Thermoplastic starch/polyvinyl alcohol blends modification by citric acid-glycerol polyesters.

Thermoplastic starch/polyvinyl alcohol (TPS/PVA) films have limitations for being used in long-term applications due to starch retrogradation. This leads to plasticizer migration, especially when low molecular weight plasticizers such as glycerol, are used. In this work, we employed mixtures of oligomers based on glycerol citrates with higher molecular weight than glycerol as plasticizers for potato-based TPS/PVA blends obtained by melt-mixing. This constitutes an alternative to reduce plasticizer migration while keeping high swelling degree, and to provide high mechanical performance. The novelty lies in the usage of these oligomers by melt-mixing technique, aspect not deeply explored previously and that represents the first step towards industrial scalability. Prior to the blending process, oligomers mixtures were prepared with different molar ratios of citric acid (0-40 mol%) and added them. This minimizes the undesirable hydrolysis effect of free carboxylic groups on starch chains. The results demonstrated that the migration of plasticizers in TPS/PVA blends decreased by up to 70 % when the citric acid content increased. This reduction was attributed to the higher molecular weight (the majority in the range 764-2060 Da) and the 3D structure of the oligomers compared to using raw glycerol. Furthermore, the films exhibited a 150 % increase in Young's modulus and tensile strength without a reduction in elongation at break, while maintaining a high gel content, due to a moderate crosslinking.

Study of the Plasticization Effect of 1-Ethyl-3-methylimidazolium Acetate in TPS/PVA Biodegradable Blends Produced by Melt-Mixing.

The first step towards the production and marketing of bioplastics based on renewable and sustainable materials is to know their behavior at a semi-industrial scale. For this reason, in this work, the properties of thermoplastic starch (TPS)/polyvinyl alcohol (PVA) films plasticized by a green solvent, as the 1-ethyl-3-methylimidazolium acetate ([Emim+][Ac-]) ionic liquid, produced by melt-mixing were studied. These blends were prepared with a different content of [Emim+][Ac-] (27.5-42.5 %wt.) as a unique plasticizer. According to the results, this ionic liquid is an excellent plasticizer due to the transformation of the crystalline structure of the starch to an amorphous state, the increase in flexibility, and the drop in Tg, as the [Emim+][Ac-] amount increases. These findings show that the properties of these biomaterials could be modified in the function of [Emim+][Ac-] content in the formulations of TPS, depending on their final use, thus becoming a functional alternative to conventional polymers.

Effective Method for a Graphene Oxide with Impressive Selectivity in Carboxyl Groups.

The development of new applications of graphene oxide in the biomedical field requires the covalent bonding of bioactive molecules to a sheet skeleton. Obtaining a large carboxyl group population over the surface is one of the main targets, as carboxyl group concentration in conventional graphene oxide is low among a majority of non-useful sp3-C-based functionalities. In the present work, we propose a selective method that yields an impressive increase in carboxyl group population using single-layer, thermally reduced graphene oxide as a precursor in a conventional Hummers-Offemann reaction. When starting with a reduced graphene oxide with no interlayer registry, sulfuric acid cannot form a graphite intercalated compound. Then, potassium permanganate attacks in in-plane (vacancies or holes) structural defects, which are numerous over a thermally reduced graphene oxide, as well as in edges, yielding majorly carboxyl groups without sheet cutting and unzipping, as no carbon dot formation was observed. A single-layer precursor with no ordered stacking prevents the formation of an intercalated compound, and it is this mechanism of the potassium permanganate that results in carboxyl group formation and the hydrophilic character of the compound.

Exploring the effect of humidity on thermoplastic starch films using the quartz crystal microbalance.

The quartz crystal microbalance (QCM) is used as a non-destructive and efficient characterization tool for thin thermoplastic starch (TPS) films. Thin TPS films (1-2 µm) were prepared with 30% (w/w starch) plasticizers using either glycerol or an ionic liquid, 1-ethyl-3-methylimidiazolium acetate ([emim+][Ac-]), as the plasticizer. The differences in the mechanical properties and environmental effects on the plasticized TPS films were explored. The modulus of starch-glycerol films was higher than starch-[emim+][Ac-], consistent with literature data and bulk AFM measurements, likely due to superior plasticization by the ionic liquid. The starch-[emim+][Ac-] films were shown to have relative stable properties at low humidity that may be due to some antiplasticization effects at low water content despite absorbing more water than starch-glycerol films at higher humidity.

Influence of Starch Composition and Molecular Weight on Physicochemical Properties of Biodegradable Films.

Thermoplastic starch (TPS) films are considered one of the most promising alternatives for replacing synthetic polymers in the packaging field due to the starch biodegradability, low cost, and abundant availability. However, starch granule composition, expressed in terms of amylose content and phosphate monoesters, and molecular weight of starch clearly affects some film properties. In this contribution, biodegradable TPS films made from potato, corn, wheat, and rice starch were prepared using the casting technique. The effect of the grain structure of each starch on microstructure, transparency, hydration properties, crystallinity, and mechanical properties of the films, was evaluated. Potato starch films were the most transparent and corn starch films the most opaque. All the films had homogeneous internal structures-highly amorphous and with no pores, both of which point to a good starch gelatinization process. The maximum tensile strength (4.48-8.14 MPa), elongation at break (35.41-100.34%), and Young's modulus (116.42-294.98 MPa) of the TPS films were clearly influenced by the amylose content, molecular weight, and crystallinity of the film. In this respect, wheat and corn starch films, are the most resistant and least stretchable, while rice starch films are the most extensible but least resistant. These findings show that all the studied starches can be considered suitable for manufacturing resistant and flexible films with similar properties to those of synthetic low-density polyethylene (LDPE), by a simple and environmentally-friendly process.

Hybrid films with graphene oxide and metal nanoparticles could now replace indium tin oxide.

Graphene oxide (G-O), a highly oxidized sheet of sp(2)-hybridized carbon with insulating electrical properties, can be transformed into graphene if it is adequately reduced. In the past, researchers believed that reduced G-O (rG-O) could be highly conducting, but it has been shown that the presence of extended vacancies and defects within rG-O negatively affect its electrical transport. Although these observations indicated that rG-O could not be used in the fabrication of any electronic device, in this issue of ACS Nano, Ruoff's group demonstrates that rG-O can indeed be used for producing efficient transparent conducting films (TCFs) if the rG-O material is coupled with Au nanoparticles (Au-NPs) and Ag nanowires (Ag-NWs). The work further demonstrates that these hybrid films containing zero-dimensional (Au-NPs), one-dimensional (Ag-NWs), and two-dimensional (rG-O) elements exhibit high optical transmittance (e.g., 90%) and low sheet resistance (20-30 Ω/□), with values comparable to those of indium tin oxide (ITO) films. In addition, Ruoff's group notes that the presence of Ag-NWs and rG-O in the films showed antibacterial properties, thus demonstrating that it is now possible to produce flexible TCFs with bactericidal functions. The data show that smart hybrid films containing rG-O and different types of NPs and NWs could be synthesized easily and could result in smart films with unprecedented functions and applications.

Organic and inorganic pollutants from cement kiln stack feeding alternative fuels.

In this work, an analysis of the emission of different pollutants when replacing partially the fuel type used in a cement kiln is done. The wastes used to feed the kiln were tyres and two types of sewage sludge. The increasing mass flow of sludge is between 700 kg h(-1) and 5,500 kg h(-1)1, for a total production of clinker of 150th(-1), whereas the fed tyres were in the flow range of 500-1,500 kg h(-1). Dioxins and furans, polycyclic aromatic hydrocarbons (PAHs) and other hydrocarbons, heavy metals, HCl and HF, CO, CO(2), NO(x) and other parameters of the stack were analyzed, according to the standard methods of sampling and determination, through more than 1 year in six series: one blank (no sewage sludge) and five more with increasing amount of sludge and/or tyres. The emission of PAHs and dioxins seems to increase with the amount of tyres fed to the kiln, probably due to the fed point used for this waste.

Interaction between pollutants produced in sewage sludge combustion and cement raw material.

Nowadays the use of waste as secondary fuel in clinker kilns is an extensive practice, but the interaction between cement raw material (CRM) and the combustion gases of the fuels has not been extensively studied. Because of that, in this work the effect of the interaction of exhaust from the combustion of sewage sludge and CRM has been studied in a laboratory furnace. The experiments were performed at 300 degrees C, close to the temperature at the cyclones in a cement industry. The behavior of volatile compounds, polycyclic aromatic compounds (PAH) and polychloro dibenzo-p-dioxin and polychloro dibenzofurans (PCCD/F) were analysed in the presence or absence of CRM. The results obtained show that the presence of CRM at the outlet of the combustion gases is beneficial for the decrease of pollutant emissions.

Organic compounds produced during the thermal decomposition of cotton fabrics.

Used cotton fabrics, which can be considered a biomass according to its origin, were descomposed thermically in a laboratory scale reactor through a set of runs carried out in inert and air atmospheres, with temperatures between 650 and 1050 degrees C. More than 90 compounds, including carbon oxides, light hydrocarbons, and PAHs, have been identified and quantified. In the gas phase some of the main components obtained were methane, ethene, and benzene. The main semivolatile compounds detected were styrene, phenol, naphthalene, acenaphthylene, and phenanthrene. Furthermore, analyses of PCDD/Fs in the material tested and in the semivolatile compounds produced during the combustion at 850 degrees C were also performed, obtaining values of 14.5 (sample) and 7.2 pg I-TEQ/g (combustion). The congener that mostly contributes to the total I-TEQ was 2,3,4,7,8-PeCDF. The results obtained show that this waste could be used as biomass, and in this way, it is a valid alternative to disposal in landfills.