New insights into oxygen surface coverage and the resulting two-component structure of graphene oxide

Elucidating the essential details of the structure of graphene oxide (GO) is still a challenge. There is no consensus in the increasingly abundant literature, especially relating to the epoxy groups as the main surface complexes in the basal plane, as well as the simultaneous presence of GO sheets and oxidative debris (OD), with a large difference in their oxygen content. In the present work we characterized the base-washed GO (bwGO) sheets, the OD and the humic fraction of the OD obtained by base digestion, when the parent GO was dispersed by applying sonication, a routine procedure when starting from dried graphite oxide. When sonication is not applied, the amount of OD detected is considerably lower, indicative of its formation before base digestion. The presence of lactols and carboxylic anhydrides as the dominant surface complexes at graphene edges is consistent with all the characterization results, as well as with the general knowledge of surface chemistry of carbon materials ranging from coal to graphite. These findings suggest that the Hummers-Offeman reaction produces a chemical scissor effect during the water/hydrogen peroxide quenching step, yielding a broad size distribution of GO sheets, with little in-plane oxidation and the vast majority of edges being oxidized to form oxepinone-type functionalities.The authors gratefully acknowledge the financial support of the Ministerio de Economía y Competitividad of Spain (Project CTQ2013-44213-R), and Generalitat Valenciana (project PROMETEOII/2014/007). LRR is grateful for the support of CONICYT-Chile (project Fondecyt 1160949)

Comparative study on properties of starch films obtained from potato, corn and wheat using 1-ethyl-3-methylimidazolium acetate as plasticizer

Starch films are gaining attention as substitutes of synthetic polymers due to their biodegradability and low cost. Some ionic liquids have been postulated as alternatives to glycerol, one of the best starch plasticizers, due to their great capacity to form hydrogen bonds with starch and hence great ability of preventing starch retrogradation and increasing film stability. In this work, [emim+][Ac−]-plasticized starch films were prepared from potato, corn and wheat starch. The effect of starch molecular structure in terms of granular composition (amylose and phosphate monoester contents) and molecular weight (Mw) on film properties was evaluated. Potato starch films were the most amorphous because of the higher Mw and phosphate monoester content of potato starch, both contributing to a lower rearrangement of the starch chains making the crystallization process difficult. In contrast, corn and wheat starches lead to more crystalline films because of their lower Mw, which may imply higher mobility and crystal growth rate, and lower phosphate monoester content. This more crystalline structure could be the responsible of their better mechanical properties. [emim+][Ac−] can be considered suitable for manufacturing starch films showing corn and wheat starch films similar properties to synthetic low-density polyethylene, but involving a simple and environmentally-friendly process.This work was partially supported from the European Commission, European-Union and Ministerio de Economía y Competitividad (MINECO), Spain (Ref. CTQ2016-78246-R) and Generalitat Valenciana (Project PROMETEOII/2014/007). M.G. Montalbán acknowledges support from Ministerio de Economía y Competitividad (MINECO) (Juan de la Cierva-Formación contract, Ref. FJCI-2016-28081)

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.This work was partially supported by the European Commission (FEDER/ERDF), the Spanish MINECO (Ref. CTQ2016-78246-R), and Generalitat Valenciana (Project PROMETEOII/2014/007). M.G.M. acknowledges support from MINECO (Juan de la Cierva-Formación contract, Ref. FJCI-2016-28081)

Custom-Made Chemically Modified Graphene Oxide to Improve the Anti-Scratch Resistance of Urethane-Acrylate Transparent Coatings

In this work, a thermoset ultraviolet (UV)-cured polyurethane-acrylate resin was doped with different chemically-modified graphene obtained from a commercial graphene oxide (GO): as-received GO, chemically reduced GO (rGO), GO functionalized with vinyltriethoxysilane (VTES) (GOvtes), and GO functionalized with VTES and subsequently reduced with a chemical agent (rGOvtes). Modified graphene was introduced in the oligomer component via solvent-assisted process using acetone, which was recovered after completion of the process. Results indicate that the GO-doped oligomers produce cured coatings with improved anti-scratch resistance (above the resistance of conventional coatings), without surface defects and high transparency. The anti-scratch resistance was measured with atomic force microscopy (AFM). Additionally, results are presented in terms of Wolf–Wilburn scale, a straightforward method widely accepted and employed in the coating industry.This research was funded by MINISTERIO DE ECONOMÍA Y COMPETITIVIDAD (MINECO) of Spain (CTQ2014-54772-P and CTQ2013-44213-R); and GENERALITAT VALENCIANA (ROMETEOII/2014/007)

Study of the behavior of biodegradable starch/polyvinyl alcohol/rosin blends

Biodegradable potato starch/PVA samples containing different concentrations of rosin were prepared by melt-mixing in order to study the enhancement of the properties of native starch films. Glycerol and polyvinyl alcohol (PVA) are commonly used as plasticizers of starch. Their relatively low molecular weight (compared with starch) contributes to a good processability. Rosin is a renewable product whose incorporation in the starch/PVA matrix induces processing aid and reinforcing effects. Its relatively high molecular weight might prevent its migration to the surface of the final product. Water content, solubility in water, mechanical properties, microstructure and dynamic mechanical analysis of the samples were studied. The addition of 8% rosin to starch/PVA blends led to tensile strength values higher than 10 MPa and elongation at break values close to 2000%, values comparable to those offered by conventional polymers used in food packaging, for example LDPE. Furthermore, starch compounds have low cost and high biodegradability.This work was partially supported from the European Commission (FEDER/ERDF) and the Spanish MINECO (Ref. CTQ2016-78246-R) and Generalitat Valenciana (Project PROMETEOII/2014/007). M.G. Montalbán acknowledges support from MINECO (Juan de la Cierva-Formación contract, Ref. FJCI-2016-28081)

Almidón termoplástico para el diseño de aplicaciones medioambientalmente sostenibles

La contaminación por residuo plástico es un problema al que las sociedades modernas tienen que hacer frente en el corto plazo. Por un lado, los plásticos convencionales han demostrado ser uno de los mayores inventos ideados por el ser humano debido a sus propiedades (liviandad, resistencia, poca reactividad…), lo que ha permitido uno de los mayores avances de la historia, encontrándose productos plásticos en prácticamente todas las aplicaciones del día a día. Por otro lado, estas propiedades son las que provocan que, ante una mala gestión del residuo de los materiales fabricados con productos plásticos al final de su vida útil, estos lleguen a los ecosistemas naturales, provocando un problema medioambiental como el ya ampliamente conocido. Una alternativa para evitar continuar con la contribución de residuos plásticos en los ecosistemas es la modificación de los materiales convencionales con los que se fabrican, por otros que sean completamente biodegradables y que no generen un perjuicio para el medioambiente al final de su vida útil, como es el caso de aquellos basados en almidón termoplástico (TPS). En el presente trabajo, la investigación ha quedado dividida en cuatro publicaciones, en las que se ha realizado una investigación orientada a ampliar el conocimiento sobre cómo afectan diferentes características de los granos de almidón (contenido en amilosa, monoésteres fosfato, peso molecular…) en las propiedades finales de los filmes de TPS fabricados a partir de diferentes plastificantes (glicerina y líquido iónico) [Artículo_1 y Artículo_2], estudiando además el efecto que tienen en los mismos la adición de nanocargas como nanotubos de carbono [Artículo_3]. Estos filmes se han estudiado mediante la técnica conocida como "casting". Además, se han realizado blends de almidón termoplástico junto con alcohol polivinílico con la finalidad de procesar materiales de TPS mediante "mezcla en fundido". Estas mezclas se han aditivado con colofonia, con el objetivo de estudiar cómo afecta este aditivo a las propiedades finales del TPS [Artículo_4]

Pollutant emissions during the pyrolysis and combustion of starch/poly(vinyl alcohol) biodegradable films

The massive use of petroleum-based polymers and their improper waste treatment has brought on significant global environmental problems due to their non-biodegradable nature. Starch/poly(vinyl alcohol) (PVA) bioplastics are suitable substitutes for conventional polymers, such as polyethylene, due to their full biodegradability and excellent mechanical properties. Knowledge of the pollutant emissions during pyrolysis and combustion of starch/PVA films is important because they can arrive at landfills mixed with conventional polymers and be thermally degraded in uncontrolled fires. On the other hand, controlled thermal treatments could result in thermal valorization of the waste. Pyrolysis and combustion experiments were carried out at 650, 750, 850 and 950 °C in a laboratory furnace. The analysis of carbon oxides, light hydrocarbons, and semivolatile compounds, including polycyclic aromatic hydrocarbons (PAHs), is shown. Experiments showed lower pollutant emissions than those found with conventional polymers, such as polyethylene and polyester, in the same equipment. Nevertheless, the pyrolysis run at 950 °C showed the highest light hydrocarbon yield (123013 mg kg−1), but this is considerably lower than the values found for polyethylene. The main semivolatile compounds (not PAHs) emitted, with maximum yields ranging from 1351 to 4694 mg kg−1, were benzaldehyde, phenol, indene, and acetophenone. Specifically, the total semivolatile compounds emitted after pyrolysis and combustion of starch/PVA samples represent only 38 and 50%, respectively, of those emitted with polyethylene. Further, the main PAHs were naphthalene, acenaphthylene, and phenanthrene with maximum values of 4694, 2704 and 1496 mg kg−1, respectively. The PAH yield was considerably higher in experiments with low oxygen content.This work was partially supported from the European Commission (FEDER/ERDF) and the Spanish MINECO (Ref. CTQ2016-78246-R and CTQ2016-76608-R). M.G. Montalbán acknowledges support from MINECO (Juan de la Cierva-Formación contract, Ref. FJCI-2016-28081)

A correlation between the Wolf-Wilburn scale and atomic force microscopy for anti-scratch resistance determination

The quality of coatings is continuously improving due in part to the irruption of nanotechnology in material science, which has made it possible to manufacture novel nanocomposites. Similarly, the methodologies to measure the mechanical properties of polymer-based nanocomposite coatings are changing. However, a real standard to measure, for example, anti-scratch resistance using equipment such an Atomic Force Microscope (AFM), does not exist due to the strong influence of operational conditions on the final results. This means it is impossible to compare the results of different authors. Moreover, traditional methodologies used in industry, like the Wolf-Wilburn Test, are not able to measure the hardness of novel composites since they can go out of scale. In this work, an AFM is used to make nano-scratches in urethane-acrylate coating surfaces with known Wolf-Wilburn scale values, calculating the anti-scratch resistance. These data are correlated through linear regression. This correlation could be used to obtain the Wolf-Wilburn values from the width of groove made on the polymer surface by the AFM tip. Thus, this work present a potential way to extend the Wolf-Wilburn scale using AFM for those coatings that could not be measurable with Wolf-Wilburn Test.The authors gratefully acknowledge the financial support of the Ministerio de Economía y Competitividad of Spain, MINECO (Project CTQ2014-54772-P and CTQ2013-44213-R) and Generalitat Valenciana (Project PROMETEOII/2014/007)

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

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.This work was supported by the National Science Foundation (NSF) (No. DMR-1710491) and by Financial Assistance Award No. 70NANB19H005 from the U.S. Department of Commerce, National Institute of Standards and Technology as part of the Center for Hierarchical Materials Design (CHiMaD). Additionally, this work made use of the SPID facility of Northwestern University’s NUANCE Center, which has received support from the SHyNE Resource (NSF ECCS-1542205), the IIN, and Northwestern’s MRSEC program (NSF DMR-1720139). We also acknowledge support from the US Department of Defense National Defense Science and Engineering Graduate (NDSEG) fellowship and support from the Richter Trust Funds. We also acknowledge support from Spain’s Ministry of Science (PID2019-108632RB-I00, CTQ2016-78246-R and FJCI-2016-28081)