Tesis por compendio / Packaging plays an important role in ensuring food safety and quality. The development antimicrobial packaging enables actively inhibiting/killing the spoilage microorganisms, and thus extending food product's shelf life. Generally, 50% shelf life extension is possible. The interest for using metallic nanoparticles in active packaging derives from its superior antimicrobial efficacy and no negative impact on the food sensory properties. In this thesis, the packaging material of concern is a PLA (Polylactic Acid) coated paper incorporating zinc oxide nanoparticles (ZnO NPs) in the coating layer. The material was characterized and its antimicrobial activity was evaluated. The SEM images show that the nanoparticles were homogenously distributed across the surface thanks to its surface modification. Antimicrobial assay indicates that the active material was effective in inactivating E. coli and S. aureus. Furthermore, E. coli was found to be more susceptible to this type of agent, showing 3.14 log reduction for 0.5 wt% agent loading in the PLA coating layer. This result was compared across the publications using the same agent for treating both Gram-positive and Gram-negative microorganisms. The discrepancy between the results can be explained by the fact that ZnO nanoparticles have multiple action mechanisms, and different antimicrobial testing methods may activate part of the action mechanisms. On the other hand, recyclability is regarded as an important attribute for paper-based packaging material, as it enables to conserve the resources and reduce the environmental impacts. Accordingly, when it comes to the nano-enabled paper packaging material, recyclability should be maintained. In this case, a recyclability test was carried out in a lab-scale paper recycling line. The protocol was based on a method adapted from the ATICELCA MC501-13, which enabled to recover over 99% of the solids material. The mass balance result indicates that 86%-91% zinc oxide nanoparticles ended up in the rejected material stream, mostly embedded within the polymer coating; whereas 7%-16% nanoparticles ended up in the accepted material stream. Besides, the tensile strength of the recycled handsheets suggests that the nano-enabled coating had no negative impacts on the recovered fibre quality. Active packaging plays a positive role in reducing food losses. If food and packaging are considered as a whole system, its overall environmental impact can be justified by incorporating the food loss reduction due to the application of active packaging. The LCA calculation shows that a breakeven point can be easily achieved for the case of red meat products of high environmental impact. / El envase juega un papel importante asegurando la seguridad y calidad de los alimentos. El desarrollo de envases activos, especialmente envase antimicrobiano, permite inhibir o matar los microorganismos causantes del deterioro de los alimentos, alargando por tanto su vida útil. De forma general es posible extender la vida útil de los alimentos en un 50%. El interés por el uso de nanopartículas metálicas en el envasado activo se deriva de su gran efectividad antimicrobiana sin causar un efecto negativo en sus propiedades sensoriales. En la presente tesis, se ha desarrollado un papel recubierto de PLA (ácido poliláctico) con nanopartículas de óxido de zinc (ZnO NPs) incorporadas en la capa de recubrimiento. Se ha caracterizado el material y se ha evaluado su capacidad antimicrobiana. Las imágenes obtenidas mediante SEM muestran que las nanopartículas fueron distribuidas a lo largo de la superficie gracias a su modificación. Los ensayos de efectividad antimicrobiana indicaron una actividad del material frente a E. coli y a S. aureus. Además, E. coli resultó ser más susceptible a este agente activo incorporado al 0.5 % en peso en el recubrimiento de PLA, mostrando una reducción de 3.14 log. Este resultado fue comparado con publicaciones donde se emplearon los mismos agentes activos para frente a microorganismos Gram-positivos y Gram-negativos. Las discrepancias encontradas entre los resultados pueden deberse a que las nanopartículas de ZnO tienen múltiples mecanismos de acción, y los diferentes métodos de ensayo poder estimular parte de estos mecanismos. Por otra parte, el reciclado juega un importante papel en la conservación de los recursos y en la reducción de los impactos medioambientales. Por tanto, cuando se trata de un material de envase de papel con sustancias de tamaño nano, el reciclado debe tratarse adecuadamente. El ensayo de reciclabilidad fue llevado a cabo a escala laboratorio en una línea de reciclado de papel. El protocolo de ensayo se basó en el método adaptado de ATICELCA MC501-13, permitiendo una recuperación del 99% de material sólidos. Los resultados del balance de materia indicaron que el 86%-91% de las nanopartículas de óxido de zinc llegaron al flujo de material de rechazo, principalmente mezclado en el recubrimiento polimérico. Además, los resultados de tracción de las láminas recicladas sugieren que el recubrimiento con partículas nano no tiene un efecto negativo sobre la calidad de la fibra recuperada. El envase activo juega un papel positivo en la reducción de los residuos alimentarios. Como resultado del uso del envase activo, considerando el envase y el alimento como un todo, el impacto ambiental sobre este sistema completo puede ser compensado por la reducción de pérdidas de alimentos. El cálculo LCA muestra que el punto de equilibrio se puede conseguir fácilmente en el caso de productos de carne roja de elevado impacto ambiental. / L'envàs té un paper prou important en la seguretat i la qualitat del aliments. El desenvolupament dels envasos actius, especialment l'envàs antimicrobià, el qual permeteix l'inhibició o mort dels microorganismes que produeixen el deteriorament dels aliments i, per tant, allargant la seua vida útil. De manera general, es possible l'allargament de la vida útil dels aliments en un 50%. L'interès per la utilització de nanopartícules metàl·liques en l'envasat actiu es deriva de la seua gran efectivitat antimicrobiana sense produir un efecte negatiu en les seus propietats sensorials. En aquesta present tesis, s'ha desenvolupat un paper recobert de PLA (àcid polilàctic) amb nanopartícules d'òxid de zinc (ZnO NPs) incorporades a la capa de recobriment. S'ha caracteritzat el material i s'ha avaluat la seua capacitat antimicrobiana. Les imatges obtingudes per mitjà del SEM mostren que les nanopartícules foren distribuïdes en tota la superfície gràcies a la seua modificació. Els assajos d'efectivitat antimicrobiana varen indicar una activitat del material front a E.coli i a S. aureus. A més, E. coli va resultar ser més susceptible a aquest agent actiu incorporat al 0.5 % en pes en el recobriment de PLA, mostrant una reducció de 3.14 log. Aquest resultat va ser comparat amb publicacions on es van emprar els mateixos agents actius front a microorganismes Gram-positiu i Gram-negatiu. Les discrepàncies trobades entre els resultats poden deure's a que les nanopartícules de ZnO tenen diversos mecanismes d'acció, i els diferents mètodes d'assaig poder estimular part d'aquestes mecanismes. Per altra banda, el reciclatge també té un paper important en la conservació dels recursos i en la reducció dels impactes mediambientals. Per tant, quan es tracta d'un material d'envàs de paper amb substàncies de la grandària 'nano', el reciclatge ha de tractar-se adequadament. El assaig de reciclabilitat va ser dut a terme a escala de laboratori en una línia de reciclatge de paper. El protocol de l'assaig es va basar en el mètode adaptat d'ATICELCA MC501-13, permetent una recuperació del 99% del material sòlid. Els resultats del balanç de matèria van indicar que el 86-91% de les nanopartícules d'òxid de zinc varen arribar al fluix material de rebuig, principalment mesclat en el recobriment polimèric. A més, els resultats de tracció de les làmines reciclades suggereixen que el recobriment amb nanopartícules nano no tenen un efecte negatiu sobre la qualitat de la fibra recuperada. L'envàs actiu juga un paper positiu en la reducció dels residus alimentaris. Com a resultat de l'ús de l'envàs actiu, considerant l'envàs i l'aliment com un tot conjunt, l'impacte ambiental sobre aquest sistema complet pot ser compensat per la reducció de pèrdues d'aliments. El càlcul LCA mostra que el punt d'equilibri es pot aconseguir fàcilment en el cas de productes de carn roja d'elevat impacte ambiental. / Zhang, H. (2016). Sustainability assessment of active packaging incorporating nanomaterials [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/75348 / Compendio

Chalcogenide perovskites with a distorted ABX3 structure (A: Ca, Ba, Sr; B: Zr, Hf; X: S, Se) are a prominent focus in optoelectronic materials. One of these is BaZrS3 which has garnered significant attention in perovskite materials due to its distinctive distorted perovskite structure and valuable optical properties that are viable for a single-junction solar cell and present a compelling option for tandem solar cell configurations. Another promising material is SrZrS3 which exists in two phases: needle-like non-perovskite α-SrZrS3 and distorted perovskite β-SrZrS3. The distorted perovskite phase shows promising luminescence properties in bulk, making it potentially viable for LED applications. In this work, we show that the non-perovskite α-SrZrS3 was accessed through colloidal synthesis at 330 °C and 365 °C by increasing concentrations of precursors. In order to favor the perovskite phase, we conducted alloying experiments incorporating varying percentages of doped Sr2+ into BaZrS3 to first synthesize a distorted perovskite Ba(1-x)SrxZrS3. Through varying percentages and varying reaction conditions such as temperature, time of reaction, and doping concentrations, we aim to optimize the synthesis of colloidal Ba(1-x)SrxZrS3 nanocrystals.

Yes

Despite the rapid growth in nanotechnology, very little is known about the unintended health or environmental effects of manufactured nanomaterials. The development of nanotechnology risk assessments and regulations requires quantitative information on the potential for exposure to nanomaterials. In addition, to facilitate life-cycle assessments and inhalation toxicology studies, robust methods are needed to generate aerosolized engineered nanoparticles. We conducted a set of field studies to measure the fine particle mass concentrations (PM2.5) as well as nanoparticle number concentrations and size distributions in two nanomaterial manufacturing facilities. Measurements were performed near the reactor, in the breathing zone, and at a background site. Increases in PM2.5 and particle number concentrations were associated with physical handling of nanomaterials. The highest PM2.5 concentration observed was 2700 ug m-3 during sweeping of the reactor in the commercial plant. In most cases, an increase in the number of sub-100 nm particles accounted for the increase in total number concentrations. The results of this research can be used to develop guidelines for workplace regulations to minimize workers' exposure to nanoparticles. Furthermore, we used an atomizer to aerosolize C60 aggregates from a fullerene-water suspension. Measurement of particle size distributions and number concentrations showed that increasing the initial fullerene concentration resulted in increased number of aerosolized particles, while the average size of particles remained relatively constant. To return the aerosolized fullerenes into water, we passed the aerosol sample through an impinger. Reducing the flow rate through the impinger resulted in an increase in the collection efficiency of airborne nanoparticles. / Master of Science

Yes / The bond between FRP bars and concrete, the foremost performance for implementation of such reinforcements to corrosion-free concrete structures, is still unsatisfied due to the weak nature of duplex film in the interface. The existing approaches show low efficiency in improving the microstructures and bond between FRP bars and concrete. To address these issues, this paper provided a new approach for improving the bond between FRP bars and concrete by incorporating nanomaterials, as well as explored the modifying mechanisms and established the bond-slip models. For these purposes, the pull-out test, scanning electron microscope observation, as well as energy dispersive spectrometry analysis were performed. The experimental results demonstrated that the presence of nanomaterials increased the ultimate bond strengths between glass/carbon FRP bars and concrete by up to 16.2% and 37.8%, while the corresponding slips decreased by 28.7% and 35.4%, respectively. Such modification effects can be attributed to the optimized intrinsic composition and the reduced pore content of hydration products in the interface, especially in the duplex film, through the nanomaterial enrichment and nano-core effects. The bond-slip relationship between FRP bars and concrete with nanomaterials can be accurately predicted by the mBPE model. / The authors would like to thank the funding offered by the National Science Foundation of China (51978127 and 51908103), and the Fundamental Research Funds for the Central Universities (DUT21RC(3) 039).

Neurodegenerative disease (ND) is a collection of progressive disorders which is marked by gradual degeneration of the central nervous system (CNS). The damage of brain and nervous system causes diminishing of brain and nerve cell which lead to body dysfunction, organ failure, paralysis and ultimately death of a patient. Neurodegenerative diseases affect millions of people worldwide. United States of America is among highest ND prevailing disease countries. Yet the number of cases is underreported because of the complexity of disease diagnosis. With the increase in aging population the rate of ND cases is also increasing. Another important concern is that viral pandemic like COVID-19 may additionally contribute to rise in ND affected population. Currently there is no cure available for ND except a few treatments which decrease some symptoms and decrease disease progression. Early-stage diagnosis of ND is therefore an important and immediate area of research which can improve the quality of life of affected people and help in health management. Many ND has been associated with abnormal expansion of tandem repeat sequence of nucleic acid and other associated protein biomarkers. The discovery of these biomarkers holds promise for improving diagnosis, treatment, and efficacy monitoring. Current detection methods such as neuroimaging techniques, Real-Time quantitative Polymerase Chain Reaction (RT-qPCR) and Enzyme-Linked Immunosorbent Assay (ELISA) are complex, expensive, require laboratory setup and/or trained operator. Electrochemical biosensing offers a promising portable, inexpensive, and sensitive platform for early and robust diagnosis and healthcare management. In this dissertation a label free electrochemical method is developed to investigate the effect of complex targets for potential genosensing applications and effect of complex biomatrix for immunosensing applications. We first prepare sensing surfaces with three different backbone microprobe nucleic acids to detect length- and sequence-dependent complex secondary structures containing RNA linked to Huntington’s disease, based on the charge transfer resistance of the interface. Then we reported an immunosensing surface using commercially available screen-printed electrode to detect ALS associated biomarker neurofilament light chain in serum samples. Finally, we establish an in-house and cost effective electrochemical immunosensing platform for the detection of ALS biomarker poly-glycine-proline dipeptide repeat in cerebrospinal fluid.

This work involves synthesis and characterization of isotropic and anisotropic noble metal nanoparticles for applications ranging from antimicrobial uses to anticancer applications. These nanomaterials are stabilized in genuinely benign biomaterials ranging from polymers to cross linked proteins for targeted cancer treatments. The nanoparticles are found to have tunable optical properties.

<p>Polymer nanocomposites are a constantly evolving material category due to the ability to engineer the mechanical, thermal, and optical properties to enhance the efficiency of a variety of systems. While a vast amount of research has focused on the physical phenomena of nanoparticles and their contribution to the improvement of such properties, the ability to implement these materials into existing commercial or newly emerging processing methods has been studied much less extensively. The primary characteristic that determines which processing technique is the most viable is the rheology or viscosity of the material. In this work, we investigate the processing methods and properties of nanocomposites for thermal interface and radiative cooling applications. The first polymer nanocomposite examined here is a two-component PDMS with graphene filler for 3D printing via a direct ink writing approach. The composite acts as a thermal interface material which can enhance cooling between a microprocessor and a heat sink by increasing the thermal conductivity of the gap. Direct ink writing requires a shear thinning ink with specific viscoelastic properties that allow for the material to yield through a nozzle as well as retain its shape without a mold following deposition. No predictive models of viscosity for nanocomposites exist; therefore, several prominent models from literature are fit with experimental data to describe the change in viscosity with the addition of filler for several different PDMS ratios. The result is an understanding of the relationship between the PDMS component ratio and graphene filler concentration with respect to viscosity, with the goal of remaining within the acceptable limits for printing via direct ink writing. The second nanocomposite system whose processability is determined is paint consisting of acrylic filled with reflective nanoparticles for radiative cooling paint applications. The paint is tested with both inkjet and screen-printing procedures with the goal of producing a thermally invisible ink. Radiative cooling paint is successfully printed for the first time with solvent modification. This work evaluates the processability of polymer nanocomposites through rheological tailoring. </p><br>

La Microscopie Electronique à Balayage Environnementale permet l'observation de liquides dans certaines conditions de pression et température. En travaillant en transmission, i.e. en mode STEM (Scanning Transmission Electron Microscopy), des nano-objets présents au sein du liquide peuvent même être analysés (mode « Wet-STEM»). Dans les solutions concentrées, l'arrangement du soluté peut changer être un paramètre microstructural important, qu’il est alors nécessaire de caractériser. Dans ce contexte, le but de ce travail est de développer la tomographie électronique sur des suspensions liquides en utilisant le mode STEM en ESEM, de manière à obtenir la structure 3D de nano-objets dispersés dans un liquide. Dans une première partie, le contraste entre des nanoparticules et le film d’eau est étudié en combinant des images expérimentales Wet-STEM (en 2D) et des simulations Monte Carlo. Deux types de nano-matériaux sont choisis : des nanoparticules d’or sphériques, de diamètre environ 40 nm, dispersées dans l’eau, ainsi qu’une suspension aqueuse de latex SBA-PMMA, contenant 3% de PMMA utilisé comme tensioactif stérique. La comparaison entre les résultats simulés et expérimentaux permet d’estimer comment le contraste entre l’eau et les nanomatériaux est affecté par l’épaisseur du film d’eau. Dans une deuxième partie, des expériences de tomographie sont réalisées à sec sur des films de polyuréthane contenant des nanotubes de carbone multiparois greffés ou non, en utilisant une platine développée précédemment au laboratoire. Le volume a pu être reconstruit correctement. Cependant, en effectuant une acquisition 3D sur des suspensions de latex SBA-PMMA, le contrôle de la température de l’échantillon s’est révélé insuffisant. Nous proposons une amélioration à la fois de la platine et des conditions d’observations permettant de mieux contrôler l’évaporation et la condensation de l’eau sur des échantillons liquides. La troisième partie est dévolue à une analyse approfondie d’une suspension de latex SBA-PMMA, de différentes concentrations (d’un état dilué à très concentré), les acquisitions étant effectuées avec les conditions optimisées. L’arrangement des particules de latex est comparé à des modèles issus de la littérature, et avec des résultats expérimentaux obtenus par cryo-SEM sur suspensions congelées. Nous présentons ensuite une étude du même latex en présence de tensioactif. La couche de tensioactif peut être mise en évidence dans les volumes reconstruits et segmentés. En conclusion, nous résumons les potentialités de la tomographie wet-STEM pour la caractérisation de nanomatériaux solides et liquides. Des perspectives sont proposées pour continuer dans l’exploration de ces potentialités et des limites de la technique. / ESEM (Environmental Scanning Electron Microscopy) allows the observation of liquids under specific conditions of pressure and temperature. When working in the transmission mode, i.e. in STEM (Scanning Transmission Electron Microscopy), nano-objects can even be analyzed inside the liquid (“wet-STEM” mode). Moreover, in situ evaporation of water can be performed to study the materials evolution from the wet to the dry state. This work aims at developing electron tomography on liquid suspensions using STEM-in-ESEM, to obtain the 3D structure of nano-objects dispersed in a liquid. In a first part, Monte Carlo simulations and 2D wet-STEM experimental images are combined to study the contrast. Two kinds of liquid nano-materials are chosen as the sample: spherical gold particles (diameter around 40 nm) in suspension in water; latex SBA-PMMA suspension, a copolymer derived from styrene and metacrylic acid esters in aqueous solution, 3% PMMA shell included as steric surfactant. The comparison between simulated and experimental results helps to determine how water can affect the contrast of hydrated nano-materials. Tomography experiments are then performed on dry PU-carbon nanotubes nanocomposites using a previously developed home-made tomography device, and the volume is well reconstructed. When performing tomography on latex suspension, limitations are found on the temperature control of samples. We propose an optimization of the device with new observations conditions to better control water evaporation and condensation of liquid samples. Afterwards, a full 3D analysis on SBA-PMMA latex from dilute suspension to very concentrated one is performed, and a further study is presented in presence of a surfactant. The encouraging reconstruction results are used to model the particles arrangement. This shows the potentialities of wet-STEM tomography for the characterization of both solid and liquid nano-materials.

The exceptional properties of carbon nanomaterials make them ideal reinforcements for polymers. However, the main challenges in utilizing their unique properties are their tendency to form agglomerates, their non-controlled orientation, non-homogeneous distribution and finally the change in their shape/size due to processing. All the above are the result of the nanomaterial/polymer interfacial interactions which dictate the overall performance of the composites including the mechanical properties. The aforementioned uncertainties are the reason for the deviation observed between the experimentally determined properties and the theoretically expected ones. The focus of this study is to understand the reinforcing efficiency of carbon nanomaterials in polymers through finite element modeling that captures the effect of the interfacial interactions on the tensile modulus of polymer nanocomposites (PNCs). The novelty of this work is that the probability distribution functions of nanomaterials dispersion, distribution, orientation and waviness, determined through image analysis by extracting 3-D information from 2-D scanning electron micrographs, are incorporated into the finite element model allowing thus for fundamental understanding of how the nanostructure parameters affect the tensile modulus of the PNCs. The nanocomposites are made using melt mixing followed by either injections molding or melt spinning of fibers. Polypropylene (PP) is used as the polymer and carbon nanotubes (CNT) or exfoliated graphite nanoplatelets (xGnP) are used as nanoreinforcements. The presence of interphase, confirmed and characterized in terms of stiffness and width using atomic force microscopy, is also accounted for in the model. The dispersion and distribution of CNT within the polymer is experimentally altered by using a surfactant and by forcing the molten material to flow through a narrow orifice (melt spinning) that promotes alignment of CNT and even of the polymer chains along the flow/drawing direction. The effect of nanomaterials' geometry on the mechanical behavior of PNCs is also studied by comparing the properties of CNT/PP to those of xGnP/PP composites. Finally the reinforcing efficiency of CNT is determined independently of the viscoelastic behavior of the polymer by conducting tensile testing at temperatures below the glass transition temperature of PP. The finite element model with the incorporated image analysis subroutine has sufficient resolution to distinguish among the different cases (dispersion, distribution, geometry and alignment of nanomaterials) and the predicted tensile modulus is in agreement with the experimentally determined one. In conclusion, this study provides a tool, that integrates finite element modeling and thorough experiments that enables design of polymer nanocomposites with engineered mechanical properties.