The course of polymer film functioning has been a crucial concern in the advent of packaging technology. The thesis project aims towards obtaining an understanding of mechanical properties for a class of these materials, namely LDPE and PET. A constitutive understanding of this behavior in the case of LDPE is acquired through incorporating a plastic stress strain relationship in an iterative approach with focus put on the sensitivity of a few parameters by following a simple linear curve-fit technique in a way that the global as well as the local response are predictable. FE-models also developed in this way are validated with experimental data. An inverse analysis testing validity or usefulness of DIC technique in identifying a material model is done and some discussions are drawn towards this area. A relative numerical study with respect to experimentally obtained global response for tearing of these polymers is done through use of a similar material model developed from tensile tests and the challenges faced in this area have been addressed.

This thesis is intended to identify the mode I and mode II fracture toughness to characterize the thin laminate interface by using the Double Cantilever Beam test (DCB) and End Notched Flexure test (ENF). This study’s thin laminate was Polyethylene Terephthalate and Low-Density Polyethylene (PET-LDPE), which is mostly used by packaging industries in the manufacturing of packages to store liquid food. As PET-LDPE film is very flexible and difficult to handle, DCB and ENF tests cannot be performed directly so, sheet metal (Aluminium) was used as carrier material. PET-LDPE film is placed between two aluminum plates to reduce the flexibility and perform the tests. Therefore, the Aluminium plate was also studied to find the constitutive parameters (young’s modulus (E) and mixed hardening parameters (Plastic properties)) under the tensile test and three-point bending test. From the test response, energy release rate calculation has been done for different Pre-crack lengths to validate the DCB and ENF experimental setup, study the different Pre-crack lengths, and characterize the laminate interface. Finite Element simulation (FE simulation) for those tests were carried out in AbaqusTM2020. When needed, the force versus displacement response from FE simulation was optimized against experimental response to find the required constitutive parameters (Young’s modulus, Hardening parameters, and PET-LDPE material properties). Implementing of optimization algorithm and automated simulation has been done with the help of MATLAB code. In contrast, MATLAB works as a server, and Abaqus works as a client and connected two interfaces to run the optimization. The results obtained from experiments and FE simulations were compared to the results found in the literature.

No description available.

The crystallization and melting behaviors of an ethylene/1-hexene copolymer and series of narrow molecular weight linear polyethylene and poly(ethylene oxide) fractions were studied using a combination of ultra-fast and conventional differential scanning calorimetry, optical microscopy, small angle X-ray scattering, and wide angle X-ray diffraction. In the case of linear polyethylene and poly(ethylene oxide), the zero-entropy production melting temperatures of initial lamellae of isothermally crystallized fractions were analyzed in the context of the non-linear Hoffman-Weeks method. Using the Huggins equation, limiting equilibrium melting temperatures of 141.4 ± 0.8oC and 81.4 ± 1.0oC were estimated for linear polyethylene and poly(ethylene oxide), respectively. The former and the latter are about 4oC lower and 12.5oC higher than these predicted by Flory/Vrij and Buckley/Kovacs, respectively. Accuracy of the non-linear Hoffman-Weeks method was also examined using initial lamellar thickness literature data for a linear polyethylene fraction at different crystallization temperatures. The equilibrium melting temperature obtained by the Gibbs-Thomson approach and the C2 value extracted from the initial lamellar thickness vs. reciprocal of undercooling plot were similar within the limits of experimental error to those obtained here through the non-linear Hoffman-Weeks method. In the next step, the Lauritzen-Hoffman (LH) secondary nucleation theory was modified to account for the effect of stem length fluctuations, tilt angle of the crystallized stems, and temperature dependence of the lateral surface free energy. Analysis of spherulite growth rate and wide angle X-ray diffraction data for 26 linear polyethylene and 5 poly(ethylene oxide) fractions revealed that the undercooling at the regime I/II transition, the equilibrium fold surface free energy, the strength of the stem length fluctuations and the substrate length at the regime I/II transition are independent of chain length. The value of the equilibrium fold surface free energy derived from crystal growth rate data using the modified Lauritzen-Hoffman theory matches that calculated from lamellar thickness and melting data through the Gibbs-Thomson equation for both linear polyethylene and poly(ethylene oxide). Larger spherulitic growth rates for linear polyethylene than for poly(ethylene oxide) at low undercooling is explained by the higher secondary nucleation constant of poly(ethylene oxide). While the apparent friction coefficient of a crystallizing linear polyethylene chain is 2 to 8 times higher than that of a chain undergoing reptation in the melt state, the apparent friction coefficient of a crystallizing poly(ethylene oxide) chain is about two orders of magnitude lower. This observation suggests that segmental mobility on the crystal phase plays a significant role in the crystal growth process. In case of the statistical ethylene/1-hexene copolymer, the fold surface free energies of the copolymer lamellae at the time of crystallization and melting increase with increasing undercooling, approaching the same magnitude at high undercooling. As a result of this temperature dependence, the experimental melting vs. crystallization temperature plot is parallel to the Tm = Tc line and the corresponding Gibbs-Thomson plot is non-linear. This behavior is attributed to the fact that longer ethylene sequences form a chain-folded structure with lower concentration of branch points on the lamellar surface at lower undercooling, while shorter ethylene sequences form lamellar structures at higher undercooling exhibiting a higher concentration of branch points on the lamellar surface. Branch points limit the ability of lamellar structures to relax their kinetic stem-length fluctuations during heating prior to melting. / Ph. D. / Morphology of semi-crystalline polymers is strongly affected by their crystallization conditions. Thermodynamic and kinetic models allow us to understand the crystallization mechanism of a semi-crystalline polymer and relate its crystallization conditions to the final morphology. In this research, we studied the molar mass dependence of the crystallization and melting behaviors of narrow molecular weight distribution linear polyethylene (LPE) and poly(ethylene oxide) (PEO) fractions using a modified Lauritzen-Hoffman (LH) secondary nucleation theory. We have shown that the equilibrium melting temperature of LPE and PEO fractions found from the non-linear Hoffman-Weeks method are within the experimental uncertainty identical with these measured directly for extended chain crystals or derived from a Gibbs-Thomson analysis. The value of the equilibrium fold surface free energy derived from crystal growth rate data using the modified LH theory matches that calculated from lamellar thickness and melting data through the Gibbs-Thomson equation for both LPE and PEO. We reported that the higher segmental mobility of PEO in the crystalline phase leads to significantly lower apparent chain friction coefficients during crystal growth compared to LPE. We also studied the role of short-chain branching in the crystal growth kinetics of ethylene/1-hexene copolymers. We observed that the fold surface free energies during crystallization and during melting are both function of the undercooling while the ratio of the former to the latter decreases with increasing undercooling. We proposed that this behavior may be related to the concentration of short-chain branches at the surface of the lamellae, where higher concentration leads to lower relaxation.

M. Tech. (Civil Engineering, Faculty of Engineering and Technology), Vaal University of Technology) / Modified asphalt concrete is one of the important construction materials for flexible pavements. The addition of polymers and natural hydrocarbon modifiers to enhance the properties of asphalt concrete over a wide temperature range in paving applications has been the common practice. Currently these modified asphalt mixtures are relatively expensive. However, recycled polymers and rubber added to asphalt have also shown similar results in improving the performance of road pavements. In this study, an attempt has been made to use low density polyethylene (LDPE) obtained from plastic waste and crumb rubber obtained from worn out vehicle tyres. The aim was to optimise the proportions of LDPE in the bitumen binder using the ‘wet process’ and crumb rubber aggregates in the hot mix asphalt (HMA) using the ‘dry process’. The Marshall method of bituminous mix design was carried out for varying percentages of LDPE namely 2%, 4%, 6%, 8% and 10% by weight of bitumen binder and 1%, 2%, 3%, 4% and 5% crumb rubber by volume of the mineral aggregates. The characteristics of bitumen modified with LDPE were evaluated. The modified asphalt mix was also evaluated to determine the different mix characteristics. The results from laboratory studies in terms of the rheological properties of the LDPE modified bitumen binder showed an increase in viscosity, softening point and stiffness of the binder. The optimum Marshall stability values for HMA mixtures containing 2% crumb rubber tyre and 4% LDPE were found to be 30% higher than the conventional asphalt concrete mix. The wheel tracking test done at 50ºC was 9.81mm rut depth showing a good rutting resistance of the optimized mixture compared to the conventional asphalt mixes. The Modified Lottman test gave a Tensile Strength Ratio value of 0.979 which indicates a low degree of moisture susceptibility of the modified asphalt mix. The above results showed improved properties of the asphalt mixture. The economic assessment done using the present worth of costs indicated a reduction in maintenance cost due to the extended service life of the modified asphalt pavement.

Made available in DSpace on 2015-03-26T13:51:59Z (GMT). No. of bitstreams: 1 texto completo.pdf: 1426624 bytes, checksum: 8ec26861eeae9b5c7bd7e331f352548c (MD5) Previous issue date: 2009-07-24 / Conselho Nacional de Desenvolvimento Científico e Tecnológico / The oil extraction from Jatropha curcas seeds as raw material to biodiesel production releases a large quantity of solid residue, called cake.This Jatropha cake is formed by lignocellulolytic residues, water, minerals salts, but also contains toxic compounds and antinutritional factors. The correct destination of this residue is of great interesting to biofuel industries. The use of these residues as a substrate to grow the white rot fungi, Pleurotus ostreatus, may be a low cost alternative to produce the economic and industrial interesting products such as enzymes, proteins and edible mushrooms. Moreover, this fungus produces enzyme capable of degrade different toxic compounds and antinutritional factors. ln this study Jatropha cake, pure or in mixture with agro-industrial residues, was used as substrate to grow P. ostreatus objecting to produce mushrooms, eliminate phorbol ester, antinutritional factors and also, to evaluate the reduce lignin, cellulose and hemicellulose. After 45 days of P. ostreatus mycelia inoculation in the substrate, it was observed high production of fungus biomass, and degradation of 50 % of lignin and 20 % of cellulose and hemicellulose. The substrates which present higher fungus biomass production and lignocellulolitic degradation were used to assess the ability of P. ostreatus to produce mushroom and to degrade phorbol ester, phytic acid and tannins. After 60 d of incubation, it was observed good production of mushroom, reduction of lignocellulolytic compounds and loss of dry mass, reduction of phytic acid in 95 % and 85 % of tannins (equivalent a tannin acid) and 99 % of phorbol ester. These mushrooms and the substrates after 60 d of colonization by P. ostreatus had concentrations of phorbol esters smaller than that found in provenances of non toxic J. curcas from México. Therefore, P. ostreatus has the ability of degrade toxic compounds, antinutritional factors and lignooellulosio compounds present in Jatropha cake. The alternative of using Jatropha cake as substrate to mushroom and enzymes production, add value to this residues, as well as detoxifying it show high potential to use Jatropha cake as animal food, beyond deoreasing the environmental damage. / A produção de biodiesel utilizando o óleo da semente de pinhão manso (Jatropha curcas) como matéria-prima libera grande quantidade de resíduos sólidos, denominado de torta.Essa torta apresenta composição diversificada, contendo não só compostos ligninocelulósicos, água e sais minerais, mas também compostos tóxicos e fatores antinutricionais. A destoxificação e o reaproveitamento dessa torta de pinhão manso são de grande interesse da indústria do biocombustível. A utilização desses resíduos como substrato para cultivo de fungos de podridão branca, Pleurotus ostreatus, pode ser uma alternativa de baixo custo e que permite a produção de produtos de interesse econômico e industrial como enzimas, proteínas e cogumelos comestíveis. Além disso, esse fungo produz enzimas capazes de degradar diferentes substâncias tóxicas, fatores antinutricionais e compostos ligninocelulósicos. Neste trabalho, a torta de pinhão manso pura, ou em mistura com outros resíduos agroindustriais, foi utilizada como substrato para crescimento micelial de P. ostreatus visando à eliminação de compostos tóxicos, fatores antinutricionais e a redução do teor de lignina, celulose e hemicelulose. Inicialmente, para verificar a viabilidade micelilal e a degradação compostos ligninocelulósicos presente na torta de pinhão manso. P. ostreatus PLO 6 foi inoculado em substratos à base da torta de pinhão manso, adicionado ou não de resíduos agroindustriais. Após 45 dias de incubação, verificou-se elevada produção de biomassa fúngica, 50 % de degradação de lignina e 20 % de consumo de celulose e hemicelulose. Os substratos que apresentaram maior produção de biomassa fúngica e também a maior degradação de compostos ligninocelulósicos foram utilizados para avaliar a capacidade de P. ostreatus formar cogumelos, além de degradar éster de forboI, ácido fítico e taninos. Após 60 dias de incubação, observou-se boa produção de cogumelos e degradação de compostos Iigninocelulósicos, com significativa perda da massa seca, redução de 95 % de ácido fítico, 85 % de taninos (equivalente a ácido tânico), 99 % de éster de forboI e aIta produtividade de cogumelos. Após o período de incubação, tantos os cogumelos de P. ostreatus como os substratos utilizados apresentaram concentrações de éster de forboI menor que o encontrado em variedade de J. curcas não tóxicas do México. Conclui-se que P. ostreatus tem capacidade de degradar composto tóxico, fatores antinutricionais e compostos Iigninocelulósicos presentes na torta de pinhão manso. O uso alternativo de torta de pinhão manso como substrato para cultivo de cogumelos e enzimas, destoxificando-o, agrega vaIor a esse resíduo, e apresenta um aIto potencial do uso dessa torta como alimento, além de diminuir os danos ambientais causados peIo descarte direto.

Les matières plastiques ont désormais envahi notre quotidien. Elles sont le symbole de la société de consommation, car elles sont considérées comme un matériau non noble : les consommateurs l'assimilent à un produit jetable après usage. N'étant pas dégradables, les plastiques représentent donc un réel danger pour l'environnement, la faune et la flore.L’objectif de ce travail de thèse a été de développer en collaboration avec l’Institut des Sciences Analytiques et de Physico-Chimie pour l'Environnement et les Matériaux (Université de Pau) de nouvelles formulations avec des additifs naturels pour obtenir des plastiques résistants et recyclables. Deux types de résines ont été utilisées : le polypropylène isotactique (i-PP) et le polyéthylène à basse densité (LDPE). Des antioxydants naturels tels que l’acide ascorbique, l’alpha-tocophérol et l’huile de lin ont été testés et leur encapsulation a permis d’améliorer leur résistance à la dégradation. Les caractérisations thermique et rhéologique des résines ont montré des qualités supérieures aux résines commerciales actuelles. Nous avons pu démontrer que les plastiques obtenus pouvaient être recyclés 9 fois sans perte de leurs caractéristiques. Des essais avec des barquettes fabriquées avec les produits élaborés sont en cours pour valider les modèles développés. / Plastics have now invaded our daily lives. They are the symbol of the consumer society, because they are considered a non-noble material: consumers equate it with a disposable product after use. Since plastics are not degradable, they represent a real danger to the environment, fauna and flora.The objective of this thesis work was to develop in collaboration with the Institute of Analytical Sciences and Physico-Chemistry for Environment and Materials (Pau University) new formulations with natural additives to produce resistant and recyclable plastics. Two types of resins were used: isotactic polypropylene (i-PP) and low density polyethylene (LDPE). Natural antioxidants such as ascorbic acid, alpha-tocopherol and flaxseed oil were tested and encapsulated to improve their resistance to degradation. Thermal and rheological characterizations of resins have shown superior qualities to current commercial resins. We were able to demonstrate that the plastics obtained could be recycled 9 times without losing their characteristics. Tests with trays made with the developed products are underway to validate the developed models.

Les déchets plastiques s'accumulent depuis plusieurs décennies dans les océans où ils se fragmentent en particules appelés microplastiques lorsque leur taille est inférieure à 5 mm. Ces microplastiques sont retrouvés dans toutes les eaux du globe, dans les sédiments ainsi que dans de nombreux organismes marins. Le devenir physicochimique à long terme de ces particules et leur possible fragmentation en nanoplastiques sont complexes, encore peu documentés et nécessitent des études en laboratoire.Afin de comprendre les processus liés à la photodégradation et à la fragmentation des polymères dans l’environnement, mais également dans le but d’'appréhender l’évolution des fragments générés au cours de l’irradiation, un protocole de vieillissement accéléré en milieu abiotique a été mis en place sur des polymères modèles. Le suivi de l’oxydation et de la fragmentation des deux polymères étudiés,polyéthylène basse densité et polypropylène, a été mené à l’aide de techniques spectroscopiques (infrarouge, Raman), DSC, angles de contact, et microscopiques (lumière polarisée, MEB, AFM…).Ce travail a permis de mettre en évidence l’influence significative de l’environnement et de la morphologie initiale des polymères sur leurs cinétiques de vieillissement et leurs mécanismes de fissuration. Ainsi des distributions en nombres, tailles et formes de fragments très différentes ont été obtenues pour les deux polymères selon la présence d’eau. Enfin, après un long temps d’irradiation, des produits de dégradation ont pu être détectés mais la production significative de nanoplastiques n’a pas été démontrée. L'hypothèse d'une taille limite de fragmentation devrait être envisagée. / Plastic wastes have been accumulating for several decades in the oceans where they break up into particles called microplastics when their size is less than 5 mm. These microplastics are found in all earth’s waters, in sediments and in many marine organisms. Their long-term physico-chemical fate and their possible fragmentation into nanoplastics are complex, still poorly documented and require laboratory studies.In order to understand the processes related to photodegradation and fragmentation of polymers, but also in order to understand the evolution of these fragments during irradiation, an accelerated aging protocol in abiotic conditions has been set up. The oxidation and fragmentation of two model polymers, low density polyethylene and polypropylene, were monitored using spectroscopic techniques (InfraRed, Raman), DSC, contact angles and microscopic technics (light microscopy, polarized light, SEM, AFM ...).This work has demonstrated a significant influence of the environment and the initial morphology of the polymers on their kinetics of aging and cracking mechanisms. This lead to significantly different distributions in numbers, sizes and shapes of the generated fragments. Moreover, after a long time of irradiaiton, other degradation products could be detected but the significant production of nanoplastics has not been demonstrated. The possibility of a size limit below which the fragmentation rate of plastics would strongly decrease should be considered.

Este trabajo contribuye a la organización estudiada a mejorar los procedimientos del proceso de laminación (compuestas por BOPP y PEBD) para así reducir las mermas y los productos defectuosos, estas representan un 15% de desperdicios del total de materia prima que ingresa al proceso, sin embargo, con la aplicación de las metodologías se logró reducir a un 6.2% de desperdicios, resultando en ahorros operacionales en el rango de s/. 46,580 al año. La utilización de las fases DMAIC y Lean, cada uno a su manera, son las principales técnicas estratégicas de resolución de problemas en el mundo industrial. La integración de los dos métodos de calidad traerá la herramienta necesaria para eliminar las mermas y mejorar la productividad a través del comportamiento de los trabajadores, el trabajo en equipo y optimizando los procesos. Los gerentes e ingenieros encargados de mejorar las operaciones y los procesos pueden beneficiarse de este documento, ya que puede servir de guía para dirigir la realización de futuros proyectos y la aplicación empírica de sus principios y herramientas. / This work contributes to help the organization studied to improve procedures for the lamination process (compound of BOPP and LDPE) to reduce waste and defective products, represent 15% of waste of all raw material entering To the process, however, with the application of the methodologies was reduced to a 6.2% of waste, resulting in operational savings in the range of s /. 46,580 per year. The use of the DMAIC and Lean phases, each in its own way, are the main strategic techniques for solving problems in the industrial world. The integration of the two quality methods will bring the necessary tool to eliminate the losses and improve the productivity through the behavior of the workers, the team work and optimizing the processes. Managers and engineers in charge of improving operations and processes can benefit from this document as it can guide future projects and the empirical application of their principles and tools. / Trabajo de Suficiencia Profesional

Recycled material produced during three months from packing polyethylene foils coming from three suppliers was analysed together with one recycled material under complaint from the point of melt flow index (MFI), composition and mechanical properties. The addition of linear low density polyethylene (LLDPE) into the recycled material was studied as well. It was measured melt flow index (MFI), Differential scanning calorimetry (DSC) together with Thermogravimetry methods were used to determine composition. Selected materials were pressed to obtain films with the thickness of 1 mm to determine tensile properties. Recycled materials contained 40–65% LLDPE, small amount of polypropylene as well as chalk. The content of LDPE and LLDPE varied within one supplier and thus mechanical properties did. The results showed the difference in quality of PE films separation among all suppliers. The problems with workability of material under complaint were caused by the material composition – the amount of LLDPE predominated. The addition of LLDPE into the recycled material in the range of 5–20 % increased MFI by 13-78%. Mechanical properties of blends rich in LLDPE were similar to those of clear LLDPE. The presence of LDPE influenced more markedly only the strength to break. The blends of LDPE and LLDPE were evaluated as immiscible but with high affinity of the components with increasing contend of LLDPE. No material was chemically degraded. The methods commonly performed in manufacture, especially MFI, are not able to differentiate LDPE form LLDPE – recommended is DSC.