Despite the potential of kafirin (sorghum prolamin protein) films, up until now there has been no in-depth investigation on the plasticization of kafirin films, similar to that done on zein films. Since protein films tend to be very brittle, plasticization is a very important aspect. Cast films were produced from kafirin and plasticized with different combinations of plasticizers (glycerol (G), polyethylene glycol 400 (PEG) and lactic acid (LA)) according to a rotatable central composite statistical design. The effects of the different plasticizer combinations on the film properties (tensile-, Tg-, moisture and oxygen barrier properties), were investigated through a series of tests performed on the films. Plasticization of kafirin films was investigated further by determining the effect of an emulsifier, diacetyl tartaric ester of monoglyceride (DATEM) and an acidulant, glucono-_-lactone (GDL) on the films. To investigate the distribution and migration of the plasticizers in kafirin films, the films were studied by light microscopy. It was clear that G, PEG and LA together were necessary to plasticize kafirin films. G and PEG were found to be effective plasticizers, leading to a decrease in film strength and an increase in strain as the plasticizer amount increased. LA was, however, found to act rather as a solvent for kafirin during film casting, instead of acting as a plasticizer. An increase in plasticizer content also brought about a lowering in the Tg of the films, as well as an increase in film permeability to water vapour and oxygen. G and PEG were found to attract water from the atmosphere, which proved to be very influential on the properties of the films; the more plasticizer present in the film, the more moisture attracted, the greater the effect on the film properties. DATEM was not found to be a plasticizer for kafirin films. However, GDL did bring about changes in film properties, similar to G and PEG. It caused film strength to decrease and film strain to increase, but with less detrimental effects on the moisture barrier properties of kafirin films. Microscopy showed that the plasticizer migrated over time, apparently leading to plasticizer molecule coalescence, and the formation of plasticizer pools. The plasticizer combination of G, PEG and LA improved the qualities of kafirin films, reducing film brittleness, but it is not an ideal plasticizer combination due to the fact that it attracts water to the film and it is not stable over time. Moisture is another plasticizer to be taken into account, since it will be absorbed by the plasticizers in high relative humidity areas and will have an additional plasticizing effect on films properties. GDL proved to have potential as a kafirin film plasticizer as it affected the barrier properties of the films less. Further research is recommended into the plasticization mechanism of GDL. / Dissertation (MSc(Agric))--University of Pretoria, 2008. / Food Science / unrestricted

PVC are extensively applied in many fields, such as cables, pipes, vehicles, shoes, toys and infusion bags. Generally, plasticizers are blended with PVC to improve the ability of process in industrial production; however, the toxic plasticizers will gradually migrate to the surface of products and such a leakage results in brittleness of plasticized PVC and environmental pollution. In other words, humans are frequently exposed to the potential risks. According to previous researches, cross-linked PVC was proved that it was able to hinder the migration of plasticizer. Thus, in this research, we selected some commercially used cross-linking agents and employed six different tests based on mechanical, tribological and microscopy analysis in order to seek the best solution against plasticizer migration. Thus, we expected to develop a cross-linked flexible PVC which performed improved long-term performance and extended lifetime.

No description available.

No description available.

Le polychlorure de vinyle (PVC) plastifié est un plastique très présent dans les collections patrimoniales et dans un état de conservation jugé souvent médiocre. Les dégradations les plus fréquentes sont l’exsudation et la perte de souplesse des objets qui sont liées à la migration progressive du plastifiant vers la surface du matériau.Les travaux de thèse visaient à mieux comprendre les processus d’altération des objets en PVC plastifiés et à préconiser des conditions de conservation et des traitements de restauration. Cette étude a été réalisée en parallèle sur des PVC de formulation simplifiée et sur des PVC anciens vieillis naturellement en musée. La cinétique de migration du plastifiant et les modifications structurales des chaînes PVC ont été caractérisées au cours d’un vieillissement artificiel des films réalisé dans les conditions les plus représentatives d’un environnement muséal d’exposition ou de conservation.L’impact du nettoyage des surfaces a été étudié en terme d’efficacité mais surtout de dégradation ultérieure du PVC et notamment de réapparition des exsudats. L’effet de différents conditionnements sur le vieillissement des PVC souples, nettoyés ou non, a également été évalué. Des matériaux d’emballage régulièrement utilisés par les restaurateurs ont été considérés.Ces travaux ont permis d’apporter un éclairage sur l’effet des méthodes utilisées lors de la restauration et la conservation des œuvres en PVC plastifié. / Plasticized polyvinyl chloride (PVC) is a plastic widely used in patrimonial collections but its state of preservation is often considered as poor. The most frequent degradations are the exudation and the loss of flexibility of objects which are related to the progressive migration of the plasticizer towards the surface of the material.The project thesis aimed to better understand the alteration of plasticized PVC objects and predict conditions of conservation and restoration treatments.This study was conducted with both a simplified formulation of PVC and an ancient PVC naturally aged in museum.The kinetics of plasticizer migration and structural modifications of PVC chains were characterized during artificial ageing of films conducted through the most representative conditions of a museum environment of exposure or conservation.The impact of surface cleaning was studied in terms of efficiency but also subsequent degradation of the PVC, in particular the recurrence of exudates. The effect of different conditionings on the ageing of flexible PVC, either cleaned or not, was also estimated. Packaging materials frequently used by conservators have been considered.This work allowed achieving new insights on the effect of methods used for conservation and preservation of plasticized PVC artefacts.

Detection of volatile organic compounds (VOC’s) in the environment is important for human health and wellness. Long term exposure of certain VOC’s like benzene, toluene, ethylbenzene and xylene (BTEX) has a severe effect on human health. There are techniques such as gas chromatography, photo ionization, and mass spectroscopy that are time consuming, require gas sampling and are ineffective in real time sensing in air. Acoustic wave devices such as surface acoustic wave (SAW) devices can be used for sensing BTEX compounds in both vapor and liquid phase. The quartz crystal microbalance (QCM) is a low-frequency acoustic wave device, which can be used to characterize polymer film sensing quickly and easily by studying the sorption properties of BTEX compounds in them. In this work, thin films (~ 0.5 microns) of polymer/plasticizer blends are spin-coated on a 5MHz QCM for the detection of VOC’s. A polymer/plasticizer combination of poly (ethyl methacrylate) (PEMA) and a copolymer of poly (ethyl methacrylate) and poly (methyl methacrylate) (PEMA/PMMA) with di n-butyl phthalate (DBP), di-n-butyl sebacate (DBS) and n-butyl stearate (BS) are used for the detection of benzene, toluene and ethylbenzene in vapor phase. The working apparatus consists of a stream of solvent vapor diluted with nitrogen to an arbitrary concentration passing over the QCM oscillated to its resonant frequency. The sorption data are reported at 298.15 K in terms of activity as a function of weight fraction curves and are interpreted with the Flory-Huggins ternary model. The addition of plasticizer modifies the free volume properties of the polymer, thereby increasing diffusion and sensitivity of BTEX vapors. The plasticizer composition is tailored to 17.5%, for maximum sorption with minimal viscoelastic effects. The sorption and sensitivity of BTEX are interpreted and studied in terms of plasticizer type and concentration.

This thesis is concerned with the development of engineering technologies that facilitate melt spinning of carbon fiber precursors in both an environmentally sound and cost effective manner. More specifically, methods were developed to avoid a degradative process in acrylonitrile copolymers (typically used in textiles and as carbon fiber precursors) that occurs as melt spinning temperatures are approached. The following set of analyses was developed to define the rheological properties required for a melt processable acrylic copolymer suitable for use as a carbon fiber precursor, and accordingly facilitated development of a processing window: measurement of steady shear viscosity as a function of both temperature and time, measurement of the magnitude of the complex viscosity (|η*|) as a function of temperature using a temperature sweep, and measurement of the angular frequency dependence of |η*|. Through a systematic screening process, the following properties were identified to afford melt spinnable acrylic precursors suitable for conversion to carbon fibers: emulsion polymerization, 85-88 mole % acrylonitrile, 11-14 mole % methyl acrylate, 1 mole % acryloyl benzophenone, intrinsic viscosity < 0.6 dL/g, steady shear viscosity ≤ 1000-2000 Pa*s at a shear rate (γ) of 0.1 s⁻¹, viscosity increases ≤ 45% over a period of 1800 seconds at 200-220°C and γ=0.1 s⁻¹. Use of the rheological analyses assisted in development of a melt spinnable carbon fiber precursor, which resulted in carbon fibers possessing a tensile strength and modulus of approximately 1.0 and 120 GPa, respectively. A second approach was evaluated using carbon dioxide (CO₂) to plasticize AN copolymers to an extent that facilitates processing at reduced temperatures, below where thermal degradation is significant. A batch saturation method to absorb CO₂ in AN copolymers was developed. Differential scanning calorimetry and thermogravimetric analyses were used to measure the glass transition temperature (T_g) reduction and amount of absorbed CO₂ (respectively). A pressurized rheometer and measurement procedure was designed to obtain viscosity measurements of saturated AN copolymers. Up to 6.7 wt. % CO₂ was found to absorb into a 65 mole % AN copolymer with the saturation method used, resulting in a 31°C glass transition temperature (T_g) reduction, 60% viscosity reduction, and 30°C potential processing temperature reduction. It was found that CO₂ can absorb into copolymers containing up to 90 mole % AN (with the absorption methods used) with the following results (for a 90/10 mole % AN/MA copolymer): 3.0 wt. % uptake, 27°C T_g reduction, 56% viscosity reduction, and potential processing temperature reduction of 9°C. Via estimates of the required pressure, sealing fluid flow rate, and length of a pressure chamber to prevent foaming of the saturated polymer melt during extrusion, melt spinning of saturated AN copolymers appears feasible. / Ph. D.

Chapas de poli(metacrilato de metila) podem ser modificadas por meio da adição de um agente promotor de ligações cruzadas e um plastificante objetivando incrementar seu desempenho durante a termoformagem. A interação intermolecular, modificada com a adição de diferentes quantidades de um agente promotor de ligações cruzadas (TEGDMA) e pela presença de um plastificante (DOP) faz com que as macromoléculas sejam ancoradas e afastadas respectivamente. O desenvolvimento deste trabalho objetivou, avaliar as propriedades físicas, mecânicas, térmicas e o processamento via termoformagem para duas diferentes temperaturas de termoformagem em um molde cilíndrico, a uma mesma taxa de deformação e determinado a influência da formulação, para cinco chapas que se diferenciaram nas quantidades de TEGDMA e uma quantidade fixada de DOP para duas das formulações. Os resultados mostraram que há incremento na deformação com as modificações introduzidas quando comparado a uma chapa sem adição de TEGDMA ou DOP e as propriedades destas chapas como dureza superficial, módulo de rigidez e temperatura de transição vítrea apresentaram mudanças sensíveis, que caracterizam vantagens no uso dos dois componentes. / Poly(methyl methacrylate) sheets can be modified adding a cross-linking agent and a plasticizer, to increase performance during thermoforming. The intermolecular interaction modification can be achieved adding different amount of cross-linking agent (TEGDMA) and a plasticizer (DOP). They have an effect on the network polymer system improving the intermolecular interaction and increasing the macromolecular distances, respectively. The aim of this study was to prepare acrylic sheets formulations with differents amounts of TEGDMA and a fixed amount of DOP, and thermoformed using at differents process temperatures and a mould cylinder at the same strain rate. Samples were carried out and their properties physical, mechanical, thermal and thermoformability was characterized. The results have shown strain increases, changes in surface hardness, Young moduli and glass transition temperature, compared to a reference acrylic sheet.

Chapas de poli(metacrilato de metila) podem ser modificadas por meio da adição de um agente promotor de ligações cruzadas e um plastificante objetivando incrementar seu desempenho durante a termoformagem. A interação intermolecular, modificada com a adição de diferentes quantidades de um agente promotor de ligações cruzadas (TEGDMA) e pela presença de um plastificante (DOP) faz com que as macromoléculas sejam ancoradas e afastadas respectivamente. O desenvolvimento deste trabalho objetivou, avaliar as propriedades físicas, mecânicas, térmicas e o processamento via termoformagem para duas diferentes temperaturas de termoformagem em um molde cilíndrico, a uma mesma taxa de deformação e determinado a influência da formulação, para cinco chapas que se diferenciaram nas quantidades de TEGDMA e uma quantidade fixada de DOP para duas das formulações. Os resultados mostraram que há incremento na deformação com as modificações introduzidas quando comparado a uma chapa sem adição de TEGDMA ou DOP e as propriedades destas chapas como dureza superficial, módulo de rigidez e temperatura de transição vítrea apresentaram mudanças sensíveis, que caracterizam vantagens no uso dos dois componentes. / Poly(methyl methacrylate) sheets can be modified adding a cross-linking agent and a plasticizer, to increase performance during thermoforming. The intermolecular interaction modification can be achieved adding different amount of cross-linking agent (TEGDMA) and a plasticizer (DOP). They have an effect on the network polymer system improving the intermolecular interaction and increasing the macromolecular distances, respectively. The aim of this study was to prepare acrylic sheets formulations with differents amounts of TEGDMA and a fixed amount of DOP, and thermoformed using at differents process temperatures and a mould cylinder at the same strain rate. Samples were carried out and their properties physical, mechanical, thermal and thermoformability was characterized. The results have shown strain increases, changes in surface hardness, Young moduli and glass transition temperature, compared to a reference acrylic sheet.

De récentes études ayant pointé les potentiels effets de perturbation endocrinienne d’esters organophosphorés (OPE), dont l’utilisation globale en tant que retardateurs de flamme et plastifiants est en constante augmentation, font apparaître le besoin d’une évaluation approfondie des risques. Malgré des efforts passés pour l'analyse de ces contaminants ré-émergents dans divers compartiments environnementaux abiotiques, peu d'informations sont disponibles pour le biote, en partie en raison de l'absence de stratégie analytique efficace. La thèse visait d'abord à développer une stratégie d'analyse robuste dédiée à l’analyse d’une large gamme d'OPE à l’état de traces dans le poisson et d’autres denrées alimentaires. La stratégie retenue est basée sur l'extraction liquide sélective sous pression et la chromatographie par perméation de gel. La détection a été réalisée par chromatographie en phase gazeuse couplée à la spectrométrie de masse en tandem, avec ionisation par impact électronique ou chimique à pression atmosphérique, cette dernière étant plus spécifique et innovante. Le second objectif visait à produire des données de prévalence originales et utiles à l'évaluation de l'exposition en France. Des jeux de poissons et de denrées emballées ont présenté des niveaux totaux inférieurs à 10 et jusqu'à 100 ng/g pf, respectivement. Une première exploitation des données sur poissons en termes d'évaluation quantitative de risque pour l’Homme a dévoilé des ratios de risques faibles au regard de données toxicologiques disponibles. Néanmoins, des données complémentaires sur l'exposition et la toxicologie seront indispensables pour conclure quant aux implications en santé publique. / As recent studies highlighted that several organophosphate esters (OPEs) exhibit potential endocrine disrupting effects, in-depth risk assessment is required, when their global use as flame retardants and plasticizers is considerably increased. Despite previous efforts on the analysis and exposure assessment of these re-emerging contaminants in various abiotic environmental compartments, still limited information is available in biota samples, partly due to the lack of efficient analytical strategies. The thesis aimed first at developing a robust analytical strategy dedicated to the determination of a wide range of OPEs at trace levels in fish and other foodstuffs. The developed strategy involved selective pressurized liquid extraction with Florisil® as lipid sorbent, followed by further purification step by gel permeation chromatography. The extract analysis was then performed by gas chromatography coupled to tandem mass spectrometry fitted with electron impact or atmospheric pressure chemical ionisation mode, the latter being a more specific and innovative approach. The second aim was to apply the developed strategy to produce original occurrence data that can be useful for exposure assessment at the French level. Fish sample sets exhibited levels below 10 ng/g fw while packaged foodstuffs presented levels up to 100 ng/g fw. A first interpretation of these data in terms of dietary human quantitative risk assessment through fish consumption tended to show low risk ratios in connection with available toxicological data. However, additional exposure and toxicological data is required before any conclusions regarding public health implication can be drawn