Maria Rubino

Assessment of aliphatic–aromatic copolyester biodegradable mulch films. Part I: Field study

The objective of this work was to study the use of new biodegradable films in agriculture under open field conditions. Three biodegradable mulch films made from modified biodegradable polyester of different thicknesses and colors (black and white) and a conventional low density polyethylene (LDPE) mulch film were used to cover the beds of tomato plants. Changes in physical appearance of the films were recorded as well as changes in their mechanical, optical, and physical properties. Once tomato harvest was completed, the conventional LDPE mulch film was removed and all the tomato plants were cut using a mower. The biodegradable mulch films were plowed into the soil. The change in the appearance of the film was recorded and samples of each film after plowing were characterized according to the properties mentioned above. After the biodegradable films photodegraded, cross-link formation occurred within the films which promoted brittleness. Titanium dioxide, an additive used to produce white color in the films, catalyzed the photodegradation, while carbon black used for black color stabilized the photodegradation. The white films started to degrade after two weeks while it took about eight weeks for the black films to significantly degrade. The black biodegradable film seems to be a more promising alternative as a mulch film because of the comparable yields and weed suppression ability to conventional mulch film.

Assessment of aliphatic-aromatic copolyester biodegradable mulch films. Part II: Laboratory simulated conditions

In a previous paper, we demonstrated that the main mechanism of degradation of poly(butylene adipate-co-terephthalate) (PBAT) biodegradable mulch films when exposed to field conditions was crosslinking due to the photodegradation from solar radiation. The aim of this work was to determine the effect of crosslinking on the biodegradability of PBAT samples. PBAT films were subjected to UV photodegradation in laboratory simulated conditions to investigate the effects of crosslinking and other major changes in the structure and mechanical properties of the films. Crosslinking caused the films to become more brittle and produced a reduction of the tensile strength and percent elongation. Besides the crosslinking degradation mechanism, chain scission also occurred in the samples. After 45d of biodegradation test, the non-crosslinked PBAT sample reached 60% of mineralization. However, the percent mineralization was reduced when samples were crosslinked. The percent mineralization of samples with 10%, 30%, 50%, and 70% gel content was 36%, 43%, 21%, and 24%, respectively. Our results indicate that crosslinking is a key process underlying the degradation of the PBAT film and did affect the biodegradability of the films, since the samples with greater amount of gel content generally showed less percent mineralization in the biodegradation tests.

Postharvest shelf life extension of blueberries using a biodegradable package

Small berries are commonly packaged and sold to consumers in vented petroleum-based clamshell containers. Biodegradable and compostable packages may be used as an alternative package to reduce waste generation and landfill disposal. In addition, the current clamshell container design does not allow the development of a modified atmosphere that could prolong berry shelf life. Thus, in this study, a non-ventilated biodegradable container was evaluated as a possible alternative to the containers normally used in commercial distribution of small berries. To determine the potential of biodegradable containers for small berries, highbush blueberries were packaged in polylactide (PLA) containers and stored at 10°C for 18 days and at 23°C for 9 days. Commercial vented clamshell containers were used as controls. Physicochemical and microbiological studies were carried out in order to compare the efficacy of both packages. Results showed that the PLA containers prolonged blueberry shelf life at different storage temperatures.

Impact of Nanoclays on the Biodegradation of Poly(Lactic Acid) Nanocomposites

Poly(lactic acid) (PLA), a well-known biodegradable and compostable polymer, was used in this study as a model system to determine if the addition of nanoclays affects its biodegradation in simulated composting conditions and whether the nanoclays impact the microbial population in a compost environment. Three different nanoclays were studied due to their different surface characteristics but similar chemistry: organo-modified montmorillonite (OMMT), Halloysite nanotubes (HNT), and Laponite® RD (LRD). Additionally, the organo-modifier of MMT, methyl, tallow, bis-2-hydroxyethyl, quaternary ammonium (QAC), was studied. PLA and PLA bio-nanocomposite (BNC) films were produced, characterized, and used for biodegradation evaluation with an in-house built direct measurement respirometer (DMR) following the analysis of evolved CO2 approach. A biofilm formation essay and scanning electron microscopy were used to evaluate microbial attachment on the surface of PLA and BNCs. The results obtained from four different biodegradation tests with PLA and its BNCs showed a significantly higher mineralization of the films containing nanoclay in comparison to the pristine PLA during the first three to four weeks of testing, mainly attributed to the reduction in the PLA lag time. The effect of the nanoclays on the initial molecular weight during processing played a crucial role in the evolution of CO2. PLA-LRD5 had the greatest microbial attachment on the surface as confirmed by the biofilm test and the SEM micrographs, while PLA-QAC0.4 had the lowest biofilm formation that may be attributed to the inhibitory effect also found during the biodegradation test when the QAC was tested by itself.

Toughening of Poly(lactic acid) and Thermoplastic Cassava Starch Reactive Blends Using Graphene Nanoplatelets

Poly(lactic acid) (PLA) was reactively blended with thermoplastic cassava starch (TPCS) and functionalized with commercial graphene (GRH) nanoplatelets in a twin-screw extruder, and films were produced by cast-film extrusion. Reactive compatibilization between PLA and TPCS phases was reached by introducing maleic anhydride and a peroxide radical during the reactive blending extrusion process. Films with improved elongation at break and toughness for neat PLA and PLA-g-TPCS reactive blends were obtained by an addition of GRH nanoplatelets. Toughness of the PLA-g-TPCS-GRH was improved by ~900% and ~500% when compared to neat PLA and PLA-g-TPCS, respectively. Crack bridging was established as the primary mechanism responsible for the improvement in the mechanical properties of PLA and PLA-g-TPCS in the presence of the nanofiller due to the high aspect ratio of GRH. Scanning electron microscopy images showed a non-uniform distribution of GRH nanoplatelets in the matrix. Transmittance of the reactive blend films decreased due to the TPCS phase. Values obtained for the reactive blends showed ~20% transmittance. PLA-GRH and PLA-g-TPCS-GRH showed a reduction of the oxygen permeability coefficient with respect to PLA of around 35% and 50%, respectively. Thermal properties, molecular structure, surface roughness, XRD pattern, electrical resistivity, and color of the films were also evaluated. Biobased and compostable reactive blend films of PLA-g-TPCS compounded with GRH nanoplatelets could be suitable for food packaging and agricultural applications.

Novel Active Surface Prepared by Embedded Functionalized Clays in an Acrylate Coating

The research on a self-decontaminating surface has received significant attention because of the growth of pathogenic microorganisms on surfaces. In this study, a novel and simple technique for producing an active surface with antimicrobial functionality is demonstrated. A tethering platform was developed by grafting the biocide ampicillin (Amp) to a nanoclay and dispersing the nanoclay in a UV-curable acrylate coating applied on polypropylene films as the substrate. A coupling agent, [3-(glycidyloxy)propyl]trimethoxysilane, was used as a linker between the nanoclay and Amp. The Amp-functionalized clay was further modified with an organic surfactant to improve the compatibility with the coating. Several characterization assays, such as Fourier infrared transform analysis, thermogravimetric analysis, and X-ray diffraction, were conducted to confirm the presence of Amp in the nanoclay. Transmission electron microscopy images revealed that the clay particles were well dispersed in the coating and had a partial exfoliated morphology. The active coating surface was effective in inhibiting the growth of Gram-positive Listeria monocytogenes and Gram-negative Salmonella Typhimurium via contact. These findings suggest the potential for the development of active surfaces with the implementation of nanotechnology to achieve diverse functionalities.

Photooxygenation of furans in water and ionic liquid solutions

Photooxygenation of differently functionalized furans is investigated in aqueous solutions and in ionic liquids [emim]Br and [bmim]BF4. The reaction is generally selective and the final products derive from rearrangement of the intermediate endoperoxides, depending mainly on the polarity and/or nucleophilic nature of the solvent.

Phototransformation of amlodipine in aqueous solution. Toxicity of the drug and its photoproduct on aquatic organisms

The phototransformation of amlodipine in water was investigated under various conditions. A quantum yield ΦS2.2×10−4 and a half-life time t1/2 0.419 days were calculated when the drug in water (10−4 M) was exposed to sunlight. The only photoproduct found was its pyridine derivative. Formation of this product was explained on the basis of a radical cation intermediate. The acute and chronic toxicity of the drug and its photoproduct were evaluated on different organisms of the freshwater chain (Brachionus calyciflorus, Thamnocephalus platyurus, Daphnia magna, Ceriodaphnia dubia). The photoproduct exhibited a stronger toxic potential than the parent drug on the long time for C. dubia.

Migration of antioxidants from polylactic acid films: A parameter estimation approach and an overview of the current mass transfer models

Migration studies of chemicals from contact materials have been widely conducted due to their importance in determining the safety and shelf life of a food product in their packages. The US Food and Drug Administration (FDA) and the European Food Safety Authority (EFSA) require this safety assessment for food contact materials. So, migration experiments are theoretically designed and experimentally conducted to obtain data that can be used to assess the kinetics of chemical release. In this work, a parameter estimation approach was used to review and to determine the mass transfer partition and diffusion coefficients governing the migration process of eight antioxidants from poly(lactic acid), PLA, based films into water/ethanol solutions at temperatures between 20 and 50°C. Scaled sensitivity coefficients were calculated to assess simultaneously estimation of a number of mass transfer parameters. An optimal experimental design approach was performed to show the importance of properly designing a migration experiment. Additional parameters also provide better insights on migration of the antioxidants. For example, the partition coefficients could be better estimated using data from the early part of the experiment instead at the end. Experiments could be conducted for shorter periods of time saving time and resources. Diffusion coefficients of the eight antioxidants from PLA films were between 0.2 and 19×10-14m2/s at ~40°C. The use of parameter estimation approach provided additional and useful insights about the migration of antioxidants from PLA films.

In situ characterization of organo-modified and unmodified montmorillonite aqueous suspensions by UV-visible spectroscopy.

UV-visible (UV-Vis) spectroscopy (Tyndall spectra) was applied and tested for its ability to measure organo-modified and unmodified montmorillonite (MMT) clays in aqueous suspensions. A full factorial design of experiments was used to study the influence of pH, NaCl and clay concentrations on the average particle size of the clay agglomerates. The methodology was evaluated by observing results that were consistent with previous research about the unmodified clays behavior in aqueous suspensions. The results from this evaluation corresponded to accepted theories about the unmodified clays behavior, indicating that the methodology is precise enough to distinguish the effects of the studied factors on these clay suspensions. The effect of clay concentration was related to the amount of ions per clay particle for the unmodified clay, but was not significant for the organo-modified MMT. The average particle size of the organo-modified MMT in suspension was significantly larger than that of the unmodified clay. Size of the organo-modified MMT agglomerates in suspension decreased in the presence of NaCl and at both high and low pH; this behavior was opposite to that of the unmodified clay. These results demonstrate that the UV-Vis methodology is well-suited for characterizing clay particle size in aqueous suspensions. The technique also is simple, rapid, and low-cost.