Polymers films and membranes with immobile and irreversible reactive sites can provide significant barrier properties for packaging materials. There is a need to develop mathematical models to understand the behavior of these reactive materials and to confidently extrapolate experimental data. Due to mechanical and optical requirements, barrier films may consist of composites, such as polymer blends and multilayer films with alternating reactive and inert layers. The reactive term that consumes the mobile species in the governing transport equations for such materials is a function of both the mobile species and the immobilized reactive sites, leading to non-linear partial differential equations that typically have to be solved numerically. Composite structures add to the complexity of the model. For the polymer blend, a multiscale model was developed, incorporating the reactive details within the particle into the bulk transport equation. For the multilayer film, initial conditions and diffusion coefficients were assigned independently for reactive or inert layers. The models developed for the three configurations were solved numerically over a wide parameter space. Three regimes were identified, namely early times characterized by an initial flux plateau, and intermediate regime, and long times, characterized by the time lag. Asymptotic analysis of the homogeneous model was used to develop analytical predictions for the three regimes, obviating the need to numerically solve the model’s non-linear equations. These predictions were generalized to polymer blends. For multilayer films, predictions for early and long times were developed. Results for polymer blends and multilayer composites were compared and discussions of the most suitable configuration for different scenarios were presented. The reactive barrier configurations studied require the knowledge of parameters such as reaction rates and coefficients of diffusion and solubility of the reactive polymer. Model and predictive equations have been developed to describe the transient mass uptake in reactive homogeneous films, enabling the extraction of these parameters from sorption experiments. / text

Solutes are often most efficiently deployed in discrete pulses, for example in the delivery of herbicides or drugs. Manual application of each pulse can be labor-intensive, automated application of each pulse can be capital intensive, and both are often costly and impractical. Barrier-Mediated Pulsatile Release (BMPR) systems offer a materials-based alternative for automated pulsatile drug delivery, without pumps, power supplies, or complex circuitry. While earlier materials-based approaches such as delayed-release microcapsules are limited to two or three pulses due to the independent nature of each pulse’s timing control, BMPR systems link the timing of each pulse to the previous pulse. Each dose of drug is sequestered in its own stimuli-sensitive depot, releasing only upon contact with the stimulant. These depots are stacked with sacrificial barriers in between, each of which block the stimulant for a predetermined time. For instance, layers of soluble drug may be separated by degradable polymer layers. Water, as the stimulant, will erode the polymer layer over a fixed period of time, followed by quick dissolution and release of the underlying drug and the start of degradation for the next polymer layer. This example, however, is quickly limited by irregular polymer erosion, a single stimulant (water), and difficulty in scaling delay times. The research work presented in this thesis reports the development of a generalized BMPR system which overcomes those limitations. Model drugs (methylene blue and methyl orange) were immobilized in a pH-sensitive polymer [poly(methyl methacrylate-co-dimethylaminoethyl methacrylate)] which released only at low pH. Zinc oxide (ZnO) nanoparticles immobilized in a pH-insensitive matrix [poly(vinyl alcohol)] served as the barrier layer. The time required for acid to penetrate the barrier layer scaled with the ZnO concentration and with the square of the polymer thickness, allowing wide scaling of the delay time with only minor changes to the barrier layer. Harnessing the swelling pressure of the acid-sensitive hydrogel, each barrier/depot bilayer can delaminate upon solute release, directly exposing the next bilayer to the stimulant source. This system has demonstrated tuned release using a citric acid stimulant to produce up to ten pulses of model drug (methylene blue) over various preset timescales. This system has also demonstrated the alternate release of multiple solutes (methylene blue and methyl orange) at regular time intervals up to five pulses from a single BMPR device. For non-delaminating BMPR systems, spent bilayers impede stimulant diffusion to the inner layers and solute diffusion from the inner layers, increasing the delay time and the pulse width. To predict these changes, a computational model was constructed in FORTRAN. This model was extensively explored over a wide range of parameter space to understand the release behavior of various kinds of non-delaminating BMPR systems. The computer model also validates the performances of experimental delaminating BMPR system. This model can be used to guide the physical modeling of BMPR systems. The model also allows to incorporate variety of stimulants other than just acid. BMPR technology introduces efforts to further generalize the delivery strategy by incorporating glucose as a stimulant.

Every year, many archeological findings are discovered. It is necessary to document and conserve these items dug up from the ground. However, archeologists and conservators cannot handle such a big amount of newly found items. This work offers an alternative approach to standard conservation techniques, increasing the processing capacity and lowering the cost on items’ conservation. Studied alternative, mainly for protection of metallic artefacts, includes thin films based on parylene and organosilicons. Thin films were prepared on two experimental apparatuses. Parylene films were deposited by chemical vapour deposition (CVD). Final product was a thin film of parylene C. Organosilicon thin films were deposited via plasma enhanced chemical vapour deposition (PECVD). PECVD apparatus operates with capacitively coupled radiofrequently initiated plasma. Using hexamethyldisiloxane, thin films very similar to silicon dioxide were produced, thus called SiOx. Thin films were characterized by several methods and compared to standard treatment used by conservators – tannate layer, acrylic furnish Paraloid B72 and microcrystalline wax Revax 30. Parylene films showed excellent conformity and resistance to corrosion on iron substrate. First signs of corrosion were observed on layer of 5 µm thickness after 24 hours in salt fog. On samples coated by SiOx films, corrosion was spreading wide even during 1st hour of the corrosion test. Most probable cause was that SiOx film has thermal expansion coefficient different from iron substrate and due to this fact cracking occurs during cooling down of the treated substrate. On samples coated by standard treatment, corrosion occurred after 1-3 hours of the test. Oxygen transmission rate (OTR) measurements (performed on polypropylene substrate) confirmed good barrier properties of parylene C. Best parylene thin films had OTR approximately 170 cm3•m-2•atm-1•day-1. SiOx films reached good results with OTR 300 cm3•m-2•atm-1•day-1, compared to clean polypropylene substrate with OTR 1700 cm3•m-2•atm-1•day-1. Standard conservation layers could not be applied on polypropylene substrate, thus their OTR was not measured. We did not succeed in finding a substrate which is compatible for all types of treatments. Next, the study focused on combinations of thin films forming sandwich structures. All types let the corrosion attack the substrate during the 1st hour of the test. The cause was insufficient film thickness as well as crack ing of SiOx films due to different thermal expansion properties from the iron substrate. Although SiOx thin films were not deposited on substrate directly, they have excellent adhesion to parylenu and thus they could tear parylenu films due to thermal expansion. However, OTR measurements showed improvement in barrier properties. Multilayer parylene C–SiOx–parylene C–SiOx had OTR 5 cm3•m-2•atm-1•day-1. Final result is that parylene C thin films have better barrier properties than standard coatings and are suitable for conservation of metallic archaeological artefacts. SiOx films and multilayers showed poor anticorrosion protection of metallic substrates but they have good barrier and chemical properties in combination with other types of substrates. Mainly deposited on polymers, there is great potential for their application in many fields. Further research would be focused on new substrates for SiOx thin films and on the improvement of UV stability of parylene films.

Yes / Organic photovoltaics (OPVs) die due to their interactions with environmental gases, i.e., moisture and oxygen, the latter being the most dangerous, especially under illumination, due to the fact that most of the active layers used in OPVs are extremely sensitive to oxygen. In this work we demonstrate solution-based effective barrier coatings based on composite of poly(vinyl butyral) (PVB)and mica flakes for the protection of poly (3-hexylthiophene) (P3HT)-based organic solar cells (OSCs)against photobleaching under illumination conditions. In the first step we developed a protective layer with cost effective and environmentally friendly methods and optimized its properties in terms of transparency, barrier improvement factor, and bendability. The developed protective layer maintained a high transparency in the visible region and improved oxygen and moisture barrier quality by the factor of ~7. The resultant protective layers showed ultra-flexibility, as no significant degradation in protective characteristics were observed after 10 K bending cycles. In the second step, a PVB/mica composite layer was applied on top of the P3HT film and subjected to photo-degradation. The P3HT films coated with PVB/mica composite showed improved stability under constant light irradiation and exhibited a loss of <20% of the initial optical density over the period of 150 h. Finally, optimized barrier layers were used as encapsulation for organic solar cell (OSC) devices. The lifetime results confirmed that the stability of the OSCs was extended from few hours to over 240 h in a sun test (65◦C, ambient RH%) which corresponds to an enhanced lifetime by a factor of 9 compared to devices encapsulated with pristine PVB. / Higher Education Commission of Pakistan through NED University of Engineering and Technology, Karachi, Pakistan and “The APC was funded by Deanship of Scientific Research, King Saud University for funding through Vice Deanship of Scientific Research Chairs”.

Nitric oxide (NO) is an important mediator of angiogenesis and is primarily produced endogenously through the action of nitric oxide synthase (NOS). An alternate pathway for NO production is the conversion of nitrite to NO, which depends on the presence of hemoglobin (Hb) and hypoxic conditions. The angiogenic effects of topically applied sodium nitrite on two vascular beds in the ex ovo chicken embryonic model of angiogenesis were assessed. Gas barrier films were used to modulate local oxygen levels in the chorioallantoic membrane (CAM), a respiratory vascular network, and the area vasculosa (AV) on the yolk sac, a typical peripheral vascular network. The low-permeable film polyvinylidene chloride (PVDC) and highly permeable regenerated cellulose (RC) were applied to the surface of the vasculature to alter oxygen diffusion and transport and produce a local environment of low or high oxygen, respectively. Phosphorescence Quenching Microscopy (PQM) was used to verify the oxygen levels in the vascular membranes underneath the films. Following 48 hours of continuous application of sodium nitrite (330 μg/kg/day), saline, or sodium nitrite + cPTIO (a NO scavenger) (1mg/kg/day), the angiogenic response was quantified by measuring vascular density and network complexity. The PVDC film reduced CAM PO2 to 17.9±5.5 mmHg and AV PO2 to 29.5±3.6 while the RC film maintained a PO2 of 115 mmHg. At the edge of PVDC film, there was found to be a small area of transition between the nearby low and high PO2 regions. After nitrite application, significant increases in vascularity were observed in the AV under hypoxic conditions, but not normoxic conditions (p<0.03). cPTIO inhibited nitrite-induced angiogenesis and returned vascularity to levels observed with saline application. No significant changes were observed in the CAM, but a trend of reduced angiogenesis after nitrite application was observed compared to saline and saline+cPTIO. These results indicate that two highly diffusible gases, NO and O2, play important roles in the growth of new blood vessels, but in a way that appears to depend on the gas exchange function of the vascular network.

Paper and cellulosic materials hold a good promise of being candidates for flexible packaging materials provided suitable barrier properties such as water repellence and grease resistance are imparted to them. One of the methods to achieve these objectives is to surface modify paper/cellulose by applying thin fluorocarbon coatings on the surface. Fluorocarbon thin films produced by plasma enhanced chemical vapor deposition (PECVD) offer several advantages over the films produced by conventional polymerization means. Plasma deposited films are pinhole-free, chemically inert, insoluble, mechanically tough, thermally stable and highly coherent and adherent to variety of substrates. In this work, we investigate the use of PECVD technique to produce barrier films on paper and cellulosic materials. These films, with composition and properties not much different from PTFE, repel water and act as a good barrier to lipophilic materials. Two different monomers, pentafluoroethane (PFE; CF3CHF2) and octafluorocyclobutane (OFCB; C4F8), were investigated and compared in terms of deposition rates and final film properties. Various analytical techniques (XPS, FT-IR, SEM, Ellipsometry, Contact Angle Goniometry, etc.) were used to characterize the fluorocarbon films. The fluorocarbon coated paper exhibited hydrophobic character as evidenced by high water contact angles. Although the films allow water vapor diffusion, the films are hydrophobic and are not wetted when liquid water contacts these layers. Based on various thickness of these films deposited on surface of cellulose, there was a minimum PFE film thickness required to achieve a stable hydrophobic behavior. The fluorocarbon films investigated in this work also exhibited good resistance to lipophilic materials (e.g. oils, fatty acids, etc.). While techniques such as oleic acid penetration and TAPPI "oil-kit" test are commonly used in paper industry to qualitatively test the grease barrier properties of paper/cellulose, this work attempts to quantify the grease barrier properties of fluorocarbon coated paper using techniques such as magnetic resonance imaging (MRI) and quartz crystal microbalance (QCM). Finally, the feasibility of deposition of dual layer films by PECVD was investigated using PFE and n-isopropylacrylamide (NIPAAM) as precursors for applications in barrier packaging and printing.

Tesis por compendio / [ES] La producción y consumo de plásticos derivados de petróleo ha crecido exponencialmente en las últimas décadas, impactando en la naturaleza y los seres vivos. Los envases alimentarios son considerados la principal fuente de contaminación por plásticos. Por ello, el estudio y desarrollo de nuevos materiales derivados de recursos renovables y biodegradables ha emergido como un nuevo campo de gran interés. La presente tesis doctoral se enfocó en el desarrollo y caracterización de biopolímeros de polihidroxialcanoato (PHA) derivados de subproductos industriales y de la fracción orgánica de aguas residuales municipales, los residuos biológicos municipales, sintetizados por cultivos microbianos mixtos y producidos mediante las tecnologías de electroestirado y mezclado en fundido. Los materiales resultantes fueron desarrollados para obtener monocapas y multicapas activas y de alta barrera a oxígeno para su uso en envases alimentarios basados en la Bioeconomía Circular. Para lograr los objetivos, esta tesis doctoral se ha dividido en tres bloques según la tecnología utilizada en la obtención de los materiales. El primer bloque consistió en la extracción de los PHAs derivados de residuos agro-industriales para su óptima utilización en los procesos de producción. Posteriormente, se realizó el procesado de los PHAs mediante la técnica de electroestirado, por la cual se obtuvieron fibras poliméricas que fueron tratadas térmicamente para formar films continuos y homogéneos. Estas monocapas presentaron buenas propiedades térmicas y mecánicas, así como alta barrera tanto a vapores como a gases. Además, las fibras fueron funcionalizadas con compuestos orgánicos presentes en aceites esenciales para proporcionarles una función antimicrobiana activa contra microorganismos trasmitidos por los alimentos. Por otro lado, se realizó el electroestirado de copolímeros de etileno-alcohol vinílico, un polímero sintético que se biodegrada en condiciones específicas y que posee alta barrera a oxígeno. Además, nanocristales de celulosa fueron añadidos al EVOH, para crear monocapas híbridas de alta barrera más sostenibles. En el segundo bloque, los materiales se procesaron mediante la técnica de mezclado en fundido. Para ello, los PHAs derivados de biomasa del primer bloque se mezclaron con PHAs comerciales, así como con cargas celulósicas para formar "compuestos verdes", en el que todos los materiales estaban basados en recursos renovables y biodegradables. Las mezclas mostraron buena miscibilidad y propiedades ópticas, una flexibilidad mejorada, así como propiedades de barrera similares a las del material de biopoliéster puro. Finalmente, en el tercer bloque, se produjeron sistemas multicapas utilizando mezclas de PHA desarrolladas ad-hoc, y materiales monocapa de PHA electroestirado del primer bloque. Estas estructuras multicapas se basaron en las propiedades adhesivas que poseen las fibras electroestiradas tras aplicarles el tratamiento térmico y en el uso de los revestimientos de CNCs como capas intermedias de barrera a oxígeno. Así, los sistemas multicapas desarrollados fueron totalmente compostables, con alta barrera a oxígeno, siendo potenciales candidatos para sustituir a los actuales envases alimentarios basados en materiales no renovables provenientes del petróleo. Por lo tanto, los materiales aquí desarrollados son tanto bioadhesivos muy prometedores que muestran propiedades antimicrobianas y de alta barrera, como capas exteriores con fines estructurales o para uso como films finos. Así, por laminación, estos materiales pueden dar lugar a films multicapas autoadhesivos, empleados tanto en envases rígidos, semirrígidos o flexibles. Estas estructuras son sostenibles y respetuosas con el medio ambiente y además son biodegradables mediante compostaje y, en algún caso, biodegradables en el medio ambiente. Asimismo, son potencialmente capaces de proporcionar una calidad y seguridad alimentaria comparables a las derivadas de fuentes petroquímicas. / [CA] La producció i el consum de plàstics derivats de petroli ha crescut exponencialment en les últimes dècades, impactant en la naturalesa i els éssers vius. Els envasos alimentaris són considerats la principal font de contaminació per plàstics. Per això, l'estudi i el desenvolupament de nous materials derivats de recursos renovables i biodegradables ha emergit com un nou camp de gran interès. Aquesta tesi doctoral es va enfocar en el desenvolupament i la caracterització de biopolímers de polihidroxialcanoat (PHA) derivats de subproductes industrials i de la fracció orgànica d'aigües residuals municipals, els residus biològics municipals, sintetitzats per cultius microbians mixtos i produïts mitjançant les tecnologies d'electroestirat i barrejat en fosa. Els materials resultants van ser desenvolupats per obtenir monocapes i multicapes actives i d'alta barrera a oxigen per utilitzar-los en envasos alimentaris basats en la Bioeconomia Circular. Per assolir els objectius, aquesta tesi doctoral s'ha dividit en tres blocs segons la tecnologia utilitzada per obtenir els materials. El primer bloc va consistir en l'extracció dels PHA derivats de residus agroindustrials per a la seva òptima utilització en els processos de producció. Posteriorment, es va realitzar el processament dels PHA mitjançant la tècnica d'electroestirat, per la qual es van obtenir fibres polimèriques que van ser tractades tèrmicament per formar films continus i homogenis. Aquestes monocapes van presentar bones propietats tèrmiques i mecàniques, així com alta barrera tant a vapors com a gasos. A més, les fibres van ser funcionalitzades amb compostos orgànics presents en olis essencials per proporcionar-los una funció antimicrobiana activa contra microorganismes transmesos pels aliments. D'altra banda, es va realitzar l'electroestirat de copolímers d'etilè-alcohol vinílic, un polímer sintètic que es biodegrada en condicions específiques i que té alta barrera a oxigen. A més, nanocristalls de cel·lulosa van ser afegits a l'EVOH, per crear monocapes híbrides d'alta barrera més sostenibles. Al segon bloc, els materials es van processar mitjançant la tècnica de barrejat en fosa. Per això, els PHAs derivats de biomassa del primer bloc es van barrejar amb PHAs comercials, així com amb càrregues cel·lulòsiques per formar "compostos verds", en què tots els materials estaven basats en recursos renovables i biodegradables. Les barreges van mostrar bona miscibilitat i propietats òptiques, una flexibilitat millorada, així com propietats de barrera similars a les del material de biopolièster pur. Finalment, al tercer bloc, es van produir sistemes multicapes utilitzant barreges de PHA desenvolupades ad-hoc, i materials monocapa de PHA electroestirat del primer bloc. Aquestes estructures multicapes es van basar en les propietats adhesives que tenen les fibres electroestirades després d'aplicar-los el tractament tèrmic i en l'ús dels revestiments de CNC com a capes intermèdies de barrera a oxigen. Així, els sistemes multicapes desenvolupats van ser totalment compostables, amb alta barrera a oxigen, sent potencials candidats per substituir els actuals envasos alimentaris basats en materials no renovables provinents del petroli. Per tant, els materials aquí desenvolupats són tant bioadhesius molt prometedors que mostren propietats antimicrobianes i d'alta barrera, com a capes exteriors amb fins estructurals o per a ús com a films fins. Així, per laminació, aquests materials poden donar lloc a films multicapes autoadhesius, emprats tant en envasos rígids, semirígids o flexibles. Aquestes estructures són sostenibles i respectuoses amb el medi ambient ia més són biodegradables mitjançant compostatge i, en algun cas, biodegradables al medi ambient. Així mateix, són potencialment capaços de proporcionar una qualitat i seguretat alimentària comparables a les derivades de fonts petroquímiques. / [EN] The production and consumption of petroleum derived plastics that are not biodegradable has grown exponentially in recent decades, with the consequent impact on nature and organisms. The food packaging sector is today considered the main source of plastic contamination. Therefore, the study and development of new materials derived from renewable and biodegradable resources has emerged as a new field of great scientific, social, economic and political interest. The current PhD thesis focused on the development and characterization of polyhydroxyalkanoate (PHA) biopolymers derived from agro-industrial by-products and from the organic fraction of municipal wastewater, the municipal biowaste, synthesized by mixed microbial cultures and produced by electrospinning and melt compounding technologies. The resultant materials were particularly developed to obtain high-oxygen-barrier active monolayers and multilayers for use in Circular Bioeconomy-based food packaging. In order to achieve the objectives, this PhD thesis has been divided into three blocks according to the technology used to obtain the materials. The first block consisted of the extraction of PHAs derived from agro-industrial waste for their optimal use in production processes. After this, the PHAs were then processed using the electrospinning technique, whereby polymeric fibers were obtained and thermally post-treated by an annealing process to form continuous and homogeneous films, also known as "biopapers". These monolayers showed good thermal and mechanical properties, as well as a high barrier to both vapors and gases. In addition, the fibers were functionalized with eugenol, an organic compound present in essential oils, to provide them with active antimicrobial function against foodborne microorganisms. On the other hand, the electrospinning of poly(ethylene-co-vinyl alcohol) copolymers, a synthetic polymer that is claimed to biodegrade under specific conditions and with high oxygen barrier, was performed. Cellulose nanocrystals were added to EVOH, to create high barrier more sustainable hybrid monolayers. In the second block, the materials were processed using the melt compounding technique. For this purpose, the biomass derived PHAs extracted in the first block were blended with commercial PHAs as well as with cellulosic fillers, in this case rice husk flour, in order to form "green composites", where all the materials were based on renewable and biodegradable resources. After film formation by hot pressing, the blends showed excellent miscibility and optical properties, improved flexibility, as well as barrier properties similar to the neat biopolyester material. Finally, in the third block, multilayer systems were produced using ad-hoc developed PHA blends, and PHA electrospun monolayer materials developed in the first block. They were based on the adhesive properties of the electrospun fibers after thermal treatment, which allowed the elimination of synthetic adhesive substances normally used in the industry, and on the use of the CNCs coatings as oxygen barrier interlayers. Thus, the multilayer systems developed were fully compostable, with high oxygen barrier, being potential candidates to replace current food packaging based on non-renewable petroleum-based materials. Therefore, the materials developed herein are very promising bioadhesives showing antimicrobial and high barrier properties, as well as outer layers for structural or thin film purposes. Thus, by lamination, these materials can result in self-standing multilayer films, which can be used in rigid or semirigid packaging as well as in flexible packaging. They are sustainable and environmentally friendly, as they are made from renewable sources or waste, and are biodegradable by composting, and, in some case, even biodegradable in the environment. Furthermore, they are potentially capable of providing comparable quality and food safety to those currently marketed from petrochemical sources. / Meléndez Rodríguez, B. (2022). Development and Characterization of Monolayers and Multilayers Based on Biodegradable Materials Derived from Waste and By-products of Interest in Food Packaging [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/184651 / TESIS / Compendio