with thermally expanded vermiculite. The filler was added in amount of 3 wt.% up to 15 wt.%. The additionally applied procedure of immersion the non-organic filler in H2O2 was performed to increase the exfoliation effect of thermally treated mineral and additional oxidation the surfaces. The effect of fillers on foaming process, cell structure, thermal insulation, apparent density, compressive strength, thermal properties, and flammability are assessed. The foaming process of PUR foams modified with vermiculite was comparable for all systems, regardless of the content of the filler. A slight increase in reactivity was observed, confirmed by a faster decrease in dielectric polarization for the system with modified vermiculite by H2O2. The modification of the reference system with the vermiculite increased the content of closed cells from 76% to 91% for the foams with the highest vermiculite content. Coefficient of thermal conductivity of reference foam and foams modified with vermiculite was in the range 24-26 mW/mK. The use of vermiculite up to 15 wt.% did not influence significantly on mechanical properties and flammability, which from an economic point of view is important because it is possible to reduce the cost of materials by introducing a cheap filler without deteriorating their properties.

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.

The Relationship between a Rotational Molding Processing Procedure and the Structure and Properties of Biobased Polyethylene Composites Filled with Expanded Vermiculite.

Rotational molding is a technology in which polymeric thin-walled products can be made. The newest descriptions of this technology concern the possibility of obtaining polymer composite materials. There are two main methods of incorporating fillers into a polymer matrix. Dry blending is based on mixing fillers with polymer powders before rotational molding by hand or using automatic mixers. In the melt compounding method, fillers are mixed with the polymer in the preliminary step by melt processing and then grinding or pulverization to obtain polymer powders for rotational molding. This work aimed to investigate the impact of the processing procedure on the structure and properties of biobased composites with expanded vermiculite. Produced rotomolded parts were examined using mechanical tests to assess changes in tensile, flexural, and impact properties. The most significant difference in mechanical properties was noted for samples with 10 wt% expanded vermiculite (EV). The elasticity modulus increases by almost 2 fold when the sample is prepared in a two-step process, the tensile strength is 4-fold higher, the flexural modulus is 3-fold higher, and the flexural strength is 5-fold higher. We also investigated thermomechanical properties in DMA measurement. The void volume content was also measured to control the quality of obtained parts. The porosity of dry blended samples containing more than 2 wt% EV is almost 2-fold higher. Other methods to control quality and structure were optical and scanning electron microscopy used for rotomolded parts and polymer powders. The investigations of rotomolded parts were supplemented with a complete description of used materials, including the particle size distributions of polymer powders and filler. Analysis of the thermal properties and chemical structure was also performed despite all the mechanical tests. The emerging conclusions from the research clearly show that the two-step process allows for achieving a more beneficial mechanical performance of the composites made of the biobased polymer in rotational molding technology.

A Novel Manufacturing Concept of LCP Fiber-Reinforced GPET-Based Sandwich Structures with an FDM 3D-Printed Core.

The presented research was focused on the development of a new method of sandwich structure manufacturing involving FDM-printing (fused deposition modeling) techniques and compression molding. The presented concept allows for the preparation of thermoplastic-based composites with enhanced mechanical properties. The sample preparation process consists of 3D printing the sandwich's core structure using the FDM method. For comparison purposes, we used two types of GPET (copolymer of polyethylene terephthalate)-based filaments, pure resin, and carbon fiber (CF)-reinforced filaments. The outer reinforcing layer "skins" of the sandwich structure were prepared from the compression molded prepregs made from the LCP (liquid-crystal polymer)-fiber fabric with the GPET-based matrix. The final product consisting of an FDM-printed core and LCP-based prepreg was prepared using the compression molding method. The prepared samples were subjected to detailed materials analyses, including thermal analyses (thermogravimetry-TGA, differencial scanning calorimetry-DSC, and dynamic thermal-mechanical analysis-DMTA) and mechanical tests (tensile, flexural, and impact). As indicated by the static test results, the modulus and strength of the prepared composites were slightly improved; however, the stiffness of the prepared materials was more related to the presence of the CF-reinforced filament than the presence of the composite prepreg. The main advantage of using the developed method is revealed during impact tests. Due to the presence of long LCP fibers, the prepared sandwich samples are characterized by very high impact resistance. The impact strength increased from 1.7 kJ/m2 for pure GPET samples to 50.4 kJ/m2 for sandwich composites. For GPET/CF samples, the increase is even greater. The advantages of the developed solution were illustrated during puncture tests in which none of the sandwich samples were pierced.

Thermomechanical and Fire Properties of Polyethylene-Composite-Filled Ammonium Polyphosphate and Inorganic Fillers: An Evaluation of Their Modification Efficiency.

The development of new polymer compositions characterized by a reduced environmental impact while lowering the price for applications in large-scale production requires the search for solutions based on the reduction in the polymer content in composites' structure, as well as the use of fillers from sustainable sources. The study aimed to comprehensively evaluate introducing low-cost inorganic fillers, such as copper slag (CS), basalt powder (BP), and expanded vermiculite (VM), into the flame-retarded ammonium polyphosphate polyethylene composition (PE/APP). The addition of fillers (5-20 wt%) increased the stiffness and hardness of PE/APP, both at room and at elevated temperatures, which may increase the applicability range of the flame retardant polyethylene. The deterioration of composites' tensile strength and impact strength induced by the presence of inorganic fillers compared to the unmodified polymer is described in detail. The addition of BP, CS, and VM with the simultaneous participation of APP with a total share of 40 wt% caused only a 3.1, 4.6, and 3 MPa decrease in the tensile strength compared to the reference value of 23 MPa found for PE. In turn, the cone calorimeter measurements allowed for the observation of a synergistic effect between APP and VM, reducing the peak heat rate release (pHRR) by 60% compared to unmodified PE. Incorporating fillers with a similar thermal stability but differing particle size distribution and shape led to additional information on their effectiveness in changing the properties of polyethylene. Critical examinations of changes in the mechanical and thermomechanical properties related to the structure analysis enabled the definition of the potential application perspectives analyzed in terms of burning behavior in a cone calorimetry test. Adding inorganic fillers derived from waste significantly reduces the flammability of composites with a matrix of thermoplastic polymers while increasing their sustainability and lowering their price without considerably reducing their mechanical properties, which allows for assigning developed materials as a replacement for flame-retarded polyethylene in large-scale non-loaded parts.