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Microbial treatment of biodegradable wastes not only ensures neutralization of harmful substances such as volatile organic compounds but also enables valorization and bio-circularity within the society. Single cell protein (SCP) is a value-added product that can be obtained from biodegradable waste materials such as food waste via microbial fermentation. In this article, SCP derived from potato starch waste was demonstrated as a viable alternative to existing plant/animal proteins used in the production of films, for example, packaging applications. Flexible glycerol-plasticized SCP films were prepared through compression molding, and tensile tests revealed strength and stiffness similar to other plasticized protein films. The oxygen barrier properties were significantly better compared to the common polyethylene packaging material, but as with other highly polar materials, the SCP material must be shielded from moisture if used in, for example, food packaging. The biodegradation test revealed a similar degradation pattern as observed for a household compostable bag. The results showed that SCP-based bioplastic films can be considered as potential alternative to the existing plant/animal protein films and certain synthetic polymers. An important advantage with these protein materials is that they do not cause problems similar to microplastics.

In this work, montmorillonite clay was organically modified using two surfactants which are largely different in their chemical structure - one is dimethyldihydrogenated ammonium chloride tallow (DDACT), that contains two long alkyl chains and the other is tributyl phosphonium molecule (TPB), a molecule containing short alkyl chains. The objective of the work is to study the effect of these surfactants’ structure on the properties of OPBI for proton exchange membrane (PEM) fuel cell applications. The morphology study of the membranes using PXRD and TEM revealed intercalated nanostructures using both the clays. The increment in thermal stability and Tg was found to be higher in the case of TPB modified clay membranes than the tallow amine modified clay membranes. Acid doping and swelling studies were performed and the values again reflected the nature of the surfactant used with phosphonium cation containing membranes showing higher PA doping levels. Specific swelling volume of the membranes portrayed the controlled swelling behaviour of all the nanocomposite membranes. Proton conductivity of the membranes were found to be lower than the pristine OPBI owing to the tortuous conduction pathway created by the clay sheets.

Biocomposites being environmentally-friendly alternative to synthetic composites are gaining increasing demand for various applications. Hence, biocomposite development should be integrated within a circular economy (CE) model to ensure a sustainable production that is simultaneously innocuous towards the environment. This review presents an overview of the state-of-the-art technologies for the adoption of the CE concept in biocomposite development. The study outlined the properties, environmental and economic impacts of biocomposites. A critical review of the life-cycle assessment of biocomposite for evaluating greenhouse gas emissions and carbon footprints was conducted. In addition, the opportunities and challenges pertaining to the implementation of CE have been discussed in detail. Recycling and utilisation of bio-based constituents were identified as the critical factors in embracing CE. Therefore, the development of innovative recycling technologies and an enhanced use of novel biocomposite constituents could lead to a reduction in material waste and environmental footprints. This article is one of the first studies to review the circularity of biocomposites in detail that will stimulate further research in enhancing the sustainability of these polymeric materials.

The global coronavirus disease 2019 (COVID‐19) pandemic has rapidly increased the demand for facemasks as a measure to reduce the rapid spread of the pathogen. Throughout the pandemic, some countries such as Italy had a monthly demand of ca. 90 million facemasks. Domestic mask manufacturers are capable of manufacturing 8 million masks each week, although the demand was 40 million per week during March 2020. This dramatic increase has contributed to a spike in the generation of facemask waste. Facemasks are often manufactured with synthetic materials that are non‐biodegradable, and their increased usage and improper disposal are raising environmental concerns. Consequently, there is a strong interest for developing biodegradable facemasks made with for example, renewable nanofibres. A range of natural polymer‐based nanofibres has been studied for their potential to be used in air filter applications. This review article examines potential natural polymer‐based nanofibres along with their filtration and antimicrobial capabilities for developing biodegradable facemask that will promote a cleaner production.

In this work, we have carried out in-situ RAFT polymerization of poly (N-vinylimidazole) (PNVI) in the inter-galleries of Cloisite nanoclay. The polymerization was carried out in two sets of different solvent-initiator combinations: N, N-Dimethyl formamide (DMF) - azobisisobutyronitrile (AIBN) and water/ethanol mixture - 4,4′-azobis (4-cyanovaleric acid) (ACV), with varying monomer ratios in order to synthesize PNVI of three different molecular weights. The three PNVI modified Cloisite clays (named as CP-1, CP-2 and CP-3 corresponding to low, medium and high molecular weight PNVI, respectively) were characterized thoroughly. X-ray diffraction and field emission scanning electron microscope analysis revealed the extent of delamination of the clay layers after the polymerization. The CP-3 clay, containing high molecular weight PNVI, was completely exfoliated, whereas the CP-1 clay with low molecular weight PNVI formed intercalated structure and CP-2 showed partial exfoliation. Gel permeable chromatography was used to determine the molecular weights of PNVI and the thermogravimetric analysis revealed the quantities of PNVI polymerized in the clays galleries. Further, the PNVI modified clays were used to prepare nanocomposites with poly (4,4′-diphenylether-5,5′-benzimidazole) (OPBI). All the nanocomposite membranes exhibited higher storage modulus (up to ~170% increase at 400 °C), tensile properties, acid doping levels (~30 mol/OPBI repeat unit), proton conductivity (0.19 S/cm at 180 °C) and controlled acid leaching. The CP-3 clay, with exfoliated clay layers and freely dispersed PNVI chains in the OPBI matrix, resulted in effective interfacial interactions with the OPBI chains and consequently demonstrated higher property enhancement of the nanocomposite membranes than when the other two clays were incorporated.

Summary Understanding structure-property relationship between polymer-nanoparticle interface and the distribution of interfacial region and its properties is crucial in establishing the bulk properties of polymer like mechanical stability and conductivity. In this article we try to draw a comparison of the effect of silica nanoparticles modified with three different modifiers on the properties of oxy-polybenzimidazole (OPBI) to understand the role played by the chemical structure of the organic modifying molecule. We highlight how small changes in the structure of the chosen molecule can bring about substantial improvements in polymer nanocomposites owing to the self-assembly of nanofillers. We use aminopropyltriethoxysilane (AMS), N-(3-trimethoxysilylpropyl) diethylenetriamine (LAMS) and ionic liquid modified silica (ILMS) for the surface modification of silica nanoparticles. The extent of interfacial interaction between each of these silica nanoparticles with OPBI matrix was found to be in the order OPBI/AMS

Despite the wide range of studies illustrating the influence of type and quantity of nanoclay on the macro properties of polymer nanocomposites, it has always remained a biggest challenge to study the chemistry of organic/inorganic interface on the final properties of polymer nanocomposites, a study that can indeed aid us in designing tailor-made materials e.g. proton exchange membranes (PEM). Hence in this study, we aimed to explore the influence of interface chemistry of nano-clay on the properties of poly(4,4′-diphenylether-5,5′-bibenzimidazole) (OPBI)/clay nanocomposite PEM for fuel cell. Cloisite clay modified organically with three surfactant molecules differing structurally in their cationic head group – cetyltrimethyl ammonium bromide (CTAB), cetylpyridinium bromide (CPyB) and cetylimidazolium bromide (CImiB) was utilized for making OPBI nanocomposite membranes by a simple solution blending route. 13 C CP MAS solid state NMR confirmed the hydrogen bonding interactions between the OPBI chains and clay particles. Formation of intercalated clay nanostructures in the OPBI matrix was revealed by WAXD and TEM analyses and this morphology was found to influence different properties in a favorable manner. TGA and DMA studies highlighted the influence of the different surfactants on the interfacial interactions in elevating/decreasing the thermal and glass transition temperatures of the nanocomposite membranes. The use of different surfactant modified clays induced sufficient hydrophobicity in the membranes that led to higher phosphoric acid (PA) loading and controlled dimensional swelling in both water and PA. The proton conductivity data particularly underscored the different degrees of interfacial interactions each of the three differently modified clays had in creating efficient proton transport pathways giving rise to higher proton conductivity while decreasing the activation energy barrier for the proton hopping. The results also revealed the critical role played by the clay particles especially by the organic modifier in preventing the leaching away of the doped acid from the nanocomposites membranes.

Although microbial fuel cells (MFCs) represent a promising bio-energy technology with a dual advantage (i.e., electricity production and waste-water treatment), their low power densities and high installation costs are major impediments. To address these bottlenecks and replace highly expensive Nafion, which is a proton exchange membrane (PEM), the current study focuses for the first time on membranes made from an easily synthesizable and more economical oxy-polybenzimidazole (OPBI) and its sulfonated analogue (S-OPBI) as alternate PEMs in single-chambered MFCs. The S-OPBI membrane exhibits better properties, with high water uptake, ion exchange capacity (IEC) and proton conductivity and a comparatively smaller degree of swelling compared to Nafion. The membrane morphology is characterized by atomic force microscopy, and the bright and dark regions of the S-OPBI membrane reveals the formation of ionic domains in the matrix, forming continuous water nanochannels when doped with water. These water-filled nanochannels are responsible for faster proton conduction in S-OPBI than in Nafion; therefore, the power output in the MFC with S-OPBI as the PEM is higher than in other MFCs. The open circuit voltage (460 mV), current generation (2.27 mA) and power density profile (110 mW/m2) as a function of time, as well as the polarization curves, exhibits higher current and power density (87.8 mW/m2) with S-OPBI compared to Nafion as the PEM.

ABSTARCT RAFT is a unique technique for the surface functionalization of nanoparticles as it enables us to tailor-make the properties of the final brush polymers by altering the parameters like graft density, chain length etc. of the grafted polymers and also to have the preferred choice of end functional groups with narrow size distribution of the nanoparticles. In this study, we successfully grafted poly(vinylimidazolium)bromide (PVImBr) polyionic liquid (PIL) brush polymers on the surface of silica nanoparticles (SiNPs) using metal-catalyst-free and a simplified RAFT technique compared to reported methods. Two sets of nanoparticles, one with low grafting and molecular weight [PVImBr(L)-g-SiNP] and the other with high grafting and molecular weight [PVImBr(H)-g-SiNP] were prepared using the versatile 4-cyanopentanoic acid dithiobenzoate (CPDB) as RAFT agent. 1H NMR, FTIR, DLS, TGA and FESEM confirmed the grafting of the polymer, amount of grafted polymer and their sizes. These two sets of PIL grafted nanoparticles were used to make two sets of nanocomposites with poly(4,4′-diphenylether-5,5′- bibenzimidazole) (OPBI) at three different filler concentrations. The aim was to study the effect of PIL grafting and their molecular weights on the morphology and macro-scale properties of OPBI nanocomposites. It was found that PVImBr(H)-g-SiNP incorporated nanocomposite membranes resulted in better interfacial properties owing to the greater miscibility and interfacial interactions with imidazolium functional groups of OPBI chains. These membranes displayed greater tensile strength, storage modulus, acid loading, proton conductivity and more importantly significantly lowered acid leaching.

In this article, we report a new amorphous-crystalline polymer blend system consisting of poly (4, 4′-diphenylether-5, 5′-bibenzimidazole) (OPBI) and poly (aminophosphonate ester) (PAPE) polymers, the membranes of which were fabricated using the solution blending route. A series of blend membranes at different ratios were prepared and systematically analysed for chemical interactions, morphological changes and their physico-chemical properties studied for use as proton exchange membrane. While FT-IR spectroscopy established the hydrogen bonding interactions between N–H of OPBI and phosphonate ester group of PAPE, X-ray diffraction studies revealed the development of crystallinity in the membrane matrix. Interestingly, the gradual induction of crystallinity in an amorphous OPBI matrix was found to influence the properties of the blend membranes favourably. For instance, the blend membrane containing 25 wt% PAPE in OPBI matrix displayed the maximum property enhancement in terms of storage modulus, glass transition temperature (Tg), phosphoric acid (PA) doping level (37 mol/OPBI repeat unit) and most importantly proton conductivity (0.135 S/cm at 180 °C) which is almost twice the value for pristine OPBI (0.05 S/cm at 180 °C) under identical conditions. Although improved properties were observed at other blend ratios as well, the studies ascertain that the membrane with 25 wt% PAPE was found to be the threshold ratio up to which properties increase and beyond which i.e. at >25 wt% PAPE, there is a decrement in properties like mechanical stability and proton conductivity. An important reason for this was attributed to the creation of a right balance of amorphous and crystalline domains and appropriate intra and inter-polymer hydrogen bonding interactions in the matrix of 75/25 (OPBI/PAPE) blend membrane.

Despite the remarkable advances in recent times on polybenzimidazole (PBI) based proton exchange membranes (PEM), there are two most important limitations that restrict their uses: (1) declining of the mechanical strength at high acid doping level and (2) leaching of doped acid when membrane is in contact with water. In continuation with our earlier success (J. Mater. Chem. 2011, 21, 14897; ACS Appl. Mater. Interfaces 2014, 6, 21286) on the former concern, in this article we also addressed the latter problem associated with ‘Acid leaching’ along with the issue of mechanical strength at high PA loading. We have made an attempt to study how the surface modifier molecule plays a role in altering the morphology and structure of poly (4, 4′-diphenylether-5, 5′-bibenzimidazole) (OPBI) nanocomposite membranes thereby enhancing the PEM properties especially acid retention capability. Silica nanoparticles of 25 nm size were prepared and successfully modified with phosphate anion containing imidazolium ionic liquid (IL) and were incorporated in OPBI by solution blending method. The chemical interactions between the polymer and ionic liquid modified silica (ILMS) were confirmed by FTIR, NMR and WAXD studies. TEM images disclosed how these interactions led to the formation of self-assembled clusters in the OPBI matrix. All the ILMS nanocomposite membranes displayed high thermal, mechanical and oxidative stabilities. The IL-decorated silica nanoparticles prevented the leaching of phosphoric acid (PA), by hydrogen bonding interactions, from the PA doped membranes. This resulted in higher PA doping levels of the nanocomposites. The ability to retain more PA was also reflected in the high proton conductivity data of the ILMS nanocomposites – 15% ILMS loaded membrane which showed almost two fold increment in proton conductivity compared to the neat OPBI. This was attributed to the self – assembled clusters of ILMS nanoparticles in the matrix.

Although increased number of reports in recent years on proton exchange membrane (PEM) developed from nanocomposites of polybenzimidazole (PBI) with inorganic fillers brought hope to end the saga of contradiction between proton conductivity and variety of stabilities, such as mechanical, thermal,chemical, etc.; it still remains a prime challenge to develop a highly conducting PEM with superior aforementioned stabilities. In fact the very limited understanding of the interactions especially interfacial interaction between PBI and inorganic filler leads to confusion over the choice of inorganic filler type and their surface functionalities. Taking clue from our earlier study based on poly(4,4'-diphenylether-5,5'-bibenzimidazole) (OPBI)/silica nanocomposites, where silica nanoparticles modified with short chain amine showed interfacial interaction-dependent properties, in this work we explored the possibility of enhanced interfacial interaction and control over the interface by optimizing the chemistry of the silica surface. We functionalized the surface of silica nanoparticles with a longer aliphatic chain having multiple amine groups (named as long chain amine modified silica and abbreviated as LAMS). FTIR and (13)C solid-state NMR provided proof of hydrogen bonding interactions between the amine groups of modifier and those of OPBI. LAMS nanoparticles yielded a more distinguished self-assembly extending all over the OPBI matrix with increasing concentrations. The crystalline nature of these self-assembled clusters was probed by wide-angle X-ray diffraction (WAXD) studies and the morphological features were captured by transmission electron microscope (TEM). We demonstrated the changes in storage modulus and glass transition temperature (Tg) of the membranes, the fundamental parameters that are more sensitive to interfacial structure using temperature dependent dynamic mechanical analysis (DMA). All the nanocomposite membranes displayed enhanced mechanical, thermal and chemical stability than neat OPBI. The lower water uptake and swelling ratio and volume in both acid and water reflected the more hydrophobic characteristic of the nanocomposites. All the nanocomposite membranes showed phosphoric acid (PA) values to be higher than OPBI but the levels showed decreasing trend with increasing silica content; the reason attributed to the interparticle interaction. The self-assembled clusters of LAMS nanoparticles in the matrix created more sites for proton hopping as a result of which the proton conductivity of all the nanocomposites displayed an increasing trend.