Increasing interest in bio-based polymers and fibers has led to the development of several alternatives to conventional plastics and fibers made of these materials. Biopolymer fibers can be made from renewable, environmentally friendly resources and can be fully biodegradable. Biogenic resources with a high content of carbohydrates such as starch-containing plants have huge potentials to substitute conventional synthetic plastics in a number of applications. Much literature is available on the production and modification of starch-based fibers and blends of starch with other polymers. Chemistry and structure–property relationships of starch show that it can be used as an attractive source of raw material which can be exploited for conversion into a number of high-value bio-based products. In this review, possible spinning techniques for the development of virgin starch or starch/polymer blend fibers and their products are discussed. Beneficiation of starch for the development of bio-based fibers can result in the sustainable replacement of oil-based high-value materials with cost-effective, environmentally friendly, and abundant products.

Biobased poly(butylene succinate) (PBS) represents one promising sustainable alternative to petroleum-based polymers. Its sensitivity to thermo-oxidative degradation is one reason for its limited application. In this research, two different varieties of wine grape pomaces (WPs) were investigated as fully biobased stabilizers. WPs were prepared via simultaneous drying and grinding to be used as bio-additives or functional fillers at higher filling rates. The by-products were characterized in terms of composition and relative moisture, in addition to particle size distribution analysis, TGA, and assays to determine the total phenolic content and the antioxidant activity. Biobased PBS was processed with a twin-screw compounder with WP contents up to 20 wt.-%. The thermal and mechanical properties of the compounds were investigated with DSC, TGA, and tensile tests using injection-molded specimens. The thermo-oxidative stability was determined using dynamic OIT and oxidative TGA measurements. While the characteristic thermal properties of the materials remained almost unchanged, the mechanical properties were altered within expected ranges. The analysis of the thermo-oxidative stability revealed WP as an efficient stabilizer for biobased PBS. This research shows that WP, as a low-cost and biobased stabilizer, improves the thermo-oxidative stability of biobased PBS while maintaining its key properties for processing and technical applications.

Bio-based polyamide 10.10 (PA 10.10) has excellent properties compared to other bio-based polymers such as polylactic acid (PLA) or polyhydroxyalkanoates (PHAs) and is therefore used in more technical applications where higher strength is required. For foam and filament extrusion, a good balance between strength and stiffness of the polymer is needed. Therefore, two commercial chain-extenders (Joncryl^® ADR types) with different epoxy functionalities are used to modify the melt properties of PA 10.10. The chain-extenders are used in a concentration range up to 1.25 wt.%. The range of glass transition temperature widens with increasing Joncryl^® content, and the apparent activation energy shows a maximum at a concentration of 0.5 wt.%. Furthermore, the melting temperatures are constant and the crystallinity decreases with increasing chain-extender content due to the formation of branches. During the second heating run, a bimodal melting peak appeared, consisting of $\alpha$-triclinic and pseudo $\gamma$-hexagonal crystals. The weight average molar masses (M_w) measured by gel permeation chromatography (GPC) increased linearly with increasing ADR 4400 content. In contrast, the compounds containing ADR 4468 show a maximum at 0.5 wt.% and it begins to decrease thereafter. The rheological data show an increase in viscosity with increasing chain-extender content due to branch formation. ATR spectra of the compounds show a decrease at the wavelength of the primary (3301 cm⁻¹) and secondary (1634 cm⁻¹) (-NH stretching in PA 10.10) amine, indicating that chain-extension, e.g., branching, takes place during compounding.

Fermented polymers like biobased poly(butylene succinate) (BioPBS) have become more relevant as technical substitutes for ductile petrochemical-based polymers but require biogenic functional additives to deaccelerate undesired thermo-oxidative degradation and keep a fully biobased character. In this paper, the influence of coffee parchment (PMT) from two different varieties and processings on the thermo-oxidative stabilization and mechanical properties of poly(butylene succinate) composites up to 20 wt.-% PMT were investigated. Micronized with a TurboRotor mill, both PMT powders differ in particle size and shape, moisture ab- and adsorption behavior and antioxidative properties. It could be shown that pulped-natural PMT consists partially of coffee cherry residues, which leads to a higher total polyphenol content and water activity. The homogeneous PMT from fully washed processing has a higher thermal degradation resistance but consists of fibers with larger diameters. Compounded with the BioPBS and subsequent injection molded, the fully washed PMT leads to higher stiffness and equal tensile strength but lower toughness compared to the pulped-natural PMT, especially at lower deformation speed. Surprisingly, the fully washed PMT showed a higher stability against thermo-oxidative decomposition despite the lower values in the total phenol content and antioxidative activity. The required antioxidative stabilizers might be extracted at higher temperatures from the PMT fibers, making it a suitable biogenic stabilizer for extrusion processes.

When applying electron or gamma irradiation to poly-3-hydroxybutyrate (P3HB), main chain scissions are the dominant material reactions. Though propositions have been made that crosslinking in the amorphous phase of P3HB occurs under irradiation, a conclusive method to achieve controlled additive free irradiation crosslinking has not been shown and no mechanism has been derived to the best of our knowledge. By applying irradiation in a molten state at 195 °C and doses above 200 kGy, we were able to initiate crosslink reactions and achieved gel formation of up to 16%. The gel dose D_gel was determined to be 200 kGy and a range of the G values, the number of scissions and crosslinks for 100 eV energy deposition, is given. Rheology measurements, as well as size exclusion chromatography (SEC), showed indications for branching at doses from 100 to 250 kGy. Thermal analysis showed the development of a bimodal peak with a decrease in the peak melt temperature and an increase in peak width. In combination with an increase in the thermal degradation temperature for a dose of 200 kGy compared to 100 kGy, thermal analysis also showed phenomena attributed to branching and crosslinking.

Biopolyesters such as poly(butylene succinate) (PBS) show great potential to be used as biobased alternatives to conventional petroleum-based polyolefins. To access technical applications, biobased materials are mostly stabilized using conventional additives, which impair their biobased character. Wine grape pomace (WP), a largely unused, low-value by-product of winemaking, shows great potential to improve the thermo-oxidative stability. Since WP is a natural material, annual variations must be considered for its use as stabilizing bio-filler on an industrial scale. This study investigates the impact of annual variations of WP on the stabilizing effects in PBS. WP of two different varieties and three vintages were studied. The composition and properties of the native by-products were analyzed, and WP-based functional fillers were prepared by industrial mill-drying. The bio-fillers obtained were analyzed regarding their physical, thermal, biochemical, and antioxidant properties and blended into PBS with filler contents up to 20 wt.-% by twin-screw extrusion. The biocomposites’ thermal and thermo-oxidative properties were investigated subsequently. All WP varieties and vintages increased the thermo-oxidative stability of PBS by at least 24% at a filler content of 3 wt.-%, demonstrating the potential of WP as a reliable stabilizer. However, the maximum stabilization effect achieved varied slightly. The results of this study showed that minor differences in the bio-filler properties can be related to meteorological data, while the antioxidant activity, pH, and fat content could be used as bioanalytical indicators to evaluate the thermo-oxidative stabilization effects of WP-based functional fillers to enable reliable industrial applications of WP as a polymer stabilizer.