Synthetic Biopolymers and Their Composites: Advantages and Limitations-An Overview.

Recently, polymer science and engineering research has shifted toward the development of environmentally benign polymers to reduce the impact of plastic leakage on the ecosystems. Stringent regulations and concerns regarding conventional polymers are the main driving forces for the development of renewable, biodegradable, sustainable, and environmentally benign materials. Although biopolymers can alleviate plastic-related pollution, several factors dictate the utilization of biopolymers. Herein, an overview of the potential and limitations of synthetic biopolymers and their composites in the context of environmentally benign materials for a sustainable future are presented. The synthetic biopolymer market, technical advancements for different applications, lifecycle analysis, and biodegradability are covered. The current trends, challenges, and opportunities for bioplastic recycling are also discussed. In summary, this review is expected to provide guidelines for future development related to synthetic biopolymer-based sustainable polymeric materials suitable for various applications.

Flow Characteristics, Mechanical, Thermal, and Thermomechanical Properties, and 3D Printability of Biodegradable Polylactide Containing Boehmite at Different Loadings.

This work investigates the effects of modification of polylactide (PLA) using dicumyl peroxide (DCP) as a crosslinker and Joncryl as a chain extender on boehmite distribution. The PLA/boehmite (PLA/BA) composites at various concentrations were prepared via a twin-screw extruder. Transmission electron microscopy showed more agglomerations of BA particles when Joncryl and DCP were added individually to the PLA matrix, with lesser agglomeration upon simultaneous addition of DCP and Joncryl, which led to an enhancement of 10.7% of the heat distortion temperature and 8.8% of the modulus. The existence of fine dispersed BA particles in the BA3 sample improved the cold crystallization by 4 °C. Moreover, the maximum reinforcing effect in increasing the storage modulus of the prepared system was observed upon concurrent addition of DCP and Joncryl, with minimum reinforcing effect upon individual addition of DCP and Joncryl. In general, a bio-based PLA composite base BA with enhanced properties was successfully prepared for various applications.

Design of Poly(cyclotriphosphazene)-Functionalized Zirconium Phosphate Nanoplatelets To Simultaneously Enhance the Dynamic Mechanical and Flame Retardancy Properties of Polyamide 6.

To obtain polyamide 6 (PA6) composites with improved flame retardancy and thermomechanical properties, highly cross-linked supramolecular poly(cyclotriphosphazene)-functionalized α-zirconium phosphate (f-ZrP) nanoplatelets were synthesized and melt-blended with PA6 in a twin-screw extruder. The performance enhancements of composites were investigated through measuring the dynamic mechanical property and observing cone calorimeter data, toxic gas evolution, and UL-94 rating. The thermomechanical performance of PA6 was increased by 37.2% after composite formation with f-ZrP. As for the fire retardancy performance, compared to neat PA6, the composite containing 10 wt % f-ZrP showed 41.7 and 30.4% decrease in the peak heat and total heat release rates, respectively, and the UL-94 rating of the composite was V-0. Moreover, the thermogravimetric analysis combined with infrared spectroscopy revealed that the addition of f-ZrP to the PA6 led to decrease in the evolution of the volatile compounds and toxic gases, with the formation of highly cross-linked P-N-containing dense char with microspheres, providing a strong barrier to the inhibition of the heat and flammable volatile components transferring between the flame zone area and substrate during the combustion test. Finally, based on the obtained results, the possible mechanisms for improved mechanical and fire retardancy properties of the composites were proposed.

Mechanism of Thermal Degradation-Induced Gel Formation in Polyamide 6/Ethylene Vinyl Alcohol Blend Nanocomposites Studied by Time-Resolved Rheology and Hyphenated Thermogravimetric Analyzer Fourier Transform Infrared Spectroscopy Mass Spectroscopy: Synergistic Role of Nanoparticles and Maleic-anhydride-Grafted Polypropylene.

In this study, polyamide 6 (PA) is blended with ethylene vinyl alcohol (EVOH) to yield packaging materials with a balance of mechanical and gas barrier properties. However, the formation of gel-like structures in both polymers because of thermal degradation at high temperatures leads to a processing challenge, particularly during thin-gauge film extrusion. To address this challenge, nanoclays are introduced either directly or via a masterbatch of maleic-anhydride-grafted polypropylene to the PA/EVOH blend and time-resolved rheometry is used to study the effect of different modes of nanoclay incorporation on the kinetics of thermo-oxidative degradation of PA/EVOH blend and its nanocomposites. Time-resolved rheometry measurements allow the acquisition of accurate frequency-dependent linear viscoelastic behavior and offer insights into the rate of degradation or gel formation kinetics and cross-link density. The thermal degradation was studied by thermogravimetric analysis coupled with Fourier transform infrared spectroscopy and mass spectroscopy, allowing the prediction of the possible reactions that take place during the rheological property measurements. The results show that when nanoclays are incorporated directly, the oxidative reactions occur faster. In contrast, in the masterbatch method, oxidative degradation is hindered. The difference in the behaviors is shown to lie in the different nanoclay distributions in the blends; in the blends prepared by the masterbatch method, the nanoclays are dispersed at the interface. In conclusion, the masterbatch-containing blend nanocomposite would benefit processing and product development.

Cellulose Nanostructure-Based Biodegradable Nanocomposite Foams: A Brief Overview on the Recent Advancements and Perspectives.

The interest in designing new environmentally friendly materials has led to the development of biodegradable foams as a potential substitute to most currently used fossil fuel-derived polymer foams. Despite the possibility of developing biodegradable and environmentally friendly polymer foams, the challenge of foaming biopolymers still persists as they have very low melt strength and viscosity as well as low crystallisation kinetics. Studies have shown that the incorporation of cellulose nanostructure (CN) particles into biopolymers can enhance the foamability of these materials. In addition, the final properties and performance of the foamed products can be improved with the addition of these nanoparticles. They not only aid in foamability but also act as nucleating agents by controlling the morphological properties of the foamed material. Here, we provide a critical and accessible overview of the influence of CN particles on the properties of biodegradable foams; in particular, their rheological, thermal, mechanical, and flammability and thermal insulating properties and biodegradability.

Thermal Degradation Characteristic and Flame Retardancy of Polylactide-Based Nanobiocomposites.

Polylactide (PLA) is one of the most widely used organic bio-degradable polymers. However, it has poor flame retardancy characteristics. To address this disadvantage, we performed melt-blending of PLA with intumescent flame retardants (IFRs; melamine phosphate and pentaerythritol) in the presence of organically modified montmorillonite (OMMT), which resulted in nanobiocomposites with excellent intumescent char formation and improved flame retardant characteristics. Triphenyl benzyl phosphonium (OMMT-1)- and tributyl hexadecyl phosphonium (OMMT-2)-modified MMTs were used in this study. Thermogravimetric analysis in combination with Fourier transform infrared spectroscopy showed that these nanocomposites release a smaller amount of toxic gases during thermal degradation than unmodified PLA. Melt-rheological behaviors supported the conclusions drawn from the cone calorimeter data and char structure of the various nanobiocomposites. Moreover, the characteristic of the surfactant used for the modification of MMT played a crucial role in controlling the fire properties of the composites. For example, the nanocomposite containing 5 wt.% OMMT-1 showed significantly improved fire properties with a 47% and 68% decrease in peak heat and total heat release rates, respectively, as compared with those of unmodified PLA. In summary, melt-blending of PLA, IFR, and OMMT has potential in the development of high-performance PLA-based sustainable materials.

The Distribution of Nanoclay Particles at the Interface and Their Influence on the Microstructure Development and Rheological Properties of Reactively Processed Biodegradable Polylactide/Poly(butylene succinate) Blend Nanocomposites.

The present work investigates the distribution of nanoclay particles at the interface and their influence on the microstructure development and non-linear rheological properties of reactively processed biodegradable polylactide/poly(butylene succinate) blend nanocomposites. Two types of organoclays, one is more hydrophilic (Cloisite®30B (C30B)) and another one is more hydrophobic (BetsopaTM (BET)), were used at different concentrations. Surface and transmission electron microscopies were respectively used to study the blend morphology evolution and for probing the dispersion and distribution of nanoclay platelets within the blend matrix and at the interface. The results suggested that both organoclays tended to localize at the interface between the blend's two phases and encapsulate the dispersed poly(butylene succinate) phase, thereby suppressing coalescence. Using small angle X-ray scattering the probability of finding neighboring nanoclay particles in the blend matrix was calculated using the Generalized Indirect Fourier Transformation technique. Fourier Transform-rheology was utilized for quantifying nonlinear rheological responses and for correlating the extent of dispersion as well as the blend morphological evolution, for different organoclay loadings. The rheological responses were in good agreement with the X-ray scattering and electron microscopic results. It was revealed that C30B nanoparticles were more efficient in stabilizing the morphologies by evenly distributing at the interface. Nonlinear coefficient from FT-rheology was found to be more pronounced in case of blends filled with C30B, indicating better dispersion of C30B compare with BET which was in agreement with the SAXS results.

Thermal and rheological properties of biodegradable poly[(butylene succinate)-co-adipate] nanocomposites.

The thermal and rheological properties of clay-containing poly[(butylene succinate)-co-adipate] (PBSA) nanocomposites are reported. The nanocomposites of PBSA with various weight percentages of organically modified montmorillonite (OMMT) loadings have been prepared by melt-mixing in a batch-mixer. The melting and crystallization behaviours of PBSA and its nanocomposites have been studied using differential scanning calorimeter (DSC). The melt-state rheological properties of pure PBSA and its nanocomposites containing different amounts of OMMT have been studied in detail. The reason for this is that the rheological responses of any nanofilled polymeric materials are strongly related by their dispersed structure and the interfacial characteristic. Results show that the structural strength of all samples remains constant in the examined time interval at an experimental temperature. The dominant viscous behaviour of pure PBSA is getting suppressed up to a certain OMMT loading (4 wt%). Nanocomposite containing 5 wt% OMMT is showing almost "at the gel point" behaviour, suggesting that the material is behaving near the borderline between liquid and solid; while nanocomposite containing 6 wt% OMMT is showing the gel character. The dispersed structure of the clay particles in the PBSA matrix was studied by scanning transmission electron microscopy (STEM). Results show that the stacked and intercalated silicate layers are nicely dispersed in the case of all nanocomposites. However, with a systematic increase in OMMT loading, the dispersed clay structure of the nanocomposites changes from a highly delaminated to a flocculated and then to a stacked-intercalated structure. In the case of all nanocomposites, melt-state rheological properties are in good agreement with the STEM observations.

Nonisothermal crystallization kinetics of poly(ethylene terephthalate) nanocomposites.

This article reports the nonisothermal crystallization kinetics of poly(ethylene terephthalate) (PET) nanocomposites. The non-isothermal crystallization behaviors of PET and the nanocomposite samples are studied by differential scanning calorimetry (DSC). Various models, namely the Avrami method, the Ozawa method, and the combined Avrami-Ozawa method, are applied to describe the kinetics of the non-isothermal crystallization. The combined Avrami and Ozawa models proposed by Liu and Mo also fit with the experimental data. Different kinetic parameters determined from these models prove that in nanocomposite samples intercalated silicate particles are efficient to start crystallization earlier by nucleation, however, the crystal growth decrease in nanocomposites due to the intercalation of polymer chains in the silicate galleries. Polarized optical microscopy (POM) observations also support the DSC results. The activation energies for crystallization has been estimated on the basis of three models such as Augis-Bennett, Kissinger and Takhor methods follow the trend PET/2C20A < PET/1.3C20A < PET, indicating incorporation of organoclay enhance the crystallization by offering large surface area.