Fully biobased and biodegradable materials have attracted a growing interest in the food packaging sector as they can help to reduce the negative impact of fossil-based plastics on the environment. Moreover, the addition of functionalities to these materials by introducing active molecules has become an essential requirement to create modern packaging able to extend food's shelf-life while informing the consumer about food quality and freshness. In this study, we present an innovative bioplastic formulation for food packaging based on poly(hydroxybutyrate-co-valerate) (PHBV) and tannins as multifunctional additives. As a proof of concept, PHBV/tannin films were prepared by solvent casting, increasing the tannin content from 1 to 10 per hundred of resin (phr). Formic acid was used to reach a homogeneous distribution of the hydrophilic tannins into hydrophobic PHBV, which is remarkably challenging by using other solvents. Thanks to their well-known properties, the effect of tannins on the antioxidant, UV protection, and gas barrier properties of PHBV was evaluated. Samples containing 5 phr bioadditive revealed the best combination of these properties, also maintaining good transparency. Differential scanning calorimetry (DSC) investigations revealed that films are suitable for application from the fridge to potentially high temperatures for food heating (up to 200 °C). Tensile tests have also shown that Young's modulus (900-1030 MPa) and tensile strength (20 MPa) are comparable with those of the common polymers and biopolymers for packaging. Besides the improvement of the PHBV properties for extending food's shelf-life, it was also observed that PHBV/tannin could colorimetrically detect ammonia vapors, thus making this material potentially applicable as a smart indicator for food spoilage (e.g., detection of fish degradation). The presented outcomes suggest that tannins can add multifunctional properties to a polymeric material, opening up a new strategy to obtain an attractive alternative to petroleum-based plastics for smart food packaging applications.

The transport of H₂, He, CO₂, O₂, CH₄, and N₂ at three temperatures up to 65 °C was measured in dense, thick composite films formed by amorphous Polysulfone (PSf) and particles of the size-selective zeolitic imidazolate framework 8 (ZIF-8) at loadings up to 16 wt%. The morphological and structural properties of the membranes were analyzed via SEM and density measurement. The addition of ZIF-8 to PSf enhances the H₂ and He permeabilities up to 480% with respect to the pure polymer, while the ideal H₂/CO₂ and He/CO₂ selectivities of MMMs reach values up to 30–40% higher than those of pure PSf. The relative permeability and diffusivity enhancements are higher than those obtained in other polymers, such as PPO, with the same amount of filler. The Maxwell–Wagner–Sillars model is able to represent the MMM H₂/CO₂ separation performance for filler volume fractions below 10%.

Torlon^® is a thermally and plasticization-resistant polyamide imide characterized by low gas permeability at room temperature. In this work, we aimed at improving the polymer performance in the thermally-enhanced He/CO₂ and H₂/CO₂ separations, by compounding Torlon^® with a highly permeable filler, ZIF-8, to fabricate Mixed Matrix Membranes (MMMs). The effect of filler loading, gas size, and temperature on the MMMs permeability, diffusivity, and selectivity was investigated. The He permeability increased by a factor of 3, while the He/CO₂ selectivity decreased by a factor of 2, when adding 25 wt % of ZIF-8 at 65 °C to Torlon^®; similar trends were observed for the case of H₂. The MMMs permeability and size-selectivity were both enhanced by temperature. The behavior of MMMs is intermediate between the pure polymer and pure filler ones, and can be described with models for composites, indicating that such materials have a good polymer/filler adhesion and their performance could be tailored by acting on the formulation. The behavior observed is in line with previous investigations on MMMs based on glassy polymers and ZIF-8, in similar conditions, and indicates that ZIF-8 can be used as a polymer additive when the permeability is a controlling aspect, with a proper choice of loading and operative temperature.

In this work, we assessed the CO₂ and CH₄ sorption and transport in copolymers of 3-hydroxybutyrate and 3-hydroxyvalerate (PHBV), which showed good CO₂ capture potential in our previous papers, thanks to their good solubility–selectivity, and are potential biodegradable alternatives to standard membrane-separation materials. Experimental tests were carried out on a commercial material containing 8% of 3-hydroxyvalerate (HV), while molecular modelling was used to screen the performance of the copolymers across the entire composition range by simulating structures with 0%, 8%, 60%, and 100% HV, with the aim to provide a guide for the selection of the membrane material. The polymers were simulated using molecular dynamics (MD) models and validated against experimental density, solubility parameters, and X-ray diffraction. The CO₂/CH₄ solubility–selectivity predicted by the Widom insertion method is in good agreement with experimental data, while the diffusivity–selectivity obtained via mean square displacement is somewhat overestimated. Overall, simulations indicate promising behaviour for the homopolymer containing 100% of HV. In part 2 of this series of papers, we will investigate the same biomaterials using a macroscopic model for polymers and compare the accuracy and performance of the two approaches.

Anion exchange membranes are utilised in cutting-edge energy technologies including electrolysers and fuel cells. Recently, these membranes have also emerged as a promising tool in CO₂ capture techniques, such as moisture-driven direct air capture and the separation of CO₂ from other gases, leveraging the moisture-induced sorption/desorption and diffusion of CO₂ in its ionic forms. In this study, we examine the absorption and permeation of CO₂ and CH₄ in two commercially available anion exchange membranes, Fumasep^® and Sustainion^®, under dry conditions. With the exception of CO₂ sorption in Fumasep^®, these measurements have not been previously reported. These new data points are crucial for evaluating the fundamental separation capabilities of these materials and for devising innovative CO₂ capture strategies, as well as for the simulation of novel combined processes. In a dry state, both materials demonstrate similar CO₂ absorption levels, with a higher value for Sustainion^®. The CO₂ solubility coefficient decreases with pressure, as is typical for glassy polymers. Fumasep^® exhibits higher CO₂/CH₄ ideal solubility selectivity, equal to ~10 at sub-ambient pressures, and higher diffusivity. The CO₂ diffusion coefficient increases with the CO₂ concentration in both membranes due to swelling of the matrix, varying between 0.7 and 2.2 × 10⁻⁸ cm²/s for Fumasep^® and between 1.6 and 9.0 × 10⁻⁹ cm²/s for Sustainion^®. CO₂ permeability exhibits a minimum at a pressure of approximately 2–3 bar. The CO₂ permeability in the dry state is higher in Fumasep^® than in Sustainion^®: 3.43 and 0.72 Barrer at a 2-bar transmembrane pressure, respectively. The estimated perm-selectivity was found to reach values of up to 40 at sub-ambient pressures. The CO₂ permeability and CO₂/CH₄ estimated perm-selectivity in both polymers are of a similar order of magnitude to those measured in fluorinated ion exchange membranes such as Nafion^®.

The majority of materials used for membrane-based separation of gas mixtures are non-renewable and non-biodegradable, and the assessment of alternative bio-based polymers requires expensive and time-consuming experimental campaigns. This effort can be reduced by adopting suitable modelling approaches. In this series of works, we propose various modelling approaches to assess the CO₂/CH₄ separation performance of eight different copolymers of 3-hydroxybutyrate and 3-hydroxyvalerate (PHBV) using a limited amount of experimental data for model calibration. In part 1, we adopted a fully atomistic approach based on Molecular Dynamics (MD), while, in this work, we propose a multiscale methodology where a molecular description of the polymers is bridged to a macroscopic prediction of its gas sorption behaviour. PHBV structures were simulated using MD to obtain pressure–volume–temperature data, which were used to parametrise the Sanchez–Lacombe Equation of State. This, in turn, allows for the evaluation of the CO₂ and CH₄ solubility in the copolymers at various pressures and compositions with little computational effort, enabling the estimate of the sorption-based selectivity. The gas separation performance obtained with this multiscale technique was compared to results obtained with a fully atomistic model and experimental data. The solubility–selectivity for the CO₂/CH₄ mixture is in reasonable agreement between the two models and the experimental data. The multiscale method presented is a time-efficient alternative to fully atomistic methods and detailed experimental campaigns and can accelerate the introduction of renewable materials in different applications.