Yes / Binary and ternary blends of a polylactic acid matrix with polycaprolactone (PCL) and polybutylene succinate (PBS) were produced by twin screw extrusion, containing up to 30 wt% loading. Mechanical, thermal and rheological characterisation techniques were used to quantify properties of the different blend formulations and miscibility was investigated using scanning electron microscopy. PCL is known to act as an impact modifier in PLA but to cause a corresponding reduction in strength. Results showed that addition of both PBS and PCL seperatly caused a reduction in melt viscosity, elastic modulus and tensile strength, but an increase in impact strength and strain at break. Analysis of morphology suggested that immiscibility was evident, particularly at higher PCL and PBS loadings. Results indicated that incorporation of a small loading of PBS had a synergistic effect on the PLA-PCL blend properties. Miscibility was improved and enhanced mechanical properties were observed for a ternary blend containing 5 wt% of both PBS and PCL compared to blends containing 10% of each polymer alone. / Financial support of Floreon- Transforming Packaging Ltd through the PhD sponsorship and materials provision.

No description available.

The subject of this project is to study spun cellulose fibers made by Spinnova Oy inFinland. The fibers are spun using an environmentally friendly spinning process withoutuse of harsh chemicals.The spun filaments and the yarn based on these filaments were characterized and usedas reinforcement in polylactic acid biopolymer (PLA) and in biobased epoxy resin. Acomprehensive mechanical and morphological characterization of the single filamentsand their yarn was conducted. It was found that the single filaments are flat with a largewidth/thickness ratio, they are porous especially on one side and some cellulosemicrofibril orientation is observed on the filament surface. The single filaments are stiffand strong if compared to commercial regenerated cellulose filaments but are difficultto handle as they are very small and extremely light. The yarn showed to have lowermechanical properties but is easier to handle during the process of compositemanufacturing. Unidirectional fiber-reinforced composites were made using theSpinnova-yarn and PLA polymer applying film-stacking processing method. Thecomposite mechanical properties were studied and the results showed that themechanical performance of the PLA was significantly improved. The strength improvedfrom 54 MPa of the neat PLA to 95 MPa and the stiffness from 3.4 to 8.6 GPa withaddition of 22 wt% Spinnova-yarn.The main challenge of the project was handling the single filaments and their yarn todevelop a suitable manufacturing process which allows to exploit the potential of themto obtain a homogeneous fiber “preform” and to achieve good impregnation with the PLA matrix.

This thesis presents a model for the procedures of manufacturing Fused Filament Fabrication (FFF) components by calculating required process parameters using empirical equations. Such an empirical model has been required within the FFF field of research for a considerable amount of time and will allow for an expansion in understanding of the fundamental mathematics of FFF. Data acquired through experimentation has allowed for a data set of geometric characteristics to be built up and used to validate the model presented. The research presented draws on previous literature in the fields of additive manufacturing, machine engineering, tool-path programming, polymer science and rheology. Combining these research fields has allowed for an understanding of the FFF process which has been presented in its simplest form allowing FFF users of all levels to incorporate the empirical model into their work whilst still allowing for the complexity of the process. Initial literature research showed that Polylactic Acid (PLA) is now in common use within the field of FFF and therefore was selected as the main working material for this project. The FFF technique, which combines extrusion and Computer Aided Manufacturing (CAM) techniques, has a relatively recent history with little understood about the fundamental mathematics governing the process. This project aims to rectify the apparent gap in understanding and create a basis upon which to build research for understanding complex FFF techniques and/or processes involving extruding polymer onto surfaces.

Polylactic acid (PLA) is an aliphatic polyester, derived from sustainable natural sources that is biodegradable and can be industrially composted. This material has been in the spotlight recently due to its sustainability and properties. However it has been invented in 1932 by Carothers and then patented by DuPont in 1954 (Standau et al. 2019). The properties of this material though limit its use for applications mainly in the medical sector and in some cases single use packaging. In this research, PLA based blends with improved rheological and thermomechanical properties are investigated. The focus is based in proposing strategies in improving these properties based on commercial methods and processing techniques. In this work, commercial grade PLA has been blended with polycaprolactone (PCL) and polybutylene succinate (PBS) in binary and ternary formulations via twin screw extrusion. PCL has been known to act as an impact modifier for PLA, but to cause a corresponding reduction in strength. Results showed that the binary PLA blends containing PBS and PCL, had reduced viscosity, elastic modulus and strength, but increased strain at break and impact strength. Morphological and thermal analysis showed that the immiscibility of these additives with PLA caused these modifications. Incorporation of a small loading of PBS had a synergistic effect on the PLA-PCL blend properties. Miscibility was improved and enhanced mechanical properties were observed for a ternary blend containing 5wt% of both PBS and PCL compared to binary blends containing 10% of each additive. To increase heat resistance of PLA, the material’s crystallinity has to be increased. However PLA has a relatively slow crystallisation rate making it difficult and expensive to be used in commercial applications where heat resistance is needed. For this reason the chiral nature of PLA has been used to investigate the effect of stereochemistry of PLA in crystallisation. Optically pure PDLA was added to its enantiomer in small amounts (up to 15%) and the properties and crystallisation mechanism of these blends was investigated. Results showed that the addition of PDLA accelerated crystallinity and developed a stucture that increased heat resistance, melt strength and stiffness. Finally, a processing model of developing a fully stereocomplex PLA part based in commercial techniques is proposed. Injection moulded PLA showed even higher heat resistance without the need of further processing the product (increasing crystallinity). / Floreon

No description available.

No description available.

Titanium dioxide (TiO2) polymer nanocomposites improve barrier properties to gas and moisture and mechanical strength as well as providing active packaging functions. However, low compatibility between hydrophilic TiO2 nanoparticles and hydrophobic polymers such as polylactic acid (PLA) causes problems due to the tendency of TiO2 nanoparticles (TiO2) to agglomerate and form large clusters. A surface modification of TiO2 with long chain fatty acid may improve the compatibility between PLA and TiO2. The goal of this study was to enhance barrier properties of oxygen and water vapor, mechanical strength and add light protecting function to PLA composites by incorporation of oleic acid modified TiO2 nanoparticles (OA_TiO2). The objectives of this study were: 1) synthesize TiO2 and modify surface of TiO2 with oleic acid, 2) investigate dispersion stability of TiO2 and OA_TiO2 in hydrophobic media, 3) incorporate TiO2 and OA_TiO2 into a PLA matrix and to characterize properties of TiO2PLA (T-PLA) and OA_TiO2 PLA nanocomposite films (OT-PLA), and 4) to determine stability of green tea infusion in T-PLA and OT-PLA packaging model systems during refrigerated storage at 4 °C under florescent lightening. TiO2 was synthesized by using a sol-gel method and the surface of TiO2 was modified by oleic acid using a one-step method. T-PLA and OT-PLA were prepared by solvent casting. TiO2 and OA_TiO2 were analyzed by X-ray diffraction, Fourier transform infrared spectroscopy, thermal analysis and dynamic light scattering. The barrier properties to oxygen and water vapor, morphology, mechanical properties, thermal stability and light absorption properties of T-PLA and OT-PLA were characterized. Dispersion of TiO2 was improved in PLA matrix by the surface modification method with oleic acid. OT-PLA had more effective improvements in the barrier properties and flexibility than T-PLA and PLA, but toughness of the films based on Young's modules of OT-PLA was lower than the T-PLA and the PLA. The OT-PLA may have a potential to be used as transparent, functional and sustainable packaging films, but limited use for complete visible and UV-light protection for photosensitized foods. / Ph. D.

Natural disasters are affecting a significant number of people around the world. Sheltering is the first step in post-disaster activities towards the normalization of the affected people's lives. Temporary housing is being used in these cases until the construction of permanent houses are done. Disposal of temporary housing after use is leading to a significant environmental impact because most of them are filled with thermally insulative polymer foams that do not degrade in a short period. To reduce these problems this work proposes to use foams made with compostable thermoplastic polylactic acid (PLA) and degradable kenaf core as filler materials; these foams are made using CO2 as blowing agent for insulation purposes. Foams with PLA and 5%, 10% and 15% kenaf core were tested. Different properties and their relations were examined using differential scanning calorimetry (DSC), thermal conductivity, mechanical properties, scanning electron microscopy (SEM), x-ray μ-computed tomography (μ-CT) and building energy simulations were done using Energy Plus by NREL. The results show that mechanical properties are reduced with the introduction of kenaf core reinforcement while thermal conductivity display a noticeable improvement.

Tesis por compendio / [ES] Los residuos de envases alimentarios contribuyen en gran medida a la actual crisis medioambiental provocada por los plásticos. Por ello, la industria alimentaria necesita soluciones de envasado más sostenibles y respetuosas con el medio ambiente, utilizando materiales biodegradables y activos para alargar la vida útil de los alimentos. En este sentido, la presente tesis doctoral tiene como objetivo la obtención de películas activas a base de almidón y PLA mediante la incorporación de ácidos ferúlico o cinámico como compuestos activos, con el fin de desarrollar laminados multicapa que cumplan con los requisitos de envasado de alimentos, con capacidad antibacteriana para alargar la vida útil del producto. La incorporación de los ácidos ferúlico y cinámico a las matrices de almidón de yuca mediante el proceso de mezclado en fundido, al 1 y 2%, promovió la plastificación de la película, probablemente debido a la hidrólisis parcial del polímero durante el proceso de mezclado. Los análisis de la actividad antibacteriana de las películas frente a Escherichia coli y Listeria innocua, en medio de cultivo, revelaron que las películas con ácido cinámico eran más eficaces para inhibir el crecimiento bacteriano, y que Listeria innocua era más sensible a ambos ácidos que E. coli. Cuando los ácidos se incorporaron a las matrices de PLA al 1 y 2% mediante mezclado en fundido, las propiedades funcionales de las películas no se vieron muy afectadas. Sin embargo, los ensayos antimicrobianos in vitro con L. innocua y E. coli, no mostraron acción antibacteriana. Los estudios de liberación mostraron una liberación muy limitada de los ácidos desde la matriz de PLA debido al estado vítreo de la matriz polimérica y a su naturaleza hidrofóbica, que limitan el hinchamiento y la relajación del polímero en contacto con medios acuosos, como muchas matrices alimentarias. Por lo tanto, para promover la liberación del compuesto activo desde la matriz de PLA, se analizaron diferentes estrategias: 1) plastificar las películas termoprocesadas con PEG 1000, 2) aumentar la concentración de los compuestos en la película, 3) procesar las películas por casting y 4) anclar los compuestos activos a la superficie de la película. Sólo la incorporación superficial de ferúlico o cinámico en las películas de PLA dio lugar a una inhibición significativa del crecimiento bacteriano. La pulverización de las películas de PLA con soluciones etanólicas de ácido permitió la formación superficial de una capa sobre concentrada de compuestos activos en las películas, con formaciones cristalinas que dio lugar a una adecuada liberación de activos para inhibir el crecimiento bacteriano. Disoluciones de PLA-ácido, utilizando mezclas de acetato de etilo con DMSO o ácido acético glacial, fueron electrodepositadas en la superficie de las películas. Los sistemas con DMSO produjeron fibras con una elevada superficie específica que inhibieron significativamente el crecimiento bacteriano, mientras que los sistemas con ácido acético produjeron estructuras particuladas sin actividad antimicrobiana. Se consideró la incorporación superficial de los compuestos activos para obtener películas de tres capas PLA/almidón/PLA (PSP) con mejores propiedades funcionales y capacidad antimicrobiana. Las películas cargadas superficialmente, tanto por electrospinning como por pulverización, mostraron una eficaz inhibición del crecimiento de E. coli y L. innocua, siendo las películas recubiertas por electrospinning más eficaces que las pulverizadas. Por lo tanto, los laminados PSP, con incorporación superficial de ácidos ferúlico o cinámico, representan una buena alternativa para obtener materiales de envasado de alimentos activos, con capacidad para preservar la calidad de los alimentos y prolongar su vida útil. No obstante, son necesarios más estudios sobre aplicaciones específicas en alimentos reales para determinar la posible aplicación industrial y la viabilidad económica de estos materiales. / [CA] Els residus d' envasos alimentaris contribueixen en gran mesura a l' actual crisi mediambiental provocada pels plàstics. Per això, la indústria alimentària necessita solucions d' envasament més sostenibles i respectuoses amb el medi ambient, utilitzant materials biodegradables i actius per allargar la vida útil dels aliments. En aquest sentit, aquesta tesi doctoral té com a objectiu l' obtenció de pel·lícules actives a base de midó i PLA mitjançant la incorporació d' àcids ferúlic o cinàmic com a compostos actius, per tal de desenvolupar laminats multicapa que compleixin amb els requisits d' envasament d' aliments, amb capacitat antibacteriana per allargar la vida útil del producte. La incorporació dels àcids ferúlic i cinàmic a les matrius de midó de iuca mitjançant el procés de mesclament en fos, a l'1 i 2% p/p, va promoure la plastificació de la pel·lícula, probablement a causa de la hidròlisi parcial del polímer durant el procés de barret. Les anàlisis de l'activitat antibacteriana de les pel·lícules enfront d'Escherichia coli i Listeria innocua, en medi de cultiu, van revelar que les pel·lícules amb àcid cinàmic eren més eficaces per inhibir el creixement bacterià, i que Listeria innocua era més sensible a tots dos àcids que E. coli. Quan els àcids van incorporar a les matrius de PLA a l'1 i al 2% mitjançant mesclament en fos, les propietats funcionals de les pel·lícules no es van veure gaire afectades. No obstant això, els assajos antimicrobians in vitro amb L. innocua i E. coli, no van mostrar acció antibacteriana. Els estudis d'alliberament van mostrar un alliberament molt limitat dels àcids ferúlic i cinàmic des de la matriu de PLA a causa de l'estat vitri de la matriu polimèrica i a la seva naturalesa hidrofòbica, que limiten l'hinxament i la relaxació del polímer en contacte amb mitjans aquosos, com moltes matrius alimentàries. Per tant, per promoure l' alliberament del compost actiu des de la matriu de PLA, es van analitzar diferents estratègies: 1) plastificar les pel·lícules termoprocessades amb PEG 1000, 2) augmentar la concentració dels compostos a la pel·lícula, 3) processar les pel·lícules per casting i 4) ancorar els compostos actius a la superfície de la pel·lícula. Només la incorporació superficial de ferúlic o cinàmic a les pel·lícules de PLA va donar lloc a una inhibició significativa del creixement bacterià. La polvorització de les pel·lícules de PLA amb solucions etanòliques d'àcid va permetre la formació superficial d'una capa sobreconcentrada de compostos actius a les pel·lícules, amb formacions cristal·lines, que va donar lloc a un adequat alliberament d'actius per inhibir el creixement bacterià. Dissolucions de PLA-àcid, utilitzant mescles d'acetat d'etil amb DMSO o àcid acètic glacial, van ser electrodepositades a la superfície de les pel·lícules. Els sistemes amb DMSO van produir fibres amb una elevada superfície específica que van inhibir significativament el creixement bacterià, mentre que els sistemes amb àcid acètic van produir estructures particulades sense activitat antimicrobiana. Es va considerar la incorporació superficial dels compostos actius per obtenir pel·lícules de tres capes PLA/midó/PLA (PSP) amb millors propietats funcionals i capacitat antimicrobiana. Les pel·lícules carregades superficialment, tant per electrospinning com per polvorització, van mostrar una eficaç inhibició del creixement d'E. coli i L. innocua, sent les pel·lícules recobertes per electrospinning més eficaços que les polvoritzades. Per tant, els laminats PSP, amb incorporació superficial d'àcids ferúlic o cinàmic, representen una bona alternativa per obtenir materials d'envasat d'aliments actius, amb capacitat per preservar la qualitat dels aliments i prolongar la seva vida útil. No obstant això, calen més estudis sobre aplicacions específiques en aliments reals per determinar la possible aplicació industrial i la viabilitat econòmica d' aquests materials. / [EN] Food packaging waste is a major contributor to the current environmental crisis caused by conventional plastic. Therefore, the food industry needs more sustainable environmentally friendly packaging solutions, such as using biodegradable and active materials to extend the food shelf-life. In this sense, the present doctoral thesis aims to obtain active films based on starch and PLA by incorporating ferulic or cinnamic acids as active compounds, in order to develop multilayer assemblies useful to meet food packaging requirements, with antibacterial capacity to extend the product shelf life. The incorporation of ferulic and cinnamic acids into cassava starch matrices through melt-blending process, at 1 and 2% w/w, promoted the film plasticization, probably due to the partial hydrolysis of polymer during the melt-blending process. The analyses of the antibacterial activity of the films against E. coli and Listeria innocua strains, in culture medium, revealed that films with cinnamic acid were more effective at inhibiting the bacterial growth, and that L. innocua was more sensitive to both acids than E. coli. When the acids were incorporated into PLA matrices at 1 and 2% w/w by melt blending, the functional properties of the films were not greatly affected. However, the in vitro antimicrobial tests with L. innocua and E. coli, did not show antibacterial action. Release studies showed very limited release of the ferulic and cinnamic acids from the PLA matrix due to the glassy state of polymer matrix and its hydrophobic nature that limits the polymer swelling and relaxation in contact with aqueous media, such as many food matrices. Therefore, in order to promote the release of active compound from the PLA matrix, different strategies were analysed: 1) plasticizing the thermoprocessed films with PEG 1000, 2) increasing the concentration of the compounds in the film, 3) processing the films by casting and 4) anchoring the active compounds to the film surface. Only the surface incorporation of ferulic or cinnamic on PLA films gave rise to significant bacterial growth inhibition. Pulverization of PLA films with ferulic or cinnamic acid ethanol solutions allows the formation of an overconcentrated layer of active compounds on the films with crystalline formations that led to an adequate release of actives to inhibit the bacterial growth. PLA-acid solutions, using blends of ethyl acetate with dimethyl sulfoxide (DMSO) or glacial acetic acid, were electrospun on the film surface. DMSO systems produced fibre-structured mats with high specific surface that significantly inhibited bacterial growth, whereas acetic acid systems produce bead-based mats that not had antimicrobial activity. The surface incorporation of the active compounds was considered for obtaining three-layered films PLA/starch/PLA (PSP) with improved functional properties and antimicrobial capacity. Superficially loaded films by both electrospinning or pulverisation, showed effective growth inhibition of E. coli and L. innocua, electrospun films being more effective than pulverised, suggesting greater ability to release the active compounds. Therefore, PSP laminates, with surface incorporation of ferulic or cinnamic acids, represent a good alternative to obtain active food packaging materials with the capacity to preserve food quality and extend shelf life. Nonetheless, further studies on the material stability and specific applications in real foods are necessary to determine the possible industrial application and economic viability of these materials. / The authors thank the Agencia Estatal de Investigación (Ministerio de Ciencia e Innovación, Spain) for the financial support through projects AGL2016-76699-R and PID2019-105207RB-I00. / Ordóñez Lagos, RA. (2022). Use of ferulic and cinnamic acids to obtain active films based on starch and PLA for food packaging applications [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/184814 / TESIS / Compendio