Thermal Decomposition of Bio-Based Plastic Materials.

This research delves into a detailed exploration of the thermal decomposition behavior of bio-based polymers, specifically thermoplastic starch (TPS) and polylactic acid (PLA), under varying heating rates in a nitrogen atmosphere. This study employs thermogravimetry (TG) to investigate, providing comprehensive insights into the thermal stability of these eco-friendly polymers. In particular, the TPS kinetic model is examined, encompassing the decomposition of three distinct fractions. In contrast, PLA exhibits a simplified kinetic behavior requiring only a fraction described by a zero-order model. The kinetic study involves a systematic investigation into the individual contributions of key components within TPS, including starch, glycerin, and polyvinyl alcohol (PVA). This detailed analysis contributes to a comprehensive understanding of the thermal degradation process of TPS and PLA, enabling the optimization of processing conditions and the prediction of material behavior across varying thermal environments. Furthermore, the incorporation of different starch sources and calcium carbonate additives in TPS enhances our understanding of the polymer's thermal stability, offering insights into potential applications in diverse industries.

Study on Physicochemical Properties of Biocomposite Films with Spent Coffee Grounds as a Filler and Their Influence on Physiological State of Growing Plants.

The aim of the study was to plasticize corn starch with two selected urea (U)-rich plasticizers: choline chloride (CC):U or betaine (B):U eutectic mixtures at a molar ratio of 1:5 with a presence of spent coffee grounds as a filler. The biomaterials were prepared via a solventless one-step extrusion method and then extrudates were thermoformed using compression molding into sheets. The materials were characterized using mechanical and sorption tests, TGA, DMTA and FTIR. Additionally, a study on the biodegradation and remaining nitrogen content in soil was conducted. For the first time, an influence on physiological state of growing plants of the materials presence in soil was investigated. The addition of the coffee filler slightly increased the mechanical properties and decreased the swelling degree of the materials. The DMTA results indicated that biocomposites were easily thermoformable and the high filler addition (20 pph per polymer matrix) did not affect the processability. According to the biodegradation test results, the materials disappeared in soil within ca. 70 days. The results from this study on the physiological state of growing plants revealed that the materials, especially plasticized with CCU, did not exhibit any toxic effect on the yellow dwarf bean. The percentage of total nitrogen in the soil substrate in comparison with the control increased indicating an effective release of nitrogen from the TPS materials into the substrate.

Treatment of food waste contaminated by bioplastics using BSF larvae: Impact and fate of starch-based bioplastic films.

The use of Black Soldier Fly (BSF) larvae in the treatment of biowaste, including food waste, represents a promising new (waste) treatment option. In line with an increasing use of starch-based bioplastics in food packaging, (e.g. shopper films), food waste contamination by these polymers is expected to rise, but the fate of these materials and impact produced on the BSF treatment process remain to be clarified. In the present study, food waste contaminated by starch-based bioplastic film was treated using a BSF larvae process with the aim of investigating both the effect of bioplastics on process performance and the effect of BSF larvae on bioplastic degradation. Larvae treatment performance was assessed by monitoring substrate degradation process and larvae growth in terms of weight variation and development time. Bioplastic degradation (both in the larvae process and in a larvae-free control test) was assessed by means of visual inspection, Scanning Electron Microscopy (SEM), Fourier Transform InfraRed spectroscopy (FTIR), Differential Scanning Calorimetry (DSC) and ThermoGravimetric Analysis (TGA). The results obtained highlighted the absence of negative impacts of bioplastics on the BSF process, revealing a modestly higher degree of degradation in the larvae process compared to control test. The process however failed to achieve complete degradation of bioplastics, suggesting the need for additional post-processing treatments.

Thermogravimetric, Morphological and Infrared Analysis of Blends Involving Thermoplastic Starch and Poly(ethylene-co-methacrylic acid) and Its Ionomer Form.

This study focuses on the thermal properties and structural features of blends consisting of thermoplastic starch (TPS) and poly(ethylene-co-methacrylic acid) copolymer (EMAA) or its ionomer form (EMAA-54Na). The aim is to investigate how carboxylate functional groups of the ionomer form intervene in blends compatibility at the interface of the two materials and how this impacts their properties. Two series of blends (TPS/EMAA and TPS/EMAA-54Na) were produced with an internal mixer, with TPS compositions between 5 and 90 wt%. Thermogravimetry shows two main weight losses, indicating that TPS and the two copolymers are primarily immiscible. However, a small weight loss existing at intermediate degradation temperature between those of the two pristine components reveals specific interactions at the interface. At a mesoscale level, scanning electron microscopy confirmed thermogravimetry results and showed a two-phase domain morphology, with a phase inversion at around 80 wt% TPS, but also revealed a different surface appearance evolution between the two series. Fourier-transformed infrared spectroscopy analysis also revealed discrepancies in fingerprint between the two series of blends, analysed in terms of additional interactions in TPS/EMAA-54Na coming from the supplementary sodium neutralized carboxylate functions of the ionomer.

Towards the Hydrophobization of Thermoplastic Starch Using Fatty Acid Starch Ester as Additive.

To bring surface hydrophobicity to thermoplastic starch (TPS) materials for food packaging, fatty acid starch esters (FASE), specifically starch tri-laurate, were incorporated into TPS formulations. A total of three different ratios of FASE (2%, 5% and 10%) were added to the TPS formulation to evaluate the influence of FASE onto physico-chemical properties of TPS/FASE blends, i.e., surface hydrophobicity, dynamic vapor sorption (DVS), and tensile behaviors. Blending TPS with FASE leads to more hydrophobic materials, whatever the FASE ratio, with initially measured contact angles ranging from 90° for the 2%-FASE blend to 99° for the 10%-blend. FT-IR study of the material surface and inner core shows that FASE is mainly located at the material surface, justifying the increase of material surface hydrophobicity. Despite this surface hydrophobicity, blending TPS with FASE seems not to affect blend vapor sorption behavior. From a mechanical behavior perspective, the variability of tensile properties of starch-based materials with humidity rate is slightly reduced with increasing FASE ratio (a decrease of maximal stress of 10-30% was observed for FASE ratio 2% and 10%), leading to more ductile materials.

Effect of biodegradable active packaging with zeolites on fresh broccoli florets.

Most of the food packaging is mainly petroleum-based, and new forms of food packaging have emerged, such as active, intelligent, and biodegradable packaging to extend the shelf life of fresh vegetables. The aim was to develop a biodegradable active packaging and senescence indicator label for fresh broccoli florets (Brassica oleracea L. var. italica), to increase shelf life and to monitor the decay of the vegetable. The biodegradable active packagings (BAP) were produced by blown extrusion containing zeolite as ethylene scavenger, and their mechanical properties, water vapor permeability, and water sorption isotherms were determined. Fresh broccoli florets were packed in perforated and non-perforated BAP and stored at 12 °C, and their weight loss, vitamin C content, color, and texture were evaluated during the storage. BAPs were efficient in reducing the metabolism of fresh broccoli florets stored at 12 °C, preserving the color, and vitamin C content for 7 days. The senescence indicator labels were able to detect CO2 in packages without perforations.

Bio-Based Thermoplastic Starch Composites Reinforced by Dialdehyde Lignocellulose.

In order to improve the mechanical properties and water resistance of thermoplastic starch (TPS), a novel reinforcement of dialdehyde lignocellulose (DLC) was prepared via the oxidation of lignocellulose (LC) using sodium periodate. Then, the DLC-reinforced TPS composites were prepared by an extrusion and injection process using glycerol as a plasticizer. The DLC and LC were characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM), and the effects of DLC content on the properties of the DLC/TPS composites were investigated via the evaluation of SEM images, mechanical properties, thermal stability, and contact angles. XRD showed that the crystallinity of the DLC decreased due to oxidation damage to the LC. SEM showed good dispersion of the DLC in the continuous TPS phase at low amounts of DLC, which related to good mechanical properties. The tensile strength of the DLC/TPS composite reached a maximum at a DLC content of 3 wt.%, while the elongation at break of the DLC/TPS composites increased with increasing DLC content. The DLC/TPS composites had better thermal stability than the neat TPS. As the DLC content increased, the water resistance first increased, then decreased. The highest tensile strength and elongation at break reached 5.26 MPa and 111.25%, respectively, and the highest contact angle was about 90.7°.

Physical-Chemical Evaluation of Active Food Packaging Material Based on Thermoplastic Starch Loaded with Grape cane Extract.

The aim of this paper is to evaluate the physicochemical and microbiological properties of active thermoplastic starch-based materials. The extract obtained from grape cane waste was used as a source of stilbene bioactive components to enhance the functional properties of thermoplastic starch (TPS). The biomaterials were prepared by the compression molding technique and subjected to mechanical, thermal, antioxidant, and microbiological tests. The results showed that the addition of grape cane extract up to 15 wt% (TPS/WE15) did not significantly influence the thermal stability of obtained biomaterials, whereas mechanical resistance decreased. On the other side, among all tested pathogens, thermoplastic starch based materials showed antifungal activity toward Botrytis cinerea and antimicrobial activity toward Staphylococcus aureus, suggesting potential application in food packaging as an active biomaterial layer.

Rheological, Thermal, Superficial, and Morphological Properties of Thermoplastic Achira Starch Modified with Lactic Acid and Oleic Acid.

The modification of achira starch a thermoplastic biopolymer is shown. Glycerol and sorbitol, common plasticizers, were used in the molten state with organic acids such as oleic acid and lactic acid obtaining thermodynamically more stable products. The proportion of starch:plasticizer was 70:30, and the acid agent was added in portions from 3%, 6%, and 9% by weight. These mixtures were obtained in a torque rheometer for 10 min at 130 °C. The lactic acid managed to efficiently promote the gelatinization process by increasing the available polar sites towards the surface of the material; as a result, there were lower values in the contact angle, these results were corroborated with the analysis performed by differential scanning calorimetry and X-ray diffraction. The results derived from oscillatory rheological analysis had a viscous behavior in the thermoplastic starch samples and with the presence of acids; this behavior favors the transitions from viscous to elastic. The mixture of sorbitol or glycerol with lactic acid promoted lower values of the loss module, the storage module, and the complex viscosity, which means lower residual energy in the transition of the viscous state to the elastic state; this allows the compounds to be scaled to conventional polymer transformation processes.

Effect of branched 1,4-butanediol citrate oligomers with different molecular weights on toughness and aging resistance of glycerol plasticized starch.

The thermoplastic starch with glycerol is easy to retrograde and sensitive to hygroscopicity. In this study, branched 1,4-butanediol citrate oligomers with different molecular weights (P1, P2, and P3) are synthesized, and then mixed with glycerol (G) as the co-plasticizers to prepare thermoplastic starch (CS/PG). The results show that the molecular weight and branching degree of the branched 1,4-butanediol citrate oligomers increase as reaction time prolongs. Compared with glycerol plasticized starch, the thermoplastic starch films with branched 1,4-butanediol citrate oligomers/glycerol (10 wt%/20 wt%) have a better toughness, transmittance, and aging resistance, and have a lower crystallinity, hygroscopicity, and thermal stability. The toughness, transmittance, and aging resistance of CS/PG films are positively correlated with the molecular weight of the branched 1,4-butanediol citrate oligomers. These are due to the fact that the branched 1,4-butanediol citrate oligomer with a high molecular weight could form a stronger hydrogen bond and the more stable cross-linked structure with starch chains than that with a lower molecular weight. The elongation at break of CS/P3G film stored for 3 and 30 d are 98.0 % and 88.1 %, respectively. The mixture of branched butanediol citrate oligomers and glycerol, especially P3/G, has a potential application in the preparation of thermoplastic starch.