Strategies to improve the mechanical properties of starch-based materials: plasticization and natural fibers reinforcement

Biodegradable polymers are starting to be introduced as raw materials in the food-packaging market. Nevertheless, their price is very high. Starch, a fully biodegradable and bioderived polymer is a very interesting alternative due to its very low price. However, the use of starch as the polymer matrix for the production of rigid food packaging, such as trays, is limited due to its poor mechanical properties, high hidrophilicity and high density. This work presents two strategies to overcome the poor mechanical properties of starch. First, the plasticization of starch with several amounts of glycerol to produce thermoplastic starch (TPS) and second, the production of biocomposites by reinforcing TPS with promising fibers, such as barley straw and grape waste. The mechanical properties obtained are compared with the values predicted by models used in the field of composites; law of mixtures, Kerner-Nielsen and Halpin-Tsai. To evaluate if the materials developed are suitable for the production of food-packaging trays, the TPS-based materials with better mechanical properties were compared with commercial grades of oil-based polymers, polypropylene (PP) and polyethylene-terphthalate (PET), and a biodegradable polymer, polylactic acid (PLA).

Investigação dos métodos de separação, uso e aplicação da Lignina proveniente da biomassa lignocelulósica

This study investigated the main methods of separation of components of lignocellulosic biomass, with an emphasis on obtaining lignin and its application. The work was developed based on the concept of Biorefinery proposing full use of renewable raw materials and / or the use of lignocellulosic agricultural residues by biochemical or biotechnological conversion in obtaining high value added products with minimal environmental impact. From this premise, a literature review was performed in refereed journal articles and theses in order to gather enough material for critical analysis of usual and alternative methods in the literature. When researching methods that add value to lignin, it was found that with the technology found today, the cost required to have a degree of competitiveness is still too high, preventing much of the process. However, the isolated lignin can be used as raw material in the production of numerous types of biocomposites and polymers and other products such as phenols, benzene, dispersants, vanillin, emulsifying agents, antioxidants, pesticides, fertilizers, charcoal, concrete additives, among others. As an industrial production level is necessary, because the consumption of biomass will only grow over the years, it is necessary that new methods or technologies to be created in order to facilitate the extensive use of lignocellulosic biomass

Investigação dos métodos de separação, uso e aplicação da Lignina proveniente da biomassa lignocelulósica

This study investigated the main methods of separation of components of lignocellulosic biomass, with an emphasis on obtaining lignin and its application. The work was developed based on the concept of Biorefinery proposing full use of renewable raw materials and / or the use of lignocellulosic agricultural residues by biochemical or biotechnological conversion in obtaining high value added products with minimal environmental impact. From this premise, a literature review was performed in refereed journal articles and theses in order to gather enough material for critical analysis of usual and alternative methods in the literature. When researching methods that add value to lignin, it was found that with the technology found today, the cost required to have a degree of competitiveness is still too high, preventing much of the process. However, the isolated lignin can be used as raw material in the production of numerous types of biocomposites and polymers and other products such as phenols, benzene, dispersants, vanillin, emulsifying agents, antioxidants, pesticides, fertilizers, charcoal, concrete additives, among others. As an industrial production level is necessary, because the consumption of biomass will only grow over the years, it is necessary that new methods or technologies to be created in order to facilitate the extensive use of lignocellulosic biomass

Compatible blends of thermoplastic starch and hydrolyzed ethylene-vinyl acetate copolymers

Ethylene-vinyl acetate copolymer (EVA) with 19% of vinyl acetate and its derivatives modified by hydrolysis of 50 and 100% of the initial vinyl acetate groups were used to produce blends with thermoplastic starch (TPS) plasticized with 30 wt% glycerol. The blends were characterized by Fourier transform infrared spectroscopy, scanning electron microscopy. X-ray diffraction, water absorption, stress-strain mechanical tests, dynamic mechanical analysis and thermogravimetric analysis. In contrast to the blends with unmodified EVA. those made with hydrolyzed EVA were compatible, as demonstrated by the brittle fracture surface analysis and the results of thermal and mechanical tests. The mechanical characteristics and water absorption of the TPS were improved even with a small addition (2.5 wt%) of hydrolyzed EVA. The glass transition temperature rose with the degree of hydrolysis of EVA by 40 and 50 degrees, for the EVA with 50 and 100% hydrolysis, respectively. The addition of hydrolyzed EVA proved to be an interesting approach to improving TPS properties, even when very small quantities were used, such as 2.5 wt%. (C) 2012 Elsevier Ltd. All rights reserved.

Proteins control in biomineralization processes of the freshwater pearl mussel Hyriopsis cumingii

Pearls are an amazing example of calcium carbonate biomineralization. They show a classic brick and mortar internal structure in which the predominant inorganic part is composed by aragonite and vaterite tablets. The organic matrix is disposed in concentric layers tightly associated to the mineral structures. Freshwater cultivate pearls (FWCPs) and shells nacreous layers of the Chinese mussel Hyriopsis cumingii were demineralized using an ion exchange resin in order to isolate the organic matrix. From both starting materials a soluble fraction was obtained and further analyzed. The major component of the soluble extracts was represented by a similar glycoprotein having a molecular weight of about 48 kDa in pearls and 44 kDa in shells. Immunolocalization showed their wide distribution in the organic sheet surrounding calcium carbonate tablets of the nacre and in the interlamellar and intertabular matrix. These acidic glycoprotein also contained inside the aragonite platelets, are direct regulators during biomineralization processes, participating to calcium carbonate precipitation since the nucleation step. Selective calcium carbonate polymorph precipitation was performed using the two extracts. The polysaccharides moiety was demonstrate to be a crucial factor in polymorphs selection. In particular, the higher content in sugar groups found in pearls extract was responsible of stabilization of the high energetic vaterite during the in vitro precipitation assay; while irregular calcite was obtained using shells protein. Furthermore these polypeptides showed a carbonic anhydrase activity that, even if not directly involved in polymorphs determination, is an essential regulator in CaCO3 formation by means of carbonate anions production. The structural and functional characterization of the proteins included in biocomposites, gives important hints for understanding the complicated process of biomineralization. A better knowledge of this natural mechanism can offer new strategies for producing environmental friendly materials with controlled structures and enhanced chemical-physical features.

Nuevos ecocomposites a partir de residuos plásticos y celulósicos. Absorción de agua.

El plástico se ha convertido en el material del siglo XXI. Se adapta a múltiples aplicaciones, por eso se emplea para todo tipo de propósitos, entre los cuales destaca el empaquetado por su versatilidad, flexibilidad y durabilidad. Un efecto directo de su continuo uso es la producción de residuos poliméricos, que tras su utilización, se desechan. A partir de ese momento, solo existen dos vías de acción: reciclado y vertido. El vertido de residuos se ha convertido en un grave problema del día a día. En consecuencia, se deben tomar medidas para evitar su acumulación, que implica grandes problemas medioambientales que afectan tanto a personas como a fauna y flora. Por consiguiente, para evitar el desaprovechamiento de una buena parte de los residuos, de aquellos que son plásticos, se lleva a cabo su reciclado. Existen tres tipos de reciclado para los materiales poliméricos: el mecánico o convencional, el químico y la valorización energética. El más sostenible de todos ellos es el reciclado mecánico que además es el empleado para la elaboración de las probetas de este estudio. El reciclado convencional posee varias etapas, entre las cuales destacan fundir el plástico y procesarlo posteriormente. El producto final aparece en forma de pellets, que pueden ser transformados según el uso ulterior. El polímero generado posee una calidad inferior a la de los materiales vírgenes, dado que durante su utilización ha podido ser contaminado por otras substancias. Por tanto, no puede emplearse para muchos de sus pasados usos si no es reforzado con algún otro material. Es entonces cuando surgen los ecocomposites o biocomposites. Los ecocomposites son unos materiales compuestos de matriz polimérica, que presentan especiales ventajas medioambientales, porque utilizan refuerzos celulósicos de fuentes renovables y/o matrices de plásticos reciclados. En nuestro caso, la matriz es una mezcla de residuos plásticos agrarios (RAP) y urbanos, que principalmente están formados por polietileno de alta densidad (HDPE). Por sí solos estos plásticos reciclados, no poseen las cualidades necesarias para su utilización. Por consiguiente, se refuerzan con fibras de celulosa. Estas hebras añadidas también son residuales ya que carecen de las propiedades adecuadas para la fabricación de papel y, en lugar de ser incineradas o desechadas, se emplean en los ecocomposites como ayuda para soportar los esfuerzos mecánicos. Otro beneficio medioambiental del uso de la celulosa, es que hace que los ecocomposites sean más biodegradables en comparación con las fibras minerales que se añaden en los otros composites. Cabe mencionar que, al tratarse de un material totalmente reciclado, también genera una serie de ventajas económicas y sociales. El reciclado mecánico necesita de trabajadores que lleven a cabo la labor. De este modo, aparecen nuevos puestos de trabajo que dan solución a problemas sociales de la población. El reciclado de plásticos irá aumentando durante los próximos años dado que en 2014 la Comunidad Europea fijó como objetivo una economía circular que implica procesar todos los residuos para evitar su acumulación. En la actualidad, aún no se reciclan gran cantidad de plásticos agrarios. Sin embargo, con este compromiso se espera un aumento del volumen de PE agrícola reciclado mecánicamente, ya que el origen del material obtenido a partir de ellos es ecológico y favorece el cuidado del medio ambiente, al emplear materiales de desecho en la generación de los nuevos. Combinando los plásticos reciclados y la celulosa, se crea un material respetuoso con el medio ambiente. No obstante, existe un motivo mayor para su fabricación: se trata de un compuesto con propiedades mecánicas optimizadas que se adapta a numerosas aplicaciones como mobiliario urbano, señales de tráfico… Sus características aúnan los beneficios de unir ambos materiales. Por un lado, la baja densidad, las posibilidades de reciclado y la alta resistencia al impacto aportadas por el plástico. Por el otro, las hebras celulósicas mejoran notablemente el módulo de Young, la rigidez y el límite de tensión que son capaces de soportar con respecto a probetas de misma forma pero sin fibras. Estas propiedades no son las únicas que se modifican al combinar las dos substancias. El refuerzo, al tratarse de un material hidrófilo, tenderá a atrapar la humedad ambiental. Como consecuencia, se producirá un hinchamiento que es posible que repercuta en la estabilidad dimensional del material durante su uso. Asimismo, si la celulosa está en contacto continuo con agua, modifica su naturaleza ya que se producen una serie de cambios en su estructura. El agua genera también la rotura de las interacciones fibra-matriz en la interfase del material compuesto, lo que reduce grandemente las propiedades del ecocomposite. Así pues, la absorción de agua es uno de los principales problemas de estos materiales y limita sus aplicaciones y también la reciclabilidad de los residuos celulósicos y plásticos. Por lo tanto, el principal objetivo de este proyecto es la caracterización tanto de la cinética como del mecanismo de la absorción de agua en los ecocomposites a través de varias técnicas y ensayos siempre con el fin último de reducir la absorción de agua y mejorar las propiedades y las aplicaciones de estos materiales reciclados. Se estudiaron ecocomposites obtenidos a partir de residuos plásticos agrarios y urbanos, con una cantidad variable de celulosa residual, entre 25 y 35%. A algunos de ellos se les había añadido un peróxido orgánico en proporción del 0,025% o 0,05% en peso. Una parte de los materiales había sido sometida a un envejecimiento acelerado de 100, 250 o 500 horas en cámara climática, donde se exponen a calor y humedad. La proporción no constante de celulosa se empleó para descubrir cuánto afecta su variación en la absorción de agua. El peróxido estaba presente como ayuda para entrecruzar la matriz con el refuerzo, que ya se había comprobado que mejoraba las propiedades mecánicas del material, y se pretendía investigar si también podía causar una mejora en la absorción de agua, o bien suponía un empeoramiento. Por último, se pretendía estudiar si el envejecimiento de estos materiales altera la absorción de agua. La absorción se caracterizó principalmente a través de tres procedimientos, todos ellos basados en la medición de ciertas propiedades tras la inmersión de las muestras en viales con agua destilada. Por un lado, se controló la absorción midiendo la ganancia de masa de las muestras mediante una balanza analítica. Por otro lado, se midió el hinchamiento de las probetas a lo largo del tiempo. Finalmente, se caracterizó el agua absorbida y se midió la absorción mediante espectrofotometría infrarroja por transformada de Fourier (FTIR), lo que suministró información sobre los tipos de agua absorbida y los mecanismos de absorción. En el estudio del hinchamiento y de la absorción por gravimetría se tomaron todas las muestras, con una y dos replicaciones. Para la espectrofotometría se analizaron los filmes de código 43500, 43505, 43520 y 43525. La absorción de agua es un fenómeno que se puede explicar en muchos casos a través de la segunda ley de Fick. Para poder emplear esta ley, se toman como hipótesis que la difusión es no estacionaria, la presión y la temperatura son constantes y se trata de difusión unidireccional. Para la aplicación de esta teoría, es necesario que las muestras sean láminas bidimensionales de espesor despreciable. Los coeficientes de difusión se pueden calcular mediante una serie de métodos propuestos por Crank en The Mathematics of Diffusion [5] que recopilan soluciones a esta segunda ley de Fick. La absorción de agua fue aumentando con el tiempo. Inicialmente, el gradiente es superior; esto es, se absorbió más durante las primeras horas de inmersión. Para que la difusión sea Fickiana, el proceso debe ser reversible y alcanzarse un valor de equilibrio de absorción. Nuestros resultados indican que esto no se cumple para largos tiempos de inmersión ya que la teoría predice que la masa absorbida tiende a un valor constante en el equilibrio, mientras que los datos experimentales muestran una tendencia de la absorción a crecer indefinidamente Para tiempos cortos inferiores a 50h, al tratarse de pocas horas de inmersión, el material no se degrada, por lo que el proceso puede describirse como Fickiano. Se calcularon los coeficientes de difusión aparentes y valor estable de cantidad de agua al que tiende la absorción cuando el comportamiento es Fickiano. Los resultados indican que la celulosa afecta considerablemente a la absorción, favoreciéndola cuanto mayor es el porcentaje de fibras. Asimismo, el peróxido no tiene un efecto reseñable en la absorción, porque aúna dos efectos contrarios: favorece el entrecruzamiento de la interfase matriz-refuerzo y degrada parcialmente el material, sobre todo las impurezas de polipropileno en el rHDPE. Finalmente, el envejecimiento muestra una tendencia a facilitar la absorción, pero es importante señalar que esta tendencia desaparece cuando se utiliza peróxido en la composición del ecocomposite, por lo que el peróxido puede aumentar la duración del material. Por último, la espectroscopía FTIR fue muy útil para conocer los tipos de agua que se encuentran en el interior del material, ya que el espectro infrarrojo del agua absorbida depende de cómo se encuentre unida al material. La espectroscopía FTIR ha permitido también observar la cinética de absorción de los diferentes tipos de agua por separado. La absorción del agua libre y el agua ligada se describe bien mediante un modelo Fickiano. La bondad del ajuste para un comportamiento Fickiano es alta. Así pues, los resultados obtenidos aportan información sobre la cinética y los mecanismos de absorción de agua y han mostrado que la absorción depende del contenido en celulosa y no empeora por la adición de peróxido. Por el contrario, el peróxido añadido parece reducir la absorción en materiales envejecidos, lo que puede contribuir a aumentar la duración de estos materiales y mejorar así la reciclabilidad de los residuos empleados.

Characterization of Poly(ε-caprolactone)-Based Nanocomposites Containing Hydroxytyrosol for Active Food Packaging

Antioxidant nano-biocomposites based on poly(ε-caprolactone) (PCL) were prepared by incorporating hydroxytyrosol (HT) and a commercial montmorillonite, Cloisite®30B (C30B), at different concentrations. A full structural, thermal, mechanical and functional characterization of the developed nano-biocomposites was carried out. The presence of the nanoclay and HT increased PCL crystallinity, whereas some decrease in thermal stability was observed. TEM analyses corroborated the good dispersion of C30B into the PCL macromolecular structure as already asserted by XRD tests, since no large aggregates were observed. A reduction in oxygen permeability and increase in elastic modulus were obtained for films containing the nanoclay. Finally, the presence of the nanoclay produced a decrease in the HT release from films due to some interaction between HT and C30B. Results proved that these nano-biocomposites can be an interesting and environmentally-friendly alternative for active food packaging applications with antioxidant performance.

Natural additives and agricultural wastes in biopolymer formulations for food packaging

The main directions in food packaging research are targeted toward improvements in food quality and food safety. For this purpose, food packaging providing longer product shelf-life, as well as the monitoring of safety and quality based upon international standards, is desirable. New active packaging strategies represent a key area of development in new multifunctional materials where the use of natural additives and/or agricultural wastes is getting increasing interest. The development of new materials, and particularly innovative biopolymer formulations, can help to address these requirements and also with other packaging functions such as: food protection and preservation, marketing and smart communication to consumers. The use of biocomposites for active food packaging is one of the most studied approaches in the last years on materials in contact with food. Applications of these innovative biocomposites could help to provide new food packaging materials with improved mechanical, barrier, antioxidant, and antimicrobial properties. From the food industry standpoint, concerns such as the safety and risk associated with these new additives, migration properties and possible human ingestion and regulations need to be considered. The latest innovations in the use of these innovative formulations to obtain biocomposites are reported in this review. Legislative issues related to the use of natural additives and agricultural wastes in food packaging systems are also discussed.

Development of novel nano-biocomposite antioxidant films based on poly (lactic acid) and thymol for active packaging

Novel nano-biocomposite films based on poly (lactic acid) (PLA) were prepared by incorporating thymol, as the active additive, and modified montmorillonite (D43B) at two different concentrations. A complete thermal, structural, mechanical and functional characterization of all nano-biocomposites was carried out. Thermal stability was not significantly affected by the addition of thymol, but the incorporation of D43B improved mechanical properties and reduced the oxygen transmission rate by the formation of intercalated structures, as suggested by wide angle X-ray scattering patterns and transmission electron microscopy images. The addition of thymol decreased the PLA glass transition temperature, as the result of the polymer plasticization, and led to modification of the elastic modulus and elongation at break. Finally, the amount of thymol remaining in these formulations was determined by liquid chromatography (HPLC-UV) and the antioxidant activity by the DPPH spectroscopic method, suggesting that the formulated nano-biocomposites could be considered a promising antioxidant active packaging material.

Nano-biocomposite films with modified cellulose nanocrystals and synthesized silver nanoparticles

Ternary nano-biocomposite films based on poly(lactic acid) (PLA) with modified cellulose nanocrystals (s-CNC) and synthesized silver nanoparticles (Ag) have been prepared and characterized. The functionalization of the CNC surface with an acid phosphate ester of ethoxylated nonylphenol favoured its dispersion in the PLA matrix. The positive effects of the addition of cellulose and silver on the PLA barrier properties were confirmed by reductions in the water permeability (WVP) and oxygen transmission rate (OTR) of the films tested. The migration level of all nano-biocomposites in contact with food simulants were below the permitted limits in both non-polar and polar simulants. PLA nano-biocomposites showed a significant antibacterial activity influenced by the Ag content, while composting tests showed that the materials were visibly disintegrated after 15 days with the ternary systems showing the highest rate of disintegration under composting conditions.

Tissue engineering of co-cultured skin substitutes using biocomposite membranes based on collagen and polycaprolactone

The preparation and characterisation of collagen: PCL, gelatin: PCL and gelatin/collagen:PCL biocomposites for manufacture of tissue engineered skin substitutes are reported. Films of collagen: PLC, gelatin: PCL (1:4, 1:8 and 1:20 w/w) and gelatin/collagen:PCL (1:8 and 1:20 w/w) biocomposites were prepared by impregnation of lyophilised collagen and/or gelatin mats by PCL solutions followed by solvent evaporation. In vitro assays of total protein release of collagen:PCL and gelatin: PCL biocomposite films revealed an expected inverse relationship between the collagen release rate and the content of synthetic polymer in the biocomposite samples that may be exploited for controlled presentation and release of biopharmaceuticals such as growth factors. Good compatibility of all biocomposite groups was proven by interaction with 3T3 fibroblasts, normal human epidermal keratinocytes (NHEK), and primary human epidermal keratinocytes (PHEK) and dermal fibroblasts (PHDF) in vitro respectively. The 1:20 collagen: PCL materials exhibiting good cell growth curves and mechanical characteristics were selected for engineering of skin substitutes in this work. The tissue-engineered skin model based on single-donor PHEK and PHDF with differentiated confluent epidermal layer and fibrous porous dermal layer was then developed successfully in vitro proven by SEM and immunohistochemistry assay. The following in vivo animal study on athymic mice revealed early complete wound healing in 10 days and good integration of co-cultured skin substitutes with adjacent mice skin structures. Thus the co-cultured skin substitutes based on 1:20 collagen: PCL biocomposite membranes was proven in principle. The approach to skin modelling reported here may find application in wound treatment, gene therapy and screening of new pharmaceuticals.

Human single-donor composite skin substitutes based on collagen and polycaprolactone copolymer

The development and characterization of an enhanced composite skin substitute based on collagen and poly(e-caprolactone) are reported. Considering the features of excellent biocompatibility, easy-manipulated property and exempt from cross-linking related toxicity observed in the 1:20 biocomposites, skin substitutes were developed by seeding human single-donor keratinocytes and fibroblasts alone on both sides of the 1:20 biocomposite to allow for separation of two cell types and preserving cell signals transmission via micro-pores with a porosity of 28.8 ± 16.1 µm. The bi-layered skin substitute exhibited both differentiated epidermis and fibrous dermis in vitro. Less Keratinocyte Growth Factor production was measured in the co-cultured skin model compared to fibroblast alone condition indicating a favorable microenvironment for epidermal homeostasis. Moreover, fast wound closure, epidermal differentiation, and abundant dermal collagen deposition were observed in composite skin in vivo. In summary, the beneficial characteristics of the new skin substitutes exploited the potential for pharmaceutical screening and clinical application.

A co-cultured skin model based on cell support membranes

Tissue engineering of skin based on collagen:PCL biocomposites using a designed co-culture system is reported. The collagen:PCL biocomposites having collagen:PCL (w/w) ratios of 1:4, 1:8, and 1:20 have been proven to be biocompatible materials to support both adult normal human epidermal Keratinocyte (NHEK) and mouse 3T3 fibroblast growth in cell culture, respectively, by Dai, Coombes, et al. in 2004. Films of collagen:PCL biocomposites were prepared using non-crosslinking method by impregnation of lyophilized collagen mats with PCL/dichloromethane solutions followed by solvent evaporation. To mimic the dermal/epidermal structure of skin, the 1:20 collagen:PCL biocomposites were selected for a feasibility study of a designed co-culture technique that would subsequently be used for preparing fibroblast/biocomposite/keratinocyte skin models. A 55.3% increase in cell number was measured in the designed co-culture system when fibroblasts were seeded on both sides of a biocomposite film compared with cell culture on one surface of the biocomposite in the feasibility study. The co-culture of human keratinocytes and 3T3 fibroblasts on each side of the membrane was therefore studied using the same co-culture system by growing keratinocytes on the top surface of membrane for 3 days and 3T3 fibroblasts underneath the membrane for 6 days. Scanning electron microscopy (SEM) and immunohistochemistry assay revealed good cell attachment and proliferation of both human keratinocytes and 3T3 fibroblasts with these two types of cells isolated well on each side of the membrane. Using a modified co-culture technique, a co-cultured skin model presenting a confluent epidermal sheet on one side of the biocomposite film and fibroblasts populated on the other side of the film was developed successfully in co-culture system for 28 days under investigations by SEM and immunohistochemistry assay. Thus, the design of a co-culture system based on 1:20 (w/w) collagen:PCL biocomposite membranes for preparation of a bi-layered skin model with differentiated epidermal sheet was proven in principle. The approach to skin modeling reported here may find application in tissue engineering and screening of new pharmaceuticals. © 2005 Elsevier Inc. All rights reserved.