Linear and branched poly(butylene adipate) polyesters with number-average molecular weights ranging from 700 to 10 000 g/mol, and degrees of branching ranging from very low to hyperbranched were solution cast with PVC to study the effects of chemical structure, molecular weight, end-group functionality, and chain architecture on plasticizing efficiency and durability. Miscibility was evaluated by the existence of a single glass transition temperature and a shift of the carbonyl group absorption band. Desirable mechanical properties were achieved in flexible PVC films containing 40 weight-% of polyester plasticizer. Methyl-ester-terminated polyesters with a low degree of branching and an intermediate molecular weight enhanced the plasticizing efficiency, as shown by greater elongation, good miscibility, and reduced surface segregation. A solid-phase extraction method was developed to extract the low molecular weight products that migrated from pure poly(butylene adipate) and PVC/ poly(butylene adipate) films during aging in water. The effects of branching, molecular weight, end-group functionality, and polydispersity on plasticizer permanence were evaluated by quantification of low molecular weight hydrolysis products, weight loss, surface segregation, and the preservation of material properties during aging. A more migration-resistant polymeric plasticizer was obtained by combining a low degree of branching, hydrolysis-protecting end-groups, and higher molecular weight of the polyester. Films plasticized with a slightly branched polyester showed the best durability and preservation of material and mechanical properties during aging. A high degree of branching resulted in partial miscibility with PVC, poor mechanical properties, and low migration resistance. The thermal stability of polyester-plasticized films was higher than that of films containing a low molecular weight plasticizer, and the stabilizing effect increased with increasing plasticizer concentration. / QC 20100805

This master’s thesis deals with plasticization of poly(3-hydroxybutyrate), polylactid acid and their blend. It explores effect of chemical structure of plasticizer on mechanical properties of this polymer blend and on its diffusion from the polymer blend. Syntheses of plasticizers based on oligomeric polyadipates, citrates, lactate and esters of 2 ethylhexanoic acid with poly(ethyleneglycol) were carried out. Molecular weight distribution of synthesized plasticizers was determined using gel permeation chromatography. Poly(3-hydroxybutyrate), polylactid acid and their blend were plasticized with synthesized and commercial plasticizers. From commercial, chosed plasticizers were based on citrates and ester of 2-ethylhexanoic acid with poly(ethyleneglycol). Thermal stability of selected commercial plasticizers in polylactid acid was studied using thermogravimetry. Diffusion of plasticizers from poly(3-hydroxybutyrate), polylactid acid and their blend during exposure to 110 °C was also investigated. Mechanical properties of prepared blends were tested by tensile test. Almost all used plasticizers showed positive softening effect in blend. The highest elongation at break was detected for the blend with commercial acetyltributylcitrate, where elongation at break reached 328 % relative to 21 % for neat non-plasticized blend.

This thesis describes influence of plasticizers and setting accelerators in binder system based aluminasilikates. Following survey includes changes of characteristics of aluminate cements in combination with various setting accelerators. Practical testing and measuring summarizes and compares interdependence of structure, compressive strength, permeability and abrasion resistance. As a final part of thesis individual mixes are analysed economically and are accompanied by suggestions for future use and use in working experience.

This thesis has an approved one-year embargo applied to it. Please, refer to the corresponding forms, and please, so not publish immediately until the embargo has been sorted out. The thesis contains two unpublish papers and patents pending. Thank you! / Conventional single-use plastic packaging has contributed significantly to the health and well-being of our society but also negatively impacted our environment due to its persistence after use. Since recycling is not a complete solution, rapidly biodegradable materials like thermoplastic starch (TPS) blends offer a more sustainable alternative. Additionally, to stave off the premature breakdown of starch-containing materials as well as extend the shelf life of enclosed foods, microbial control strategies need to be developed. To overcome the inherent brittleness of TPS, this work explores the potential of xylitol and erythritol as melt plasticizers for waxy corn starch (̴100% amylose). Characterizations revealed that both xylitol and erythritol can gelatinize and plasticize starch under 25% wt. Particularly, xylitol demonstrated superior plasticizing and compatibilizing effects, leading to a ductile TPS packaging film with uncharacteristically high elongation at break (EB, 422% ± 48%). The ductile TPS was blended with up to 70% Ecovio bioplastic without requiring compatibilizers and retaining much of its EB value (298 ± 24%). Using xylitol as a melt plasticizer also enhanced the mechanical and hydrophobic qualities of the TPS/Ecovio film as well as its oxygen permeability and puncture extension. Furthermore, polymerized curcumin copolymer (PCEG) was investigated as a grafted coating onto the developed TPS/Ecovio® blend. The antimicrobial activity of PCEG and PCEG coating film was evaluated against foodborne bacteria. The polymerized curcumin by itself demonstrated antimicrobial activity against the gram-negative bacteria Escherichia coli BL21 and Pseudomonas aeruginosa PA01, as well as the gram-positive bacterium Staphylococcus aureus. Additionally, the PCEG-coated films showed surface inhibition of Glutamicibacter soli (IAI-3), a gram-positive bacterium making polymerized curcumin copolymer coatings a suitable approach to add antimicrobial features in thermoplastic starch composites for biodegradable food packaging. / Thesis / Master of Applied Science (MASc) / Canada's Zero Plastics initiative represents a commitment to the environment while upholding the advancements in food safety and public health that come with single-use food packaging. Achieving this balance demands the creation of novel materials. These materials should mimic the qualities of synthetic polymers but have the added ability to decompose naturally in the environment upon reaching the end of their utility. A significant challenge in this effort is preventing the premature degradation of starch-containing packaging materials. Moreover, extending the shelf life of the food they enclose is equally crucial. To solve this paradox, the development of microbial control strategies becomes imperative. This study highlights the antimicrobial potential of a polymerized curcumin copolymer (PCEG) as a coating on a blend of thermoplastic starch (TPS)/xylitol/Ecovio®, creating an innovative packaging film. The curcumin copolymer coating exhibited antimicrobial properties, suggesting its potential use in thermoplastic starch composites for biodegradable food packaging.

An AFM relative stiffness technique was applied to reconstituted Beta vulgaris L. wax films. Consecutive force arrays (n=100) made on the waxy surface at the same locations showed that there was no relative change in surface elasticity and this information was used as a reference to further experimental measurements. A surfactant solution was subsequently dropped on the waxy surface and the same array of indents was made at the same location as the reference test. The plant wax surface showed a reduction in its surface elasticity properties. The study has demonstrated that the AFM technique could be used to undertake a systematic assessment of the plasticising effects of agrochemicals on native and reconstituted plant wax films.

Tesis por compendio / [ES] La presente tesis doctoral tiene como principal objetivo el desarrollo de materiales poliméricos que sean respetuosos con el medio ambiente y favorezcan modelos de economía circular, centrando las líneas de investigación en el reaprovechamiento de residuos de la industria del mango y en la utilización de ácido poliláctico (PLA) como principal matriz polimérica. Para ello se emplean diferentes técnicas de procesado como el electrospinning, la extrusión, la inyección o la producción de films por disolución. Además, se plantea la utilización de diferentes aditivos como plastificantes y cargas lignocelulósicas de origen renovable para mejorar las propiedades de estos materiales sin comprometer su alto potencial medioambiental. El primer bloque de la tesis centra sus esfuerzos en el reaprovechamiento de diferentes residuos del mango (uno de los cultivos más populares del mundo), como la piel y el kernel, para desarrollar diferentes materiales con un gran contenido natural. Dentro de los estudios realizados en este bloque se incluye la extracción de almidón a partir del kernel de mango para la posterior fabricación de nanofibras por electrospinning, con gran aplicación en el sector médico. Otros estudios realizados proponen la combinación de matrices poliméricas como el biopolipropileno y el PLA, en combinación con harina de piel de mango y harina de hueso de mango, respectivamente, mediante procesos de extrusión, extrusión reactiva (REX) e inyección. En el caso del biopolipropileno se utilizan además agentes compatibilizantes basados en ácido itacónico para aumentar la adhesión entre las partículas lignocelulósicas de la piel del mango con la matriz polimérica, la cual es altamente apolar. Por otro lado, a las formulaciones de PLA y harina de hueso de mango se le añaden plastificantes como la triacetina y la tributirina para aumentar las propiedades dúctiles del PLA. Un cuarto estudio se enfoca en la producción de films de glicerol con harina de hueso de mango, rica en almidón, para observar cómo afecta el tamaño de partícula de la harina sobre las propiedades de los films. Por último, se propone el desarrollo de materiales termoplásticos ricos en almidón utilizando harina de kernel de mango en combinación con diferentes plastificantes como glicerol, sorbitol y urea. Estos materiales ricos en almidón son procesados por extrusión e inyección y son completamente biodegradables y de origen natural. El segundo y último bloque de la tesis está enfocado a la utilización del ácido poliláctico obtenido de fuentes renovables en procesos de extrusión e inyección. Este poliéster es un polímero biodegradable cuya principal desventaja es su gran fragilidad. Por ello, se han empleado diferentes tipos de plastificantes naturales para incrementar las propiedades dúctiles del PLA. En un primer trabajo, se combina el PLA con α-terpinil acetato, un plastificante de origen renovable. Además, se añade piel de mandarina molida como carga natural para evaluar si este plastificante es capaz de aumentar la ductilidad de mezclas de PLA con cargas lignocelulósicas, obtenido resultados muy positivos. Un segundo trabajo plantea la combinación de PLA con dietil-L-tartrato, un plastificante obtenido del ácido tartárico, encontrado en la uva y el tamarindo, obteniendo elongaciones de más de un 300%. Por último, dos estudios más plantean la combinación de PLA con terpenoides, más concretamente ésteres de geranilo y linalilo. En este sentido, uno de los trabajos se centra en variar la proporción de acetato de linalilo y acetato de geranilo en las composiciones, mientras que el otro trabajo evalúa como afecta la longitud de cadena de los ésteres de geranilo a la plastificación del PLA. Todos los plastificantes utilizados en este bloque ofrecieron resultados muy prometedores, con alargamientos a la rotura superiores al 200% en materiales completamente naturales y biodegradables con gran aplicación en el sector alimentario y del envase y embalaje. / [CA] La present tesi doctoral té com a principal objectiu el desenvolupament de materials polimèrics que siguen respectuosos amb el medi ambient i afavorisquen models d'economia circular, centrant les línies d'investigació en el reaprofitament de residus de la indústria del mango i en la utilització d'àcid polilàctic (PLA) com a principal matriu polimèrica. Per a això s'empren diferents tècniques de processament com l'electrospinning, l'extrusió, la injecció o la producció de films per dissolució. A més, es planteja la utilització de diferents additius com a plastificants i càrregues lignocelulòsiques d'origen renovable per a millorar les propietats d'aquests materials sense comprometre el seu alt potencial mediambiental. El primer bloc de la tesi centra els seus esforços en el reaprofitament de diferents residus del mango (un dels cultius més populars del món), com la pell i el kernel, per a desenvolupar diferents materials amb un gran contingut natural. Dins dels estudis realitzats en aquest bloc s'inclou l'extracció de midó a partir del kernel de mango per a la posterior fabricació de nanofibers per electrospinning, amb gran aplicació en el sector mèdic. Altres estudis realitzats proposen la combinació de matrius polimèriques com el biopolipropilè i el PLA, en combinació amb farina de pell de mango i farina d'os de mango, respectivament, mitjançant processos d'extrusió, extrusió reactiva (REX) i injecció. En el cas del biopolipropilè s'utilitzen a més agents compatibilitzants basats en àcid itacònic per a augmentar l'adhesió entre les partícules lignocelulòsiques de la pell del mango amb la matriu polimèrica, la qual és altament apolar. D'altra banda, a les formulacions de PLA i farina d'os de mango se li afigen plastificants com la triacetina i la tributirina per a augmentar les propietats dúctils del PLA. Un quart estudi s'enfoca en la producció de films de glicerol amb farina d'os de mango, rica en midó, per a observar com afecta la grandària de partícula de la farina sobre les propietats dels films. Finalment, es proposa el desenvolupament de materials termoplàstics rics en midó utilitzant farina de kernel de mango en combinació amb diferents plastificants com glicerol, sorbitol i urea. Aquests materials rics en midó són processats per extrusió i injecció i són completament biodegradables i d'origen natural. El segon i últim bloc de la tesi està enfocat a la utilització de l'àcid polilàctic obtingut de fonts renovables en processos d'extrusió i injecció. Aquest polièster és un polímer biodegradable el principal desavantatge del qual és la seua gran fragilitat. Per això, s'han emprat diferents tipus de plastificants naturals per a incrementar les propietats dúctils del PLA. En un primer treball, es combina el PLA amb α-terpinil acetat, un plastificant d'origen renovable. A més, s'afig pell de mandarina molta com a càrrega natural per a avaluar si aquest plastificant és capaç d'augmentar la ductilitat de mescles de PLA amb càrregues lignocelulòsiques, obtenint resultats molt positius. Un segon treball planteja la combinació de PLA amb dietil-L-tartrat, un plastificant obtingut de l'àcid tartàric, trobat en el raïm i el tamarinde, obtenint elongacions de més d'un 300%. Finalment, dos estudis més plantegen la combinació de PLA amb terpenoids, més concretament èsters de geranil i linalil. En aquest sentit, un dels treballs se centra en variar la proporció d'acetat de linalil i acetat de geranil en les composicions, mentre que l'altre treball avalua com afecta la longitud de cadena dels èsters de geranil a la plastificació del PLA. Tots els plastificants utilitzats en aquest bloc van oferir resultats molt prometedors, amb allargaments al trencament superiors al 200% en materials completament naturals i biodegradables amb gran aplicació en el sector alimentari i de l'envàs i embalatge. / [EN] The present doctoral thesis has as its main objective the development of polymeric materials that are environmentally friendly and promote circular economy models, focusing research on the reuse of waste from the mango industry and the use of polylactic acid (PLA) as the main polymer matrix. Various processing techniques such as electrospinning, extrusion, injection, or cast film are employed for this purpose. In addition, the use of different additives such as plasticizers and lignocellulosic fillers of renewable origin is proposed to improve the properties of these materials without compromising their high environmental potential. The first part of the thesis focuses on the reuse of various mango waste products (one of the most popular crops in the world), such as peel and kernel, to develop different materials with a high natural content. Studies in this section include the extraction of starch from mango kernels for the subsequent production of nanofibers by electrospinning, which have significant applications in the medical sector. Other studies propose the combination of polymeric matrices such as biopolypropylene and PLA, in combination with mango peel flour and mango kernel flour, respectively, through extrusion, reactive extrusion (REX), and injection processes. In the case of biopolypropylene, compatibilizing agents based on itaconic acid are also used to increase the adhesion between lignocellulosic particles from mango peel and the highly apolar polymer matrix. On the other hand, PLA formulations with mango kernel flour are supplemented with plasticizers such as triacetin and tributyrin to enhance the ductile properties of PLA. A fourth study focuses on the production of glycerol films with mango kernel flour, rich in starch, to observe how the particle size of the flour affects the film properties. Finally, the development of starch-rich thermoplastic materials is proposed using mango kernel flour in combination with different plasticizers such as glycerol, sorbitol, and urea. These starch-rich materials are processed by extrusion and injection and are completely biodegradable and of natural origin. The second and final part of the thesis is focused on the use of polylactic acid obtained from renewable sources in extrusion and injection processes. This biodegradable polyester has the main disadvantage of being very brittle. Therefore, different types of natural plasticizers have been used to increase the ductile properties of PLA. In the first study, PLA is combined with α-terpinyl acetate, a renewable plasticizer. In addition, ground tangerine peel is added as a natural filler to evaluate if this plasticizer can increase the ductility of PLA blends with lignocellulosic fillers, yielding very positive results. A second study proposes the combination of PLA with diethyl-L-tartrate, a plasticizer obtained from tartaric acid, found in grapes and tamarind, resulting in elongations of more than 300%. Finally, two more studies propose the combination of PLA with terpenoids, specifically geranyl and linalyl esters. In this regard, one of the works focuses on varying the proportion of linalyl acetate and geranyl acetate in the compositions, while the other study evaluates how the chain length of geranyl esters affects PLA plasticization. All the plasticizers used in this section offered very promising results, with elongations at break exceeding 200% in completely natural and biodegradable materials with significant applications in the food and packaging sectors. / This research is a part of the grant PID2020-116496RB-C22, funded by MCIN/AEI/10.13039/501100011033 and the grant TED2021-131762A-I00, funded by MCIN/AEI/10.13039/501100011033 and by the European Union “NextGenerationEU”/PRTR. Authors also thank Generalitat Valenciana-GVA for funding this research through the grant numbers AICO/2021/025 and CIGE/2021/094. Funded with Aid for First Research Projects (PAID-06-22), Vice-rectorate for Research of the Universitat Politècnica de València (UPV). J. I.-M. wants to thank FPU19/01759 grant funded by MCIN/AEI/10.13039/501100011033 and by ESF Investing in your future. J. G.-C. wants to thank FPU20/01732 grant funded by MCIN/AEI/10.13039/ 501100011033 and by ESF Investing in your future. / Gómez Caturla, J. (2024). Desarrollo y caracterización de polímeros de alto rendimiento medioambiental derivados de residuos agroindustriales y aditivos de origen renovable [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/203217 / Compendio

Global consumption of organophosphate esters (OPs), which are used as flame retardants and plasticizers, is rapidly increasing. Their use as additives in diverse applications poses a risk as they may be emitted from the products they are added to and be further transported in the environment. Therefore, the levels, distribution, and possible sources of 15 OPs, some of which are reported to be toxic, were investigated in indoor and outdoor environments. An exposure assessment was performed, and the exposure to OPs via inhalation was examined for five occupational groups. In addition, based on the findings of the studies, the total flow of OPs in Sweden was estimated. In indoor environments, the OPs detected in air and dust varied between the sites, but generally reflected the building materials, furniture etc. used in the premises. A majority of the analysed OPs were detected in all samples, and public buildings tended to have higher levels than domestic buildings. The chlorinated OPs dominated in indoor air and wipe samples from vehicles. They were also abundant in the dust samples. Some occupational groups were significantly more exposed to OPs than others. Aircraft technicians, for example, were exposed to about 500 times more tributyl phosphate than day care centre personnel. Upon domestic and industrial cleaning, OPs are discharged with the wastewater via the sewage system to sewage treatment plants (STPs). Irrespective of the size of the STPs investigated, they had similar levels of OPs in their influents, indicating that products containing OPs are widely used by the communities they serve. In some cases, it was possible to trace elevated levels of individual OPs to specific sources. The OPs were poorly removed from the wastewater, and the chlorinated OPs especially tended to pass through the STPs without being removed or degraded. Thus, levels of OPs in their effluents were also similar, as were the levels in their sludge. Of the total amounts of OPs entering the STPs, 50% was emitted to the recipients via the effluent. Hence, there is room for significant improvement in the treatment processes. Carps living in a pond, receiving STP effluent were found to contain relatively high levels of OPs compared to perch collected in lakes from background locations. Air and road traffic were also identified as sources of OPs: the concentration of total OPs in snow samples decreased with increasing distance from a major road intersection, and OPs were detected in aircraft lubricants and hydraulic fluids and in waste oil from cars and lorries. OPs are emitted from both diffuse and direct sources to the environment and may then be spread by long-range air transport, rivers and streams. This probably explains why OPs were also detected in air and fish from background locations. Finally, OPs are ubiquitous substances in both indoor and outdoor environments. The possibility that prolonged exposure to OPs at the levels found may cause adverse effects, for instance in aqueous organisms, cannot be excluded. For example, the OP levels in snow were of the same magnitude as reported effect concentrations. Similarly, in some premises, indoor exposure to OPs was close to the suggested guideline value. However, since these studies include only a limited number of samples, and data regarding the health and environmental effects of OPs are sparse, no definitive conclusions regarding their possible environmental effects can be drawn. / Den globala konsumtionen av organiska fosfatestrar (OP) för användning som flamskyddsmedel och mjukgörare har ökat kraftigt på senare tid. Det breda användningsområdet för dessa additiv medför en risk att de kan avges från de produkter de är satta till och transporteras vidare ut i miljön. Följaktligen undersöktes källor till, halter av, och fördelning i inom- och utomhusmiljöer av 15 OP, varav en del har toxiska effekter. Vidare har exponering för OP i bl.a bostäder och offentliga byggnader beräknats. Utöver detta undersöktes exponeringen för OP via inandning hos 5 yrkesgrupper. Slutligen användes resultaten för att uppskatta det totala flödet av OP i Sverige. I de olika inomhusmiljöerna uppmättes ett flertal OP i varierande halter i damm och luft, men generellt speglade halterna byggnadsmaterial, möbler etc. som fanns i lokalerna. De offentliga lokalerna tenderade att uppvisa högre halter än privata hus, förmodligen beroende på högre brandskyddskrav. Klorerade OP dominerade i inomhusluft samt i avstrykningsprov från fordon och förekom även i höga halter i damm. Vissa yrkesgrupper var exponerade för betydligt högre halter OP än andra, t.ex. exponerades flygtekniker för upp till 500 ggr högre lufthalter av tributylfosfat jämfört med förskollärare. I samband med våtskurning i inomhusmiljöer (hushåll, industrilokaler, osv.) släpps avsevärda mängder OP ut i avloppet och når till sist reningsverk. Oberoende av storlek på reningsverken var halterna av OP relativt lika, i vardera ingående vatten och slam, vilket indikerar en bred användning av OP i samhället. I vissa fall kunde specifika källor till OP i avloppsvattnet spåras. Exempelvis hade två av reningsverken högre halter av en klorerad OP jämfört med övriga reningsverk. Dessa behandlade vatten från en skumplastfabrik, respektive en fabrik som tillverkar flamskyddad färg. Avskiljningsgraden av OP från avloppsvatten visade sig generellt vara dålig, i synnerhet klorerade OP tenderade att passera genom reningsverken utan att degraderas eller avskiljas från vattnet. Av den mängd OP som nådde reningsverken släpptes 50 % ut till miljön via utflödet. Som ett resultat av detta uppvisade karpar från en damm påverkad av utflödet från ett reningsverk höga halter OP jämfört med abborrar från referenssjöar. Det finns därför anledning att förbättra tekniken på reningsverken. Flyg- och vägtrafik kunde också identifieras som källor till OP i miljön. OP uppmättes i hydrauloljor och smörjmedel för flygplan samt i spillolja från bilar och lastbilar. Vidare minskade totalhalten OP i snöprov med ökat avstånd från en större vägkorsning. OP släpps således ut från både diffusa och direkta källor och kan sedan spridas vidare via luft och vattendrag. Därmed var det inte förvånande att OP även påträffades i luft och fisk från bakgrundslokaler. Avslutningsvis förekommer OP i varierande halter i såväl inom- som utomhusmiljöer. Det kan inte uteslutas att långvarig exponering för de halter av OP som uppmätts skulle kunna orsaka negativa effekter hos t.ex vatten- eller jordlevande organismer. I smälta snöprov från en flygplats uppmättes exempelvis halter av OP i samma storleksordning som rapporterade effektkoncentrationer. Dessutom visade sig den beräknade exponeringen av OP, i några av de provtagna inomhuslokalerna, uppgå till halter nära det föreslagna riktvärdet för OP i Tyskland. Dessa studier inkluderar dock ett begränsat antal prov och provtyper och kunskapen om dessa föreningars miljö- och hälsoeffekter är bristfällig. Därför bedöms underlaget som för litet för att några definitiva slutsatser ska kunna dras angående OPs eventuella effekter på miljön.

Submitted by Sandra Pereira (srpereira@ufrrj.br) on 2016-10-13T12:25:00Z No. of bitstreams: 1 2016 - Sheyla Moreira Gon?alves.pdf: 3716146 bytes, checksum: eaee6e62414cd3d497528f597f1abab5 (MD5) / Made available in DSpace on 2016-10-13T12:25:00Z (GMT). No. of bitstreams: 1 2016 - Sheyla Moreira Gon?alves.pdf: 3716146 bytes, checksum: eaee6e62414cd3d497528f597f1abab5 (MD5) Previous issue date: 2016-02-23 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior - CAPES / The use of active packaging incorporated with natural antimicrobials as essential oils (EOs) for food preservation is a modern concept for the food industry. The objective of this study was to characterize cellulose acetate film (CA) incorporated with EOs and their combinations and/or added plasticizer, evaluating the influence of additives on the behavior of these materials. It is characterized as the thickness of the films, visual aspect, chemical structure, surface, mechanical strength, water vapor rate of transmission (WVRT) and antimicrobial activity. Through technique "casting" were obtained films incorporated with 50% (w/v) of EOs oregano or cinnamon or sweet fennel or combinations thereof and/or glycerol (5, 10, 20 and 30% (w/v)). Having as controls only films containing 50% (w/v) glycerol, and CA pure film, a total 41 treatments. The incorporation of EOs did not change the thickness and transparency of the films, but it reduced the WVRT. The color parameters L *, a* and b* were affected by the incorporation with EOs and/or glycerol the films exhibited clear with different colors compared with the AC pure film. Incorporating the most EOs cause increased tensile strength (TS) of the modulus of elasticity (ME) and reduced elongation at break (EB), except for the film with fennel EO (FEO) who presented plasticizer power differing from the other for all the evaluated mechanical parameters. The drilling force (DF) has increased to most films EOs incorporated with the exception of the film incorporated with the three EOs. The scanning electron microscopy (SEM) images revealed that most of the EOs and their combinations did not cause changes in the surface and cross-sectional area of the films, except the film with FEO. In the spectra of infrared spectroscopy with Fourier transform (FTIR), it observed that the interactions between the polymer matrix and most EOs were similar except for the film with FEO. As for the antibacterial efficiency in vitro, only the film incorporated with FEO showed no efficacy against Staphylococcus aureus (Gram +) and Escherichia coli (Gram +). It was observed that glycerol causes increased thickness and WVRT the AC films, however, the active films with EOs does not modify the parameter to most treatments. Transparency was not affected for most films. The addition of glycerol for most films incorporated with EOs caused reduction of TS, the ME and increased EB and DF. From the SEM pictures it can be observed that the glycerol promoted the emergence of porous structures, networked or compact, depending on the EO concentration and glycerol. The FTIR spectral showed that glycerol has different interactions, depending on the embedded EOs. The antibacterial efficiency of films with EO oregano or cinnamon or oregano more cinnamon has been improved with the presence of glycerol, while the others were not affected. In the face of changes in functional properties observed, it appears that with the additivation materials it is necessary to characterize them to define their applicability / O emprego de embalagens ativas incorporadas com antimicrobianos naturais, como os ?leos essenciais (OEs) para conserva??o de alimentos, representa um conceito moderno para a ind?stria aliment?cia. Objetivou-se neste trabalho caracterizar filmes de acetato de celulose (AC) incorporados com OEs e suas combina??es e/ou adi??o de plastificante, avaliando as influ?ncias da aditiva??o no comportamento f?sico e mec?nico destes materiais. Caracterizou-se os filmes quanto ? espessura, aspectos visuais, estrutura qu?mica, superf?cie, resist?ncia mec?nica, taxa de transmiss?o ao vapor de ?gua (TTVA) e atividade antimicrobiana. Atrav?s da t?cnica ?casting? foram obtidos filmes incorporados com 50% (p/v) de OEs de or?gano, canela, funcho doce ou suas combina??es e/ou glicerol (5, 10, 20 e 30% (p/v)). Tendo como controles filmes contendo somente 50% (p/v) de glicerol, e filme de AC puro, totalizando 41 tratamentos. A incorpora??o de OEs n?o modificou a espessura e transpar?ncia dos filmes, por?m causou redu??o da TTVA. Os par?metros de cor L*, a* e b* foram afetados pela incorpora??o de OEs e/ou glicerol tendo os filmes apresentado-se claros com diferentes cores em compara??o com o filme de AC puro. A incorpora??o da maioria dos OEs causou aumento da resist?ncia ? tra??o (RT), do m?dulo de elasticidade (ME) e redu??o do alongamento na ruptura (AR), com exce??o para o filme com OE de funcho (OEF) que apresentou poder plastificante diferindo dos demais para todos os par?metros mec?nicos avaliados. A for?a de perfura??o (FP) aumentou para a maioria dos filmes incorporados com OEs, a exce??o do filme incorporado com os tr?s OEs. As imagens de microscopia eletr?nica de varredura (MEV) revelaram que a maioria dos OEs e suas combina??es n?o causaram mudan?as na superf?cie e regi?o transversal dos filmes, a exce??o do filme com OEF. Nos espectros da espectroscopia no infravermelho com transformada de Fourier (FTIR), notou-se que as intera??es entre a matriz polim?rica e a maioria dos OEs foram semelhantes, com exce??o para o filme com OEF. Quanto ? efici?ncia antibacteriana in vitro, somente o filme incorporado com OEF n?o apresentou efetividade contra Staphylococcus aureus (Gram +) e Escherichia coli (Gram -). Foi observado que o glicerol causou aumento da espessura e TTVA nos filmes de AC, por?m, nos filmes ativos com OEs n?o modificou o par?metro para maioria dos tratamentos. A transpar?ncia n?o foi afetada para a maioria dos filmes. A adi??o de glicerol para a maioria dos filmes incorporados com OEs causou redu??o da RT, do ME e aumento do AR e FP. Pelas imagens do MEV observa-se que o glicerol promoveu o surgimento de estruturas porosas, em rede ou compactas, dependendo do OE e concentra??o de glicerol. Os espectros da FTIR demonstraram que o glicerol apresentou diferentes intera??es, dependendo do OE incorporado. A efici?ncia antibacteriana dos filmes com OE de or?gano ou canela ou or?gano mais canela foi melhorada com a presen?a de glicerol, enquanto os demais n?o sofreram influ?ncia. Diante das varia??es nas propriedades funcionais observadas, verifica-se que com a aditiva??o dos materiais ? necess?rio caracteriza??o para definir sua aplicabilidade

Made available in DSpace on 2014-06-11T19:35:46Z (GMT). No. of bitstreams: 0 Previous issue date: 2007-01-11Bitstream added on 2014-06-13T18:47:18Z : No. of bitstreams: 1 urban_vm_dr_arafo.pdf: 2869944 bytes, checksum: e7264bf2de7fc0a0dde924482741fd32 (MD5) / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) / Os objetivos deste estudo foram avaliar: 1. o efeito de tratamentos póspolimerização (MW-irradiação por energia de microondas e WB-imersão em água aquecida) sobre o grau de conversão (DC) de resinas acrílicas para reembasamento imediato (Ufi Gel hard-U, Kooliner-K e Tokuso Rebase Fast-T) e de uma resina acrílica para base de prótese (Lucitone 550-L), submetida a dois ciclos de polimerização (LS-curto e LL-longo) por espectroscopia FT-Raman; 2. o peso molecular (M w) do pré-polímero dos materiais U, K, T e L e das amostras polimerizadas da resina K (controle; MW e WB) por GPC; 3. o efeito de MW e WB na temperatura de transição vítrea (Tg) das resinas para reembasamento imediato (Duraliner II-D, K, New Truliner-N, U e T) e da resina para base de prótese (LS e LL) por DSC; 4. o efeito de WB na liberação de compostos residuais (isobutil metacrilato-IBMA, 1,6-hexanediol dimetacrilato-1,6-HDMA e DBNP-dibutil-n-ftalato) a partir das resinas para reembasamento imediato K, N, U e T para saliva artificial por CLAE; 5. o efeito de WB na liberação de produtos de degradação (ácido metacrílico-MA e ácido benzóico-BA) a partir das resinas para reembasamento imediato K, N, U e T para saliva artificial por CLAE. Amostras do grupo controle não foram submetidas a nenhum tratamento. Os resultados de DC (%) foram analisados pelo teste de Kruskal-Wallis ( =0,05). Os resultados de Tg (ºC) foram analisados pela análise de variância (ANOVA), seguido pelo teste de Tukey ( =0,05). Os resultados da liberação de monômero ' 224 residual e plastificante (μg/mL) foram submetidos aos testes de Wilcoxon ou de Mann-Whitney ( =0,05). Os resultados da liberação de produtos de degradação (μg/mL) foram submetidos aos testes de Wilcoxon, Mann-Whitney ou Kruskal- Wallis ( =0,05). Para as amostras do grupo controle, não houve diferenças significantes entre o DC das resinas U e LL e entre... / The aims of this study were to evaluate: 1. the effect of post-polymerization treatments (MW-microwave irradiation and WB-water-bath) on the degree of conversion (DC) of reline resins (Ufi Gel hard-U, Kooliner-K, and Tokuso Rebase Fast-T) and denture base resin (Lucitone 550-L), submitted to two polymerization cycles (LS-short and LL-long) by FT-Raman spectroscopy; 2. the molecular weight (M w) of the powder of U, K, T, and L materials and of K polymerized specimens (control; MW; and WB) by GPC; 3. the effect of MW and WB on the glass transition temperature (Tg) of the reline resins (Duraliner II-D, K, New Truliner-N, U and T) and the heat-polymerized resin (LS and LL) by DSC; 4. the effect of WB on the leaching of residual compounds (isobutyl methacrylate- IBMA, 1,6-hexanediol dimethacrylate-1,6-HDMA, and DBNP-dibutyl-nphthalate) from the reline resins (K, N, U, and T) in artificial saliva by HPLC; 5. the effect of WB on the leaching of degradation products (methacrylic acid-MA and benzoic acid-BA) from the reline resins K, N, U, and T in artificial saliva by HPLC. Control group specimens were left untreated. DC (%) data were analyzed using Kruskal-Wallis test (_=.05). Tg (ºC) data were analyzed using ANOVA/Tukey's test (_=.05). The results (æg/mL) of residual monomer and plasticizer leachability were submitted to Wilcoxon or Mann-Whitney tests (_=.05). The results (æg/mL) of degradation products leachability were submitted to Wilcoxon, Mann-Whitney or Kruskal-Wallis tests (_=.05). For DC control specimens, there were no significant differences between U and LL and among LL, K, and T. LS specimens had the highest DC. Only material K exhibited an increased DC after WB. All powders had M w from 4.0x105 to 6.5x105 and narrow M w distributions (2.1 to 3.6). Polymerization and post-polymerization produced K specimens with M w values similar to that of K powder...(Complete abstract, click electronic address below).

Made available in DSpace on 2014-12-17T14:07:17Z (GMT). No. of bitstreams: 1 FlankML.pdf: 1510639 bytes, checksum: 80a343cff9d15e912e4b6cbd66703104 (MD5) Previous issue date: 2006-10-16 / The isolation of adjacent zones encountered during oilwell drilling is carried out by Portland-based cement slurries. The slurries are pumped into the annular positions between the well and the casing. Their rheological behavior is a very important component for the cementing process. Nowadays, several alternative materials are used in oilwell cementing, with goal the modification and the improvement of their properties, mainly the increase of the fluidity. And this can be reached by using plasticizers additives able to account for different oilwell conditions, yielding compatible cement slurries and allowing enough time for the complete cementing operation. If the rheological properties of the slurry are properly characterized, the load loss and flow regime can be correctly predicted. However, this experimental characterization is difficult. Rheological models capable of describing the cement slurry behavior must be capable of predicting the slurry cement deformation within reasonable accuracy. The aim of this study was to characterize rheologically the slurries prepared with a especial class of Portland cement, water and plasticizers based on lignosulfonate, melamine and polycarboxylate at temperatures varying from 27?C to 72?C. The tests were carried out according to the practical recommendations of the API RP 10B guidelines. The results revealed a great efficiency and the dispersive power of the polycarboxylate, for all temperatures tested. This additive promoted high fluidity of the slurries, with no sedimentation. High lignosulfonate and melamine concentrations did not reduce the rheological parameters (plastic viscosity and yield stress) of the slurries. It was verified that these additives were not compatible with the type of cement used. The evaluated rheological models were capable of describing the behavior of the slurries only within concentration and temperature ranges specific for each type of additive / Pastas de cimento do tipo Portland s?o usadas para isolamento de po?os de petr?leo. Esse procedimento ? realizado por meio do bombeio da pasta no espa?o anular entre o po?o e a coluna de revestimento, de modo a se obter fixa??o e veda??o eficiente e permanente. Para isso o comportamento reol?gico da pasta de cimento ? um componente de extrema import?ncia para o processo de cimenta??o. Atualmente, diversos materiais alternativos s?o utilizados em pastas para cimenta??o, objetivando a modifica??o e a melhoria de suas propriedades, principalmente no que diz respeito ao aumento de fluidez. Isso pode ser alcan?ado por meio da utiliza??o de novos aditivos do tipo plastificantes, capazes de suportar as diversas condi??es de po?os, promovendo ?s pastas propriedades compat?veis ?s condi??es encontradas, permitindo, ainda, um tempo suficiente de trabalhabilidade para a completa execu??o do servi?o de cimenta??o. Assim, se as propriedades reol?gicas da pasta s?o bem caracterizadas, a perda de carga e o regime de fluxo podem ser prognosticados corretamente. Contudo, essa caracteriza??o ? dif?cil do ponto de vista experimental. Modelos reol?gicas capazes de descrever o que ocorre, dever?o ser capazes de predizer a deforma??o da pasta de cimento com razo?vel exatid?o. Portanto, a finalidade deste trabalho foi o estudo e a caracteriza??o reol?gica de pastas constitu?das de cimento Portland classe especial, ?gua e aditivos do tipo plastificante, a base de lignossulfonato, melamina e policarboxilato, em temperaturas na faixa de 27?C a 72?C. Os testes foram realizados de acordo com as recomenda??es pr?ticas da norma API RP 10B. Os resultados dos ensaios demonstraram a grande efici?ncia e o poder dispersivo do policarboxilato, para todas as temperaturas estudadas. O aditivo promoveu uma alta fluidez, sem efeitos de sedimenta??o. O aumento das concentra??es de lignossulfonato e melamina n?o reduziu os par?metros reol?gicos (viscosidade pl?stica e limite de escoamento). Tamb?m foi verificado que esses aditivos n?o foram compat?veis com o tipo de cimento utilizado. Por fim, os modelos reol?gicos avaliados foram capazes de descrever o comportamento das pastas apenas para faixas de temperatura e concentra??o de cada tipo de aditivo