Influence of α′‐/α‐crystal polymorphism on properties of poly(l‐lactic acid)

Poly(l ‐lactic acid) (PLLA) is a biodegradable and biocompatible thermoplastic polyester produced from renewable sources, widely used for biomedical devices, in food packaging and in agriculture. It is a semicrystalline polymer, and as such its properties are strongly affected by the developed semicrystalline morphology. As a function of the crystallization temperature, PLLA can form different crystal modifications, namely α′‐crystals below about 120 °C and α‐crystals at higher temperatures. The α′ modification is therefore of special importance as it may be the preferred polymorph developing at processing‐relevant conditions. It is a metastable modification which typically transforms into the more stable α‐crystals on annealing at elevated temperature. The structure, kinetics of formation and thermodynamics of α′‐ and α‐crystals of PLLA are reviewed in this contribution, together with the effect of α′‐/α‐crystal polymorphism on the properties of PLLA. © 2018 Society of Chemical Industry     

Development and characterization of poly(vinyl alcohol) and casein blend films

Blends of plasticized casein (CA) and poly(vinyl alcohol) (PVA) at various ratios were prepared using the solution‐casting method. The prepared blend solutions were cast onto polystyrene petri plates and bend films were obtained. The characterization of films was performed using Fourier transform infrared spectroscopy, tensile testing, thermogravimetric analysis, contact angle measurements and water vapour permeability. According to spectroscopic analysis, there were interactions between the CA and PVA molecules. The tensile test results showed that the tensile strength of CA increased with increasing PVA content. The flexibility of plasticized CA film increased with the incorporation of PVA. The thermal stability and water vapour barrier properties of plasticized CA improved on blending with PVA. As a result, it was seen that blend films were successfully produced using plasticized CA and PVA with potential for use in biodegradable packaging applications. © 2019 Society of Chemical Industry     

Manganese oxides treated with organic compounds as catalysts for water oxidation reaction

Manganese oxides of different crystalline structures: α-MnO₂, δ-MnO₂, α,γ-MnO₂ and Mn₂O₃; were treated with the organic compounds picolinic acid, ethylenediamine and pyridine; and were applied as catalysts in the chemical water oxidation reaction using Ce(IV) ammonium nitrate as sacrificial oxidant. The treatment led to modifications in the oxides properties, such as reduction of the particle size, increase of surface area and partial reduction of Mn⁴⁺ to Mn³⁺ for the Mn(IV) oxides, or of Mn³⁺ to Mn²⁺ for Mn₂O₃, because of favored interactions of the organic molecules with the lattice planes with higher d spacing. Oxygen evolution reaction (OER) tests showed the superior catalytic activity of the treated Mn(IV) oxides, for instance α,γ-MnO₂-en presented TOF five times higher than pure α,γ-MnO₂. The increase in surface area as well as the higher Mn³⁺ content caused by the treatment of the Mn(IV) oxides were correlated with the improvement in the OER catalytic activity.     

Tungsten(VI) oxide supported rhodium nanoparticles: Highly active catalysts in hydrogen generation from ammonia borane

Herein, we report the use of tungsten(VI) oxide (WO₃) as support for Rh⁰ nanoparticles. The resulting Rh⁰/WO₃ nanoparticles are highly active and stable catalysts in H₂ generation from the hydrolysis of ammonia borane (AB). We present the results of our investigation on the particle size distribution, catalytic activity and stability of Rh⁰/WO₃ catalysts with 0.5%, 1.0%, 2.0% wt. Rh loadings in the hydrolysis reaction. The results reveal that Rh⁰/WO₃ (0.5% wt. Rh) is very promising catalyst providing a turnover frequency of 749 min^?1 in releasing 3.0 equivalent H₂ per mole of AB from the hydrolysis at 25.0 °C. The high catalytic activity of Rh⁰/WO₃ catalyst is attributed to the reducible nature of support. The report covers the results of kinetics study as well as comparative investigation of activity, recyclability, and reusability of colloidal(0) nanoparticles and Rh⁰/WO₃ (0.5 % wt. Rh) catalyst in the hydrolysis reaction.     

Current trends in structural development and modification strategies for metal-organic frameworks (MOFs) towards photocatalytic H2 production: A review

Photocatalytic H₂ generation using semiconductor photocatalysts is considered as a cost-effective and eco-friendly technology for solar to energy conversion; however, the present photocatalysts have been recognized to depict low efficiency. Currently, porous coordination polymers known as metal-organic frameworks (MOFs) constituting flexible and modifiable porous structure and having excess active sites are considered to be appropriate for photocatalytic H₂ production. This review highlights current progress in structural development of MOF materials along with modification strategies for enhanced photoactivity. Initially, the review discusses the photocatalytic H₂ production mechanism with the concepts of thermodynamics and mass transfer with particular focus on MOFs. Elaboration of the structural categories of MOFs into Type I, Type II, Type III and classification of MOFs for H₂ generation into transition metal based, post-transition metal based, noble-metal based and hetero-metal based has been systematically discussed. The review also critically deliberate various modification approaches of band engineering, improvement of charge separation, efficient irradiation utilization and overall efficiency of MOFs including metal modification, heterojunction formation, Z-scheme formation, by introducing electron mediator, and dye based composites. Also, the MOF synthesized derivatives for photocatalytic H₂ generation are elaborated. Finally, future perspectives of MOFs for H₂ generation and approaches for efficiency improvement have been suggested.     

CFD model for tubular SOFC directly fed by biomass

The coupling between biomass gasification and Solid Oxide Fuel Cells can represent a sustainable and efficient system for electricity production. This work aims to develop a preliminary model for the operation of a tubular, electrolyte-supported fuel cell (SOFC) fed by a syngas mixture. The fuel required by the SOFC system is produced inside the energy generator box from an integrated biomass gasification system. This study stems from the European DB-SOFC project, that proposed the exploitation of the abundant biomasses deriving from agricultural residues for energetic purposes (as from olive oil and wine production). In this study, the main processes have been simulated to find a possible configuration to obtain a power value of 200 W. 25 cells were used in the model to produce the required power. The results showed that at 0.7 V it is possible to achieve 12.3 W, when the biomass gasification was integrated into the SOFC box, while it was possible to achieve 9.6 W when the system was fed by externally produced syngas.     

Real-time organic aerosol chemical speciation in the indoor environment using extractive electrospray ionization mass spectrometry

Understanding the sources and composition of organic aerosol (OA) in indoor environments requires rapid measurements, since many emissions and processes have short timescales. However, real-time molecular-level OA measurements have not been reported indoors. Here, we present quantitative measurements, at a time resolution of five seconds, of molecular ions corresponding to diverse aerosol-phase species, by applying extractive electrospray ionization mass spectrometry (EESI-MS) to indoor air analysis for the first time, as part of the highly instrumented HOMEChem field study. We demonstrate how the complex spectra of EESI-MS are screened in order to extract chemical information and investigate the possibility of interference from gas-phase semivolatile species. During experiments that simulated the Thanksgiving US holiday meal preparation, EESI-MS quantified multiple species, including fatty acids, carbohydrates, siloxanes, and phthalates. Intercomparisons with Aerosol Mass Spectrometer (AMS) and Scanning Mobility Particle Sizer suggest that EESI-MS quantified a large fraction of OA. Comparisons with FIGAERO-CIMS shows similar signal levels and good correlation, with a range of 100 for the relative sensitivities. Comparisons with SV-TAG for phthalates and with SV-TAG and AMS for total siloxanes also show strong correlation. EESI-MS observations can be used with gas-phase measurements to identify co-emitted gas- and aerosol-phase species, and this is demonstrated using complementary gas-phase PTR-MS observations.     

Effect of plasma treatment of polymeric tape carriers on wetting behaviour of aqueous ceramic tape casting slurry

Due to environmental and health aspects, aqueous ceramic slurries are preferred to traditional organic solvent systems in tape casting. An important obstacle associated with the high surface energy of water is poor wetting of aqueous ceramic slurries on polymeric tape carriers. Therefore, we measured the contact angles of an aqueous epoxy-based ceramic slurry on polyethylene terephtalate (PET), polypropylene (PP), polymethyl methacrylate (PMMA), and aluminium-coated polyethylene terephtalate (PET-Al) films and investigated approaches to improving their wetting. We evaluated the effect of plasma treatment of the tape carrier surface on the wetting behaviour and compared it with the effect of adding non-ionic amphiphilic surfactants to the ceramic slurry. The treatment of the tape carrier surface by low-temperature plasma substantially improved the wetting behaviour of aqueous ceramic slurry. The lowest contact angle of 31° was obtained on the PET film. Although the addition of non-ionic surfactants improved both the wetting behaviour of the slurry and the detachment of the polymeric carrier from the ceramic tape even better than the plasma treatment of the carrier surface did, the plasma-treated carriers still present a useful alternative to the surfactants. In the case of the plasma-treated PET carrier the surfactants could be fully eliminated and potential drawbacks related to the use of surfactants could be prevented.     

Adsorptive removal of methylene blue from aqueous solution on activated carbon prepared from Malawian baobab fruit shell wastes: Equilibrium,kinetics and thermodynamic studies

Baobab fruit shell (BFS), a renewable bio-waste from Malawian baobab tree was used as a precursor for the production of a low-cost activated carbon to remove methylene blue (MB) from aqueous solution. Parameters such as contact time, initial methylene blue concentration, adsorbent dose and temperature were studied. The adsorption process can be well described by both Langmuir isotherm and the pseudo-second-order kinetics. The maximum monolayer adsorption capacity of MB dye was ca. 334.45 mg/g. The negative value of the Gibb’s free energy and positive value of adsorption enthalpy showed the spontaneous nature and endothermic nature of the adsorption process, respectively.