Biotratamento de sacolas plásticas de supermercado

Supermarket plastic bags are produced by high density polyethylene (HDPE) and low density polyethylene (LDPE) resins. In Brazil, are produced annually around 150 plastic bags per capita. Disposed in landfills, the supermarket plastic bags prevent the passage of water by slowing the breakdown of biodegradable materials and hindering compaction of waste, according to their low degradability. This work investigated the biodegradation of PE bags containing additive oxo-biodegradable and bags without additives: buried in soil columns, exposed in a controlled environment and exposed to air. The analysis methods used to assess the changes brought in the bags with respect to microbial action and exposure time were weight loss, thickness measurement, infrared (FTIR), scanning electron microscopy (SEM) and contact angle. The results showed that the use of prodegradant agents such as oxobiodegradable additives in polyethylene bags, buried in soil for 270 days, was not efficient to accelerate the biodegradation by microorganisms. It seems that these additives have been more efficient to degrade the colored pigmentation of printed bags, under the influence of light and heat.

Preparação e caracterização da casca de banana prata particulada para aplicação com reforço em compósito de matriz de PEAD

The waste, exaggerated and incorrect disposal of biomass are common practices in modern times where everything is disposable. However the growing concern with the nature and the environment compel man to give nobler destinations for these products through sustainability and recycling of waste. Banana peel is a residual biomass, which is not consumed. It generates tons of waste per week in São Paulo city. This trash is disposed in dumps and landfills, which could be reduced by using it as reinforcement in natural composites. The high density polyethylene (HDPE) is a polymer derived from the ethylene polymerization and is easily recycled. Which makes it a sustainable material. In the present work characteristics of the natural composite composed with banana peel and high-density polyethylene were studied. It was noted that removing the lignin present in the banana peel, the fiber introduces a significant improvement in thermal resistance. The preparation of composite was made with a ratio of 5% and 10% of reinforcement in comparison with polymeric matrix mass. Composites were thermally, mechanically and microscopically characterized. The addition of fiber in the polymer increased the mechanical strength of the composite. The fiber surface treatment with distilled water removed the amorphous material present in the fibers, improving significantly thermal stability and increasing crystallinity of the celullose. The addition of 5% fiber in mass to the polymer increased significantly the tensile strength and elasticity modulus for the composite. With 10% of fiber addiction there were also an improvement when compared with pure HDPE, but when compared with 5% composite the mechanical properties are slightly lower. This may be due to the fiber particle size, which are small and eventually become a hub of tension ... (Complete abstract click electronic access below)

Desenvolvimento, implantação e avaliação do desempenho de biorreator anaeróbico de leito fluidizado e leito fixo com filtros biológicos em materiais diversos

This study aimed to develop, implement and evaluate the performance of a new type of bioreactor for anaerobic treatment of wastewater using different filling materials like trickling filters post-reactor. This bioreactor has mixed characteristics of the UASB reactors and horizontal flow from the point of view of removal of BOD (Biochemical Oxygen Demand) ssed (settled solids), TS (Total Solids), SS (Suspended Solid), SD (Dissolved Solids) and turbidity. The experimental model consists of a bioreactor with a volume of 12 m³, 2/3 filled by fluidized bed and 1/3 for fixed. The fluidized bed is made of polystyrene plates used as a system percolation and compartmentalized trickling filters, where each compartment was filled with a support medium with different characteristics (gravel number 4, plastic rings of polystyrene, PET and HDPE) . In addition, the output of a filter system was installed three entries filled with activated carbon. The bioreactor was installed in private residence in the city of Igarapava-SP (20° 02'40.18"S and 47° 45'01.36" W). The system was highly efficient as the removal of organic contaminant load 92% on average reducing the BOD, a significant result when compared to other anaerobic systems. For the other parameters, the mean reduction was 96% for turbidity, 99% ssed, 67.5% ST, 57% SD and 88% of SS. As for its operation the system was capable of operating in continuous flow without the need for maintenance during the entire period of evaluation and without energy, as it operates taking advantage of the natural slope of the terrain where it is installed. The environmental impacts were minimized due to the preservation of local vegetation allowing the ecosystem to remain unchanged beyond the prototype was completely sealed preventing exhalation of odors and therefore not causing inconvenience to neighboring populations. Given these facts it was concluded that the prototype is shown to be highly feasible deployed as a new alternative for treatment of sewage in rural and urban settings (individual homes, condos, farms, ranches, etc.) Due to ease of design and operability, and sustainability at all stages of execution.

Uso da cromatografia gasosa para avaliação da difusão em membrana de Polietileno de Alta Densidade (pead) em contato com hidrocarboneto

The constant petrol fuel leak in gas stations has caused concern in many countries around the world. Those fuels have toxic organic compounds in their composition, like Polycyclic Aromatic Hydrocarbons (PAH), which are harmful to the human health. In this work the efficiency of the protection layer with a High Density Polyethylene (HDPE) membrane of 2.5 mm thickness was evaluated. The study was based in the diffusive process in the intact membrane by a permeameter developed to evaluate the diffusive process. The membrane was putted in the middle of the system to separate two sides: a local soil impregnated with diesel oil (in one side) and pure water (in the other side). The chromatography technique was conducted to evaluate the contamination in the pure water. The analyses were made monthly in a total period of 6 months of research. The results tests show that the membrane was less effective to antracene and naphthalene compounds. Despite that, the results showed that the HDPE membrane is a good alternative to prevent contamination of water and soil by the compounds under study up to one year, based on the performance in the time of study.

Efeito da vinhaça na membrana impermeabilizante usada nos tanques de armazenamento

This work evaluated the effect of vinasse (residue from sugar cane) in high density polyethylene (HDPE) geomembranes having in mind that it is deposited at temperatures of 80-90˚C on the geomembrane in storage tanks. The objective was to evaluate the resistance of the geomembrane in contact with residue in a total period of 4 months. Physical and mechanical tests, and thermogravimetric analysis (TGA) were used to determine degradation of polymer membranes after chemical immersion. In general, the results obtained show that the vinasse affected the geomembranes significantly in some aspects, for instance, the thickness of the material presented a variation of 7.8%. The average values in both directions at yielding showed a significant loss of tensile strength (34.13%) and strain (23.48%) and an increase in the modulus of elasticity (9.63%). At the rupture the behavior presented the same trend: a loss of 32% for tensile strength and 24.4% for the deformation were observed. Tear strength presented small decrease (4.72%) and puncture resistance a increase of 7.9% after immersion of geomembranes. The TGA tests were not efficient to detect evidence of degradation in samples of geomembranes after exposures, but identified problems in the quality of the supplied material.

Evaluation of stress cracking on geomembranes after accelerated tests

This paper presents results of stress cracking tests performed in high density polyethylene (HDPE) geomembranes (GM). Stress cracking tests were performed in accordance to ASTM D5397: Notched Constant Tensile Load Test (NCTL) and Single Point-Notched Constant Tensile Load Test (SP-NCTL). Tests were conducted to the fresh sample at 50ºC (standard test) and at 70ºC (accelerated condition) in order to compare the SC values. Results from accelerated tests (NCTL) showed, for instance, a total economy of 390 hours (comparing load stages of 25% yield stress) to perform the tests.

Rilevati arginali in terra rinforzata con geosintetici: il caso della Vena Mazzarini a Cesenatico (FC)

Oggetto della presente tesi di laurea è quello di analizzare sia dal punto di vista teorico che da quello pratico l’impiego di geosintetici di rinforzo per il consolidamento di rilevati e sponde arginali al fine di ottenere un sistema pluricomposto terreno-rinforzo che manifesti adeguati margini di sicurezza nei confronti delle verifiche di stabilità prescritte dalla normativa vigente, soprattutto nei confronti dell’azione indotta dal sisma. In particolare il lavoro è suddiviso di due macro parti fondamentali: una prima parte dedicata allo studio degli aspetti teorici legati alla caratterizzazione dei materiali di rinforzo con particolare riferimento ai geotessili ed alle geogriglie, ai principi fondamentali di funzionamento del sistema terreno-rinforzi, alla normativa di riferimento per tali costruzioni, al dimensionamento dei pendii in terra rinforzata ed al loro inserimento ambientale; la seconda parte, basata sullo studio di un caso di reale applicazione del metodo di rinforzo con geosintetici, si svolge attraverso una approfondita e critica analisi della relazione geologica messa a disposizione dal Comune di Cesenatico (FC) con lo scopo di elaborare le prove svolte in situ, ricavare i parametri geotecnici caratteristici del terreno e definire un modello geologico e geotecnico di riferimento per le successive elaborazioni. Il progetto prevede infatti il consolidamento delle sponde del canale che attraversa, parallelamente alla linea di costa, la città di Cesenatico (FC) e denominato “Vena Mazzarini”, dal nome dell’Ingegnere che ne curò il progetto originale. In particolare si è previsto l’impiego di geogriglie di rinforzo in HDPE e tutte le verifiche sono state realizzate mediante il software di calcolo Geostru Slope® e Slope/M.R.E® messi cordialmente a disposizione dalla software house Geostru S.r.l.

Life cycle assessment per manufatti in plastica: Il caso di contenitori per rifiuti sanitari

Per lo svolgimento della tesi ci si è rivolti ad un'azienda particolarmente conosciuta per la sua attenzione alle tematiche ambientali: la Mengozzi Rifiuti Sanitari S.p.A.. L'impianto, sito a Forlì, comprende una sezione dedicata alla gestione di contenitori in materiale plastico per rifiuti sanitari e una sezione per la termovalorizzazione di questi. Si è incentrato lo studio sulla prima parte dell'impianto che si occupa della produzione, del trasporto verso la struttura in cui è utilizzato, del ritorno in azienda e del riuso per più cicli previa sanificazione fino al riciclo per lo stampaggio di nuovi contenitori. Si è pensato di prendere in considerazione i bidoni che sono gestiti dalla Mengozzi S.p.A. e se ne è svolta un'analisi LCA comparativa tra il contenitore effettivamente in carico all'azienda e un altro ipotetico con le medesime caratteristiche strutturali ma gestito diversamente (incenerito dopo un solo utilizzo). Essendo il contenitore di plastica si è inoltre svolta una comparazione tra 2 materiali termoplastici di massa aventi caratteristiche molto simili, quali sono il polietilene ad alta densità (HDPE) e il polipropilene (PP). Il software che è stato utilizzato per condurre l'analisi è SimaPro 7.3 e il metodo lo svizzero IMPACT 2002+. Nello svolgimento si sono considerati 12 bidoni monouso che hanno in pratica la stessa funzione dell'unico bidone sanificato dopo ogni utilizzo e infine riciclato. Dall'analisi è emerso (come facilmente ipotizzabile) che il bidone riusato genera un impatto ambientale nettamente minore rispetto a quello monouso mentre non vi è apprezzabile differenza tra differente tipologia di materiale termoplastico costituente il bidone stesso: L'importanza della scelta della più adeguata modalità di gestione del fine vita e del materiale di composizione in termini ambientali è più marcata a causa di un'attenzione sempre crescente verso le tematiche di sostenibilità.

Investigation of Solid-State Shear Pulverization Processing Parameters for Polyethylene-Clay Nanocomposites

Investigates multiple processing parameters, includingpolymer type, filler type, processing technique, severity of SSSP (Solid-state shear pulverization)processing, and postprocessing, of SSSP. HDPE and LLDPE polymers with pristine clay and organo-clay samples are explored. Effects on crystallization, high-temperature behavior, mechanicalproperties, and gas barrier properties are examined. Thermal, mechanical, and morphological characterization is conducted to determine polymer/filler compatibility and superior processing methods for the polymer-clay nanocomposites.

Solid-State Compatibilization of Immiscible Polymer Blends: Cryogenic Milling and Solid-State Shear Pulverization

The blending of common polymers allows for the rapid and facile synthesis of new materials with highly tunable properties at a fraction of the costs of new monomer development and synthesis. Most blends of polymers, however, are completely immiscible and separate into distinct phases with minimal phase interaction, severelydegrading the performance of the material. Cross-phase interactions and property enhancement can be achieved with these blends through reactive processing or compatibilizer addition. A new class of blend compatibilization relies on the mechanochemical reactions between polymer chains via solid-state, high energy processing. Two contrasting mechanochemical processing techniques are explored in this thesis: cryogenic milling and solid-state shear pulverization (SSSP). Cryogenic milling is a batch process where a milling rod rapidly impacts the blend sample while submerged within a bath of liquid nitrogen. In contrast, SSSP is a continuous process where blend components are subjected to high shear and compressive forces while progressing down a chilled twin-screw barrel. In the cryogenic milling study, through the application of a synthesized labeledpolymer, in situ formation of copolymers was observed for the first time. The microstructures of polystyrene/high-density polyethylene (PS/HDPE) blends fabricated via cryomilling followed by intimate melt-state mixing and static annealing were found to be morphologically stable over time. PS/HDPE blends fabricated via SSSP also showed compatibilization by way of ideal blend morphology through growth mechanisms with slightly different behavior compared to the cryomilled blends. The new Bucknell University SSSP instrument was carefully analyzed and optimized to produce compatibilized polymer blends through a full-factorial experiment. Finally, blends of varying levels of compatibilization were subjected to common material tests to determine alternative means of measuring and quantifying compatibilization,

Photodegradation and photostabilization of weathered wood flour filled polyethylene composites

Wood plastic composites (WPCs) have gained popularity as building materials because of their usefulness in replacing solid wood in a variety of applications. These composites are promoted as being low-maintenance, high-durability products. However, it has been shown that WPCs exposed to weathering may experience a color change and/or loss in mechanical properties. An important requirement for building materials used in outdoor applications is the retention of their aesthetic qualities and mechanical properties during service life. Therefore, it is critical to understand the photodegradation mechanisms of WPCs exposed to UV radiation and to develop approaches to stabilize these composites (both unstabilized and stabilized) as well as the effect of weathering on the color fade and the retention of mechanical properties were characterized. Since different methods of manufacturing WPCs lead to different surface characteristics, which can influence weathering, the effect of manufacturing method on the photodegradation of WPCs was investigated first. Wood flour (WF) filled high-density polyethylene (HDPE) composite samples were either injection molded, extruded, or extruded and then planed. Fourier transform infrared (FTIR) spectroscopy was used to monitor the surface chemistry of the manufactured composites. The spectra showed that the surface of planed samples had more wood component than extruded and injection molded samples, respectively. After weathering, the samples were analyzed for color fade, and loss of flexural properties. The final lightness of the composites was not dependent upon the manufacturing method. However the mechanical property loss was dependent upon manufacturing method. The samples with more wood component at the surface (planed samples) experienced a larger percentage of total loss in flexural properties after weathering due to a greater effect of moisture on the samples. The change in surface chemistry of HDPE and WF/HDPE composites after weathering was studied using spectroscopic techniques. X-ray photoelectron spectroscopy (XPS) was used to characterize the occurrence of surface oxidation whereas FTIR spectroscopy was used to monitor the development of degradation products, such as carbonyl groups and vinyl groups, and to determine changes in HDPE crystallinity. Surface oxidation occurred immediately after exposure for both the neat HDPE and WF/HDPE composites. After weathering, the surface of the WF/HDPE composites was oxidized to a greater extent than the neat HDPE after weathering. This suggests that photodegradation is exacerbated by the addition of the carbonyl functional groups of the wood fibers within the HDPE atrix during composite manufacturing. While neat HDPE may undergo cross-linking in the initial stages of accelerated weathering, the WF may physically hinder the ability of the HDPE to cross-link resulting in the potential for HDPE chain scission to dominate in the initial weathering stages of the WF/HDPE composites. To determine which photostabilizers are most effective for WF/HDPE composites, factorial experimental designes were used to determine the effects of adding two hindered amine light stabilizers, an ultraviolet absorber, and a pigment on the color made and mechanical properties of both unweathered and UV weathered samples. Both the pigment and ultraviolet absorber were more effective photostabilizers for WF/HDPE composites than hinder amine light stabilizers. The ineffectiveness of hindered amine light stabilizers in protecting WPCs against UV radiation was attribuated to the acid/base reactions occurring between the WF and hindered amine light stabilizer. The efficiency of an ultraviolet absorber and/or pigment was also examined by incorporating different concentration of an ultraviolet absorber and/or pigment into WF/HDPE composites. Color change and flexural properties were determined after accelerated UV weathering. The lightness of the composite after weathering was influenced by the concentration of both the ultraviolet absorber by masking the bleaching wood component as well as blocking UV light. Flexural MOE loss was influenced by an increase in ultraviolet absorber concentration, but increasing pigment concentration from 1 to 2% had little influence on MOE loss. However, increasing both ultraviolet absorber and pigment concentration resulted in improved strength properties over the unstabilized composites after 3000 h of weather. Finally, the change in surface chemistry due to weathering of WF/HDPE composites that were either unstabilized or stabilized with an ultraviolet absorber and/or pigment was analyzed using FTIR spectroscopy. The samples were tested for loss in modulus of elasticity, carbonyl and vinyl group formation at the surface, and change in HDPE crystallinity. It was concluded that structural changes in the samples; carbonyl group formation, terminal vinyl group formation, and crystallinity changes cannot reliably be used to predict changes in modulus of elasticity using a simple linear relationship. The effect of cross-linking, chain scission, and crystallinity changes due to ultraviolet exposure as well as the interfacial degradation due to moisture exposure are inter-related factors when weathering HDPE and WF/HDPE composites.

THE USE OF LIFE-CYCLE ANALYSIS TO REDUCE THE ENVIRONMENTAL IMPACT OF MATERIALS IN MANUFACTURING

This thesis is composed of three life-cycle analysis (LCA) studies of manufacturing to determine cumulative energy demand (CED) and greenhouse gas emissions (GHG). The methods proposed could reduce the environmental impact by reducing the CED in three manufacturing processes. First, industrial symbiosis is proposed and a LCA is performed on both conventional 1 GW-scaled hydrogenated amorphous silicon (a-Si:H)-based single junction and a-Si:H/microcrystalline-Si:H tandem cell solar PV manufacturing plants and such plants coupled to silane recycling plants. Using a recycling process that results in a silane loss of only 17 versus 85 percent, this results in a CED savings of 81,700 GJ and 290,000 GJ per year for single and tandem junction plants, respectively. This recycling process reduces the cost of raw silane by 68 percent, or approximately $22.6 and $79 million per year for a single and tandem 1 GW PV production facility, respectively. The results show environmental benefits of silane recycling centered around a-Si:H-based PV manufacturing plants. Second, an open-source self-replicating rapid prototype or 3-D printer, the RepRap, has the potential to reduce the environmental impact of manufacturing of polymer-based products, using distributed manufacturing paradigm, which is further minimized by the use of PV and improvements in PV manufacturing. Using 3-D printers for manufacturing provides the ability to ultra-customize products and to change fill composition, which increases material efficiency. An LCA was performed on three polymer-based products to determine the CED and GHG from conventional large-scale production and are compared to experimental measurements on a RepRap producing identical products with ABS and PLA. The results of this LCA study indicate that the CED of manufacturing polymer products can possibly be reduced using distributed manufacturing with existing 3-D printers under 89% fill and reduced even further with a solar photovoltaic system. The results indicate that the ability of RepRaps to vary fill has the potential to diminish environmental impact on many products. Third, one additional way to improve the environmental performance of this distributed manufacturing system is to create the polymer filament feedstock for 3-D printers using post-consumer plastic bottles. An LCA was performed on the recycling of high density polyethylene (HDPE) using the RecycleBot. The results of the LCA showed that distributed recycling has a lower CED than the best-case scenario used for centralized recycling. If this process is applied to the HDPE currently recycled in the U.S., more than 100 million MJ of energy could be conserved per annum along with significant reductions in GHG. This presents a novel path to a future of distributed manufacturing suited for both the developed and developing world with reduced environmental impact. From improving manufacturing in the photovoltaic industry with the use of recycling to recycling and manufacturing plastic products within our own homes, each step reduces the impact on the environment. The three coupled projects presented here show a clear potential to reduce the environmental impact of manufacturing and other processes by implementing complimenting systems, which have environmental benefits of their own in order to achieve a compounding effect of reduced CED and GHG.

Assessing the Environmental Hazard of Using Seawater for Ore Processing at the Lasail Mine Site in the Sultanate of Oman

The Lasail mining area (Sultanate of Oman) was contaminated by acid mine drainage during the exploitation and processing of local and imported copper ore and the subsequent deposition of sulphide-bearing waste material into an unsealed tailings dump. In this arid environment, the use of seawater in the initial stages of ore processing caused saline contamination of the fresh groundwater downstream of the tailings dump. After detection of the contamination in the 1980s, different source-controlled remediation activities were conducted including a seepage water collection system and, in 2005, surface sealing of the tailings dump using an HDPE-liner to prevent further infiltration of meteoric water. We have been assessing the benefits of the remediation actions undertaken so far. We present chemical and isotopic (δ18O, δ 2H, 3H) groundwater data from a long-term survey (8–16 years) of the Wadi Suq aquifer along a 28 km profile from the tailings dump to the Gulf of Oman. Over this period, most metal concentrations in the Wadi Suq groundwater decreased below detection limits. In addition, in the first boreholes downstream of the tailings pond, the salinity contamination has decreased by 30 % since 2005. This decrease appears to be related to the surface coverage of the tailings pond, which reduces flushing of the tailings by the sporadic, but commonly heavy, precipitation events. Despite generally low metal concentrations and the decreased salinity, groundwater quality still does not meet the WHO drinking water guidelines in more than 90 % of the Wadi Suq aquifer area. The observations show that under arid conditions, use of seawater for ore processing or any other industrial activity has the potential to contaminate aquifers for decades.

Control de la Fusariosis vascular en clavel en el suroeste de España mediante la biodesinfección del suelo.

El presente trabajo presenta una evaluación de las alternativas no químicas al 1,3 dicloropropeno + cloropicrina (AGROC) usado para el control de la fusariosis vascular en clavel en campos experimentales del suroeste de España. Esta enfermedad ha sido un factor limitante en todas las regiones del mediterráneo para poder mantener el cultivo durante 2 años. Tiempo éste necesario para obtener un rendimiento económico aceptable. La desinfección del suelo está basada en el compostado de la materia orgánica, que combinada o no con la solarización, es agrupada bajo la denominación de biodesinfección. Los tratamientos evaluados fueron: compost de alperujo con o sin solarización (31días), compost de residuos post-cosecha de clavel y crisantemo con y sin solarización, compost de residuos post-cosecha de clavel y crisantemo + gallinaza con y sin solarización. La gravedad de la enfermedad y la producción de flores se evaluaron semanalmente durante los 2 años que duró el experimento. Los resultados mostraron que la biodesinfección del suelo utilizando compost de clavel y crisantemo + gallinaza + solarización confiere una aceptable protección contra la fusariosis vascular durante los 2 años que dura el cultivo. La producción fue significativamente mayor que en cualquier otro de los tratamientos. Los resultados además sugieren que la adición de la gallinaza y el uso del polietileno estándar de alta densidad (HDPE) de forma conjunta fueron el factor clave en el éxito de la desinfección. No hubo efecto de la solarización sola, posiblemente debido a la época en la cual se aplicó

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.