Long-term properties and end-of-life of polymers from renewable resources

The long-term properties and end-of-life of polymers are not antagonist issues. They actually are inherently linked by the duality between durability and degradation. The control of the service-todisposal pathway at useful performance, along with low-impact disposal represents an added-value. Therefore, the routes of design, production, and discarding of bio-based polymers must be carefully strategized. In this sense, the combination of proper valorisation techniques, i.e. material, energetic and/ or biological at the most appropriate stage should be targeted. Thus, the consideration of the end-of-life of a material for a specific application, instead of the end-of-life of a material should be the fundamental focus. This review covers the key aspects of lab-scale techniques to infer the potential of performance and valorisation of polymers from renewable resources as a key gear for sustainability

Suitability of Blends from Virgin and Reprocessed Polylactide: Performance and Energy Valorization Kinetics

A blending strategy of virgin and reprocessed polylactide may be postulated as an alternative to reduce the material cost at industrial level, and as a valorization route to plastic waste management of production scraps. The performance of blends prepared from virgin polylactide and polylactide mechanically reprocessed up to two cycles (PLA-V/R) was assessed in terms of thermo-oxidative stability, morphology, viscoelasticity and thermal kinetics for energetic valorization. PLA-V/R blends showed appropriate thermo-oxidative stability. The amorphous nature of polylactide was preserved after blending. The viscoelastic properties showed an increment of the mechanical blend effectiveness, which suggested the feasibility of using PLA-V/R blends under similar mechanical conditions to those of virgin PLA goods. Finally, it was shown that the energetic valorization of PLA-V/R blends would result in a more feasible process, due to the lower required activation energy, thus highlighting the advantages of the energetic demand for the process. In conclusion, PLA-V/R blends showed similar processability, service performance and valorization routes as virgin PLA and therefore could be relevant in the sustainable circular industry of bioplastics

Performance of polyester-based electrospun scaffolds under in vitro hydrolytic conditions: From short-term to long-term applications

The evaluation of the performance of polyesters under in vitro physiologic conditions is essential to design scaffolds with an adequate lifespan for a given application. In this line, the degradation-durability patterns of poly(lactide-co-glycolide) (PLGA), polydioxanone (PDO), polycaprolactone (PCL) and polyhydroxybutyrate (PHB) scaffolds were monitored and compared giving, as a result, a basis for the specific design of scaffolds from short-term to long-term applications. For this purpose, they were immersed in ultra-pure water and phosphate buffer solution (PBS) at 37 °C. The scaffolds for short-time applications were PLGA and PDO, in which the molar mass diminished down to 20% in a 20-30 days lifespan. While PDO developed crystallinity that prevented the geometry of the fibres, those of PLGA coalesced and collapsed. The scaffolds for long-term applications were PCL and PHB, in which the molar mass followed a progressive decrease, reaching values of 10% for PCL and almost 50% for PHB after 650 days of immersion. This resistant pattern was mainly ascribed to the stability of the crystalline domains of the fibres, in which the diameters remained almost unaffected. From the perspective of an adequate balance between the durability and degradation, this study may serve technologists as a reference point to design polyester-based scaffolds for biomedical applications

Influence of the Molecular Weight on PVA/GO Composite Membranes for Fuel Cell Applications

Composite polymer electrolyte membranes were prepared with poly (vinyl alcohol) (PVA). Two different molecular weight (Mw), 67·103 and 130·103 g·mol−1 were selected, cross-linked with sulfosuccinic acid (SSA) and doped graphene oxide (GO). The effects on the membranes obtained from these polymers were characterized in order to evaluate the fuel cell performance. Electron microscopy showed a proper nanoparticle distribution in the polymer matrix. The chemical structure was evaluated by Fourier transform infrared spectroscopy. The absence of a crystalline structure and the enhancement on the thermal stability with the addition of 1% of GO was demonstrated by thermal characterization. Total transference number and protonic conductivity were correlated to the performance of a hydrogen fuel cell. Overall, a power increase in the composite membranes with lower molecular weight was observed. Shorter polymer chains may improve protonic conductivity and consequently the fuel cell performance

Effect of the dissolution time into an acid hydrolytic solvent to taylor electrospun nanofibrous polycaprolactone scaffolds

The hydrolysis of the polycaprolactone (PCL) as a function of the dissolution time in a formic/ acetic acid mixture was considered as a method for tailoring the morphology of nanofibrous PCL scaffolds. Hence, the aim of this research was to establish a correlation between the dissolution time of the polymer in the acid solvent with the physicochemical properties of the electrospun nanofibrous scaffolds and their further service life behaviour. The physico-chemical properties of the scaffolds were assessed in terms of fibre morphology, molar mass and thermal behaviour. A reduction of the molar mass and the lamellar thickness as well as an increase of the crystallinity degree were observed as a function of dissolution time. Bead-free fibres were found after 24 and 48 h of dissolution time, with similar diameter distributions. The decrease of the fibre diameter distributions along with the apparition of beads was especially significant for scaffolds prepared after 72 h and 120 h of dissolution time in the acid mixture. The service life of the obtained devices was evaluated by means of in vitro validation under abiotic physiological conditions. All the scaffolds maintained the nanofibrous structure after 100 days of immersion in water and PBS. The molar mass was barely affected and the crystallinity degree and the lamellar thickness increased along immersion, preventing scaffolds from degradation. Scaffolds prepared after 24 h and 48 h kept their fibre diameters, whereas those prepared after 72 h and 120 h showed a significant reduction. This PCL tailoring procedure to obtain scaffolds that maintain the nanoscaled structure after such long in vitro evaluation will bring new opportunities in the design of longterm biomedical patches

Degradation of Plasticised Poly(lactide) Composites with Nanofibrillated Cellulose in Different Hydrothermal Environments

In this study, bionanocomposite films based on poly(lactide) (PLA) plasticised with poly(ethylene glycol) (PEG) (7.5 wt%) and reinforced with various contents of nanofibrillated cellulose (NFC) (1, 3, 5 wt%) were prepared. The hydrothermal degradation was investigated through immersion in several aqueous environments at temperatures of 8, 23, 58, and 70 °C as a function of time (7, 15, 30, 60, 90 days). The effect of water immersion on the physicochemical properties of the materials was assessed by monitoring the changes in the morphology, thermo-oxidative stability, thermal properties, and molar mass through field emission scanning electron microscopy (FE-SEM), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), and gel permeation chromatography (GPC). The hydrothermal degradation behaviour was not critically affected regardless of the nanofibrillated cellulose content. All the materials revealed certain integrity towards water immersion and hydrolysis effects at low temperatures (8 and 23 °C). The low hydrothermal degradation may be an advantage for using these PLA biocomposites in contact with water at ambient temperatures and limited exposure times. On the other hand, immersion in water at higher temperatures above the glass transition (58 and 70 °C), leads to a drastic deterioration of the properties of these PLA-based materials, in particular to the reduction of the molar mass and the disintegration into small pieces. This hydrothermal degradation behaviour can be considered a feasible option for the waste management of PLA/PEG/NFC bionanocomposites by deposition in hot aqueous environments

Functionalised poly (vinyl alcohol)/graphene oxide as polymer composite electrolyte membranes

Crosslinked poly(vinyl alcohol) (PVA) based composite films were prepared as polyelectrolyte membranes for low temperature direct ethanol fuel cells (DEFC). The membranes were functionalised by means of the addition of graphene oxide (GO) and sulfonated graphene oxide (SGO) and crosslinked with sulfosuccinic acid (SSA). The chemical structure was corroborated and suitable thermal properties were found. Although the addition of GO and SGO slightly decreased the proton conductivity of the membranes, a significant reduction of the ethanol solution swelling and crossover was encountered, more relevant for those functionalised with SGO. In general, the composite membranes were stable under simulated service conditions. The addition of GO and SGO particles permitted to buffer the loss and almost retain similar proton conductivity than prior to immersion. These membranes are alternative polyelectrolytes, which overcome current concerns of actual commercial membranes such as the high cost or the crossover phenomenon

Performance of Sulfonated Poly(Vinyl Alcohol)/Graphene Oxide Polyelectrolytes for Direct Methanol Fuel Cells

The use of nanotechnology along with the consideration of a functionalization and stabilization approach to poly(vinyl alcohol) (PVA) is considered useful for the preparation of cost-effective polyelectrolyte membranes. A set of nanocomposite and crosslinked membranes based on PVA/sulfosuccinic acid (SSA)/graphene oxide (GO) are prepared and analyzed as polyelectrolytes in direct methanol fuel cells (DMFCs). The crosslinking and sulfonation by the use of SSA enhances the stability and increase the proton-conducting sites in the PVA structure. The presence of GO augments the stability, remarkably decreases the methanol crossover, and enhances power density curves. An optimum value for proton conductivity is found for the 0.50 wt% of GO proportion, which decreases with higher concentrations of GO. Given the power density curve dependency on both the proton conductivity and the crossover reduction, the performance of these membranes as polyelectrolytes in DMFCs is strictly related to the balance between both factors. Therefore, a proportion of GO of 0.75 wt% may assure suitable proton conductivity of 3 mS cm−1 and high resistance to methanol permeability, reaching promising power density of 16 mW cm−2 with lower hydration levels

Structure–Properties Relationship of Reprocessed Bionanocomposites of Plasticized Polylactide Reinforced with Nanofibrillated Cellulose

Bionanocomposites of polylactide (PLA), plasticized with poly(ethylene glycol) (PEG) (7.5 wt%, 400 and 1500 g/mol) and reinforced with nanofibrillated cellulose (NFC) (1, 3, and 5 wt%) were sequentially compounded, and injection and compression molded. All of the stages caused structural and morphological consequences, more relevant in the plasticized PLA, especially with low molar PEG. Small percentages of NFC (1 and 3 wt%) acted as crystalline nucleating agents and improved thermo-oxidative stability. Given the substantial degradation caused by (re)processing, a downgrading validation strategy was applied, assessing the mechanical and water contact performance during fictional first and second service life applications. After the first processing, PEG increased the ductility and reduced the strength and elastic modulus, while NFC buffered the fall in stiffness and increased rigidity compared to their PLA-PEG counterparts. Once reprocessed, PEG increased the water affinity of the blend, especially for low molar mass PEG. Low percentages of NFC (1 and 3 wt%) modulated water diffusivity and permeability, regardless of the water temperature. Overall, although reprocessing caused significant degradation, the mechanical valorization possibilities of these green bionanocomposites were proven, and are pointed out as sustainable candidates for food packaging or agricultural applications where modulated mechanical or water contact behaviors are required

Biodegradation in soil effects on PLA/sisal and PHBV/sisal biocomposites

The use of bio-based composites like lignocellulosic fibres/polymer composites as an alternative materials are continuously increasing in several applications such as automobile manufacturing, packaging, construction or household and agricultural equipments. In order to warranty the durability on green biocomposites based on polymer matrixes like poly(hydroxy butyrate-co-valerate) (PHBV) and poly(lactide) (PLA), the previous knowledge about the influence of the ambient agents on their macromolecular properties is necessary. In this sense, biodegradation in soil normalised experiments are useful. In this work, two commercial PHBV and PLA were reinforced with sisal fibres at 10 %, 20% and 30% of weight, with the aid of maleic anhydride as coupling agent.the influence of the amount of sisal fiber and the effect of the coupling agent on the impact of the biodegradation in soil on the materiales, in terms of the variation of the physico-chemical properties of the biocomposites