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Understanding the process-structure-property relationship in biodegradable polymer nanocomposite filmsSullivan, Erin M. 07 January 2016 (has links)
The focus of this study was to explore process-structure-property relationships in biodegradable polymer nanocomposite films in order to eliminate the commonly used trial and error approach to materials design and to enable manufacturing of composites with tailored properties for targeted applications. The nanofiller type and concentration, manufacturing method and compounding technique, as well as processing conditions were systematically altered in order to study the process-structure-property relationships. Polylactic acid (PLA) was used as the polymer and exfoliated graphite nanoplatelets (GNP), carbon nanotubes (CNT), and cellulose nanocrystals (CNC) were used as reinforcement. The nanocomposite films were fabricated using three different methods: 1) melt compounding and melt fiber spinning followed by compression molding, 2) solution mixing and solvent casting, and 3) solution mixing and electrospinning followed by compression molding. Furthermore, the physical properties of the polymer, namely the crystallization characteristics were altered by using two different cooling rates during compression molding. The electrical response of the composite films was examined using impedance spectroscopy and it was shown that by altering the physical properties of the insulating polymer matrix, increasing degree of crystallinity, the percolation threshold of the GNP/PLA films is significantly reduced. Additionally, design of experiments was used to examine the influence of nanofiller type (CNT versus GNP), nanofiller content, and processing conditions (cooling rate during compression molding) on the elastic modulus of the composite films and it was concluded that the cooling rate is the primary factor influencing the elastic modulus of both melt compounded CNT/PLA and GNP/PLA films. Furthermore, the effect of nanofiller geometry and compounding method was examined and it was shown that the high nanofiller aspect ratio in the CNT/PLA films led to decreased percolation threshold compared to the GNP/PLA films. The melt compounded GNP/PLA films displayed a lower percolation threshold than the solution cast GNP/PLA films most likely due to the more homogeneous distribution and dispersion of GNP in the solution cast films. Fully biodegradable and biorenewable nanocomposite films were fabricated and examined through the incorporation of CNC in PLA. Through the addition of CNC, the degree of crystallinity of the matrix was significantly increased. Focusing the design space through investigation of process-structure-property relationships in PLA nanocomposites, can help facilitate nanocomposites with tailored properties for targeted applications.
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Functionalized Nanoparticles for Biomedical ApplicationsBryant, Erika 16 September 2013 (has links)
Functionalization of nanoparticles often control the extent of their usage. With this in mind, I have explored methods of creating highly functionalized exfoliated graphite, by way of the Billups-Birch reduction, that can be used in the advancement of nanotechnology (i.e. biomedicine). The method explored the use of sodium as the source for the solvated electron. The results of this method produced exfoliated graphite the same size as graphene and with solubility similar to the substrates attached to it. It was further shown that functionalized graphite with a terminal carboxyl group allowed further synthesis to occur via an elimination-addition reaction after the acyl group was transformed into an acid chloride. This reaction makes it possible to create exfoliated graphite that contains any compound of interest as long as it has an oxygen or nitrogen group that is able to react with the acid chloride. Thus, these products have the potential to be used in biomedicine as drug delivery agents.
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Frequência de micronúcleos em células esfoliadas da mucosa bucal de pacientes obesos / Micronuclei frequency in exfoliated buccal cells of obese patientsCarvalho, Cristiane Alves Paz de 29 June 2012 (has links)
A crescente incidência da obesidade e suas comorbidades constituem-se em um grande desafio para a saúde no mundo. Além da doença cardiovascular e do diabetes, dados epidemiológicos demonstraram ligação entre a obesidade e diversos tipos de câncer. As alterações citogenéticas tem sido utilizadas como biomarcadores para identificação de danos celulares. Este estudo teve como objetivos: comparar a frequência dos tipos celulares (células basais e diferenciadas), anormalidades nucleares (células binucleadas, picnóticas, cariorréticas, cariolíticas e com cromatina condensada) e de danos celulares (micronúcleos e brotos nucleares) de células bucais esfoliadas em um grupo de obesos (teste) e em um grupo de indivíduos com peso normal (controle). A amostra foi composta por 30 indivíduos, sendo o grupo teste constituído por indivíduos obesos mórbidos (n=15) e o grupo controle por indivíduos com peso normal (n=15). A classificação do peso corporal foi feita de acordo com o Índice de Massa Corporal (IMC); um questionário forneceu informações sobre exposições ocupacionais e não ocupacionais; hábitos e dieta. As células da mucosa bucal foram coletadas da mucosa jugal, de ambos os lados, processadas e analisadas microscopicamente. Para cada indivíduo foram avaliadas 1000 células para a caracterização dos tipos celulares (basal e diferenciada) e alterações nucleares (células binucleadas, picnose, cariólise, cariorrexe, cromatina condensada) e 2000 células diferenciadas para verificar a presença de danos celulares (micronúcleos e brotos nucleares). Os dados foram processados e analisados estatisticamente, por meio do teste de Mann Whitney. Considerou-se o nível de significância de 5% (p<0,05). Observaram-se diferenças nas frequências de tipos celulares e anomalias nucleares para os dois grupos, porém estas diferenças não foram significativas (p>0,05). Quanto ao tipo de dano celular, notou-se a mesma frequência de brotos nucleares para ambos os grupos, entretanto, a frequência de micronúcleos foi maior para o grupo obeso (p<0,001). Neste estudo, verificou-se maior frequência de micronúcleos nas células esfoliadas da mucosa bucal em indivíduos obesos mórbidos que em indivíduos com peso normal. Este achado sugere que a obesidade possa levar à maior ocorrência de alterações citogenéticas. / The increasing incidence of obesity and its co-morbid conditions poses a great challenge to global health. In addition to cardiovascular disease and diabetes, epidemiological data demonstrate a link between obesity and multiple types of cancer. The buccal micronucleus cytome assay has been used as a biomarker for identification of cell damage. This study aimed to compare the frequency of cell types (basal and differentiated), nuclear anomalies (binucleated, pyknotic, karyorrhectic, karyolitic and condensed chromatin cells), and cell damage (micronuclei and nuclear buds) in exfoliated buccal cells in a group of obese (test) and a group of normal weight (control).The sample consisted of 30 subjects, the test group comprised of individuals with morbid obesity (n = 15) and a control group of normal weight (n = 15). The classification of body weight was made according to Body Mass Index (BMI), a questionnaire provided information on occupational exposures and non-occupational, lifestyle and diet. The oral mucosa cells were collected from the buccal mucosa, on both sides, processed and analyzed microscopically. For each individual 1000 cells were evaluated for the characterization of cell types (basal and differentiated) and nuclear abnormalities (binucleated cells, pyknosis, karyolysis, karyorrhexis, condensed chromatin) and 2000 differentiated cells for the presence of cellular damage (micronuclei and nuclear buds). The data were processed and statistically analyzed using the Mann-Whitney test. We considered the significance level of 5% (p <0.05). Differences were observed in the frequencies of cell types and nuclear abnormalities in both groups, but these differences were not significant (p> 0.05). Regarding the type of cell damage, we noticed the same frequency of nuclear buds for both groups, however, the frequency of micronuclei was higher in the obese group (p <0.001). In this study, there was a higher frequency of micronuclei in exfoliated cells of buccal mucosa in morbidly obese individuals than in individuals with normal weight. This finding suggests that obesity may lead to higher rates of cytogenetic changes.
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Frequência de micronúcleos em células esfoliadas da mucosa bucal de pacientes obesos / Micronuclei frequency in exfoliated buccal cells of obese patientsCristiane Alves Paz de Carvalho 29 June 2012 (has links)
A crescente incidência da obesidade e suas comorbidades constituem-se em um grande desafio para a saúde no mundo. Além da doença cardiovascular e do diabetes, dados epidemiológicos demonstraram ligação entre a obesidade e diversos tipos de câncer. As alterações citogenéticas tem sido utilizadas como biomarcadores para identificação de danos celulares. Este estudo teve como objetivos: comparar a frequência dos tipos celulares (células basais e diferenciadas), anormalidades nucleares (células binucleadas, picnóticas, cariorréticas, cariolíticas e com cromatina condensada) e de danos celulares (micronúcleos e brotos nucleares) de células bucais esfoliadas em um grupo de obesos (teste) e em um grupo de indivíduos com peso normal (controle). A amostra foi composta por 30 indivíduos, sendo o grupo teste constituído por indivíduos obesos mórbidos (n=15) e o grupo controle por indivíduos com peso normal (n=15). A classificação do peso corporal foi feita de acordo com o Índice de Massa Corporal (IMC); um questionário forneceu informações sobre exposições ocupacionais e não ocupacionais; hábitos e dieta. As células da mucosa bucal foram coletadas da mucosa jugal, de ambos os lados, processadas e analisadas microscopicamente. Para cada indivíduo foram avaliadas 1000 células para a caracterização dos tipos celulares (basal e diferenciada) e alterações nucleares (células binucleadas, picnose, cariólise, cariorrexe, cromatina condensada) e 2000 células diferenciadas para verificar a presença de danos celulares (micronúcleos e brotos nucleares). Os dados foram processados e analisados estatisticamente, por meio do teste de Mann Whitney. Considerou-se o nível de significância de 5% (p<0,05). Observaram-se diferenças nas frequências de tipos celulares e anomalias nucleares para os dois grupos, porém estas diferenças não foram significativas (p>0,05). Quanto ao tipo de dano celular, notou-se a mesma frequência de brotos nucleares para ambos os grupos, entretanto, a frequência de micronúcleos foi maior para o grupo obeso (p<0,001). Neste estudo, verificou-se maior frequência de micronúcleos nas células esfoliadas da mucosa bucal em indivíduos obesos mórbidos que em indivíduos com peso normal. Este achado sugere que a obesidade possa levar à maior ocorrência de alterações citogenéticas. / The increasing incidence of obesity and its co-morbid conditions poses a great challenge to global health. In addition to cardiovascular disease and diabetes, epidemiological data demonstrate a link between obesity and multiple types of cancer. The buccal micronucleus cytome assay has been used as a biomarker for identification of cell damage. This study aimed to compare the frequency of cell types (basal and differentiated), nuclear anomalies (binucleated, pyknotic, karyorrhectic, karyolitic and condensed chromatin cells), and cell damage (micronuclei and nuclear buds) in exfoliated buccal cells in a group of obese (test) and a group of normal weight (control).The sample consisted of 30 subjects, the test group comprised of individuals with morbid obesity (n = 15) and a control group of normal weight (n = 15). The classification of body weight was made according to Body Mass Index (BMI), a questionnaire provided information on occupational exposures and non-occupational, lifestyle and diet. The oral mucosa cells were collected from the buccal mucosa, on both sides, processed and analyzed microscopically. For each individual 1000 cells were evaluated for the characterization of cell types (basal and differentiated) and nuclear abnormalities (binucleated cells, pyknosis, karyolysis, karyorrhexis, condensed chromatin) and 2000 differentiated cells for the presence of cellular damage (micronuclei and nuclear buds). The data were processed and statistically analyzed using the Mann-Whitney test. We considered the significance level of 5% (p <0.05). Differences were observed in the frequencies of cell types and nuclear abnormalities in both groups, but these differences were not significant (p> 0.05). Regarding the type of cell damage, we noticed the same frequency of nuclear buds for both groups, however, the frequency of micronuclei was higher in the obese group (p <0.001). In this study, there was a higher frequency of micronuclei in exfoliated cells of buccal mucosa in morbidly obese individuals than in individuals with normal weight. This finding suggests that obesity may lead to higher rates of cytogenetic changes.
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Electrochemical detection of organic and inorganic water pollutants using recompressed exfoliated graphite electrodesNdlovu, Thabile 05 November 2012 (has links)
Ph.D. / This study explored the possible application of a relatively new electrode called exfoliated graphite electrode (EG electrode) in the electroanalysis of organic and inorganic water pollutants. This study also explored the applicability of this electrode in the removal of heavy metal pollutants in water. The EG material was successfully prepared by intercalating bisulphate ions into graphite flakes (>300 μm) followed by thermal shock at 800°C to obtain an exfoliated graphite. After compressing the EG at high pressure, the obtained circular sheets were used to fabricate electrodes. The electrochemical profiles of EG electrode and glassy carbon electrodes (GCE) were recorded and compared using cyclic voltammetryand square wave voltammetry in the presence of various supporting electrolytes and [Fe(CN)6]3-/4-, [Ru(NH3)6]2+/3+, ferrocene redox probes. In the supporting electrolytes (KCl, H2SO4, NaOH, tetrabutylammoniumtetraflouroborate, phosphate buffers), the potential windows of EG were found, in some cases, to be about 300 mV larger than that of GCE. The diffusion coefficients (cm2s-1) of the redox probes were calculated to be 3.638 x 10-6, 1.213 x 10-6 and 4.411 x 10-6 for [Fe(CN)6]3-/4-, [Ru(NH3)6]2+/3+ and ferrocene, respectively. These values are comparable to those obtained from GCE. Furthermore, EG was modified with various nanomaterials such as poly (propylene imine) dendrimer (PPI), gold nanoparticles, silver nanoparticles, dendrimer–gold nanoparticles composite, cobalt oxide and bismuth. The morphologies of the modified electrodes were studied using scanning electron microscopy and their electrochemical reactivities in the three redox probes were investigated. The current and the reversibility of redox probes were enhanced in the presence of modifiers in different degrees with dendrimer and gold nanoparticles having a favourable edge. The electrochemical determination of o-nitrophenol by square wave voltammetry using a nanocomposite of generation 2 poly(propyleneimine) dendrimer and gold nanoparticles modified GCEand EG electrode were compared. A characteristic reduction peak between -600 mV and -700 mV for o-nitrophenol was observed with enhanced current on both GCE and EG modified electrodes.
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The influence of three different intercalation methods on the properties of exfoliated graphiteVan Heerden, Xandra January 2015 (has links)
It is unclear whether all intercalation techniques truly lead to the insertion of atoms
between the graphite layers, or also lead to other effects which contribute to expansion.
The objective of this project is to better understand the effects caused by different
intercalation methods. Three intercalation methods were explored to determine
the method which incurs the least damage to the surface and microstructure of
the graphite intercalated compounds, yet achieves the best intercalation and therefore
expansion.
All the main findings are summarised below:
The gas phase sample had virtually no mass loss at the point where expansion
took place. Therefore the intercalation was very efficient, producing large
expansion without significant mass loss.
The mass loss that only occurs at the sublimation of iron chloride (320 ºC) indicates
the excessive "un-intercalated" or residual iron chloride.
After oxidation, before purification, the gas phase sample has 25 % residual
mass; this also proves the presence of impurities and residual iron chloride in
the exfoliated sample. For the Hummers and electrochemical samples, expansion and mass loss occur
over a wide temperature range, this indicates that graphite oxide was
formed rather than the theoretically expected "insertion of atoms between the
sheets".
The mass losses before 200 ˚C of the samples of the Hummers and electrochemical
methods are more evidence that graphite oxide and graphite surface
complexes with oxygen were produced.
The Hummers and electrochemical intercalation methods show similar expansion
and mass loss curves, therefore it can be concluded that the reaction
mechanism for both these methods is alike.
The gas phase method yields the best expansion of 250 % using the TMA,
whereas both the other methods deliver approximately 220 %.
Using microwave expansion the electrochemical intercalation method yields
the best bulk volume expansion of 1500 %, with the gas phase sample delivering
a volume expansion of 1450 %.
The Hummers samples are extremely damaged. This is clear from the several and
deep oxidation pits visible throughout the basal plane of these samples. The basal
plane and the edges are even eroded before purification and oxidation. This intercalation
technique employs oxidisers in the preparation method which additionally oxidises
the samples. This explains why the Hummers method renders the most damage.
The residual material on the gas phase sample acts as catalysts making the sample
very reactive and consequently damaging the surface during oxidation. The partially
oxidised purified gas phase sample visibly shows the pits and roughened edges.
There are two “types” of intercalation. The first intercalation “type” is the actual insertion
of atoms or molecules between the graphite layers, whereas the other “type”
of intercalation is the production of graphite oxide. The compound comprises carbon,
oxygen and hydrogen, obtained by treating graphite with strong oxidisers. The
functional groups usually found in graphite oxide are carbonyl (C=O), hydroxyl (-OH), phenol amongst others and also some impurities of sulphur when sulphuric acid is
used. Both these intercalation types lead to expansion.
It is recommended that a more efficient method for removal of residual material in
the gas phase samples be explored. It is also recommended that more research be
done to determine the reaction mechanisms during the three different intercalation
methods. The graphite surface complexes of the intercalated compounds and the
evolved gases during expansion should be analysed. / Dissertation (MEng)--University of Pretoria, 2015. / tm2015 / Chemical Engineering / MEng / Unrestricted
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Integrated Bipolar Plate – Gas Diffusion Layer Design for Polymer Electrolyte Membrane Fuel CellsNeff, David N. January 2009 (has links)
No description available.
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The Chemistry of Dimethacrylate-Styrene Networks and Development of Flame Retardant, Halogen-Free Fiber Reinforced Vinyl Ester CompositesRosario, Astrid Christa 12 December 2002 (has links)
One of the major classes of polymer matrix resins under consideration for structural composite applications in the infrastructure and construction industries is vinyl ester resin. Vinyl ester resin is comprised of low molecular weight poly(hydroxyether) oligomers with methacrylate endgroups diluted with styrene monomer. The methacrylate endgroups cure with styrene via free radical copolymerization to yield thermoset networks. The copolymerization behavior of these networks was monitored by Fourier Transform Infrared Spectroscopy (FTIR) at various cure conditions. Reactions of the carbon-carbon double bonds of the methacrylate (943 cm-1) and styrene (910 cm-1) were followed independently. Oligomers possessing number average molecular weights of 700 g/mole were studied with systematically increasing levels of styrene. The Mortimer-Tidwell reactivity ratios indicated that at low conversion more styrene was incorporated into the network at lower cure temperatures. The experimental vinyl ester-styrene network compositions deviated significantly from those predicted by the Meyer-Lowry integrated copolymer equation at higher conversion, implying that the reactivity ratios for these networks may change with conversion. The kinetic data were used to provide additional insight into the physical and mechanical properties of these materials.
In addition to establishing the copolymerization kinetics of these materials, the development of halogen free fiber reinforced vinyl ester composites exhibiting good flame properties was of interest. Flame retardant vinyl ester resins are used by many industries for applications requiring good thermal resistance. The current flame-retardant technology is dependent on brominated vinyl esters, which generate high levels of smoke and carbon monoxide. A series of halogen free binder systems has been developed and dispersed in the vinyl ester to improve flame retardance. The binder approach enables the vinyl ester resin to maintain its low temperature viscosity so that fabrication of composites via Vacuum Assisted Resin Transfer Molding (VARTM) is possible. The first binder system investigated was a polycaprolactone layered silicate nanocomposite, which was prepared via intercalative polymerization. Transmission Electron Microscopy (TEM) and X-ray Diffraction (XRD) data indicated a mixed morphology of exfoliated and intercalated structures. The mechanical properties and the normalized peak heat release rates were comparable to the neat vinyl ester resin.
Alternative binder systems possessing inherent flame retardance were also investigated. A series of binders comprised of novolac, bisphenol A diphosphate, and montmorillonite clay were developed and dispersed into the vinyl ester matrix. Cone calorimetry showed reductions in the peak heat release rate comparable to the brominated resin. / Ph. D.
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Evaulation of liquid-exfoliatedgraphene as additive in Ag-basedsliding contactsJuhlin, Stina January 2018 (has links)
This master thesis work is performed at ABB Corporate Research Center inVästerås. The aim of this study is to investigate Ag:graphene composites as slidingelectrical contacts, suitable for use in e.g. tap-changers. Three different graphenematerials, all produced by a low-cost exfoliation process, are evaluated in this study. The results are compred to an ongoing work on Ag:GO (graphene oxide) composites. This material has shown very good tribological properties, however it hasbeen difficult to handle during sintering processing. The goal of this study is to geteven better tribological, electrical and mechanical properties than Ag:GO, and also todevelop a new powder-metallurgical method to produce the Ag:graphene composites.The study also investigates the influence of graphene flake size and concentration aswell as microstructure of the Ag:graphene composites. This report focuses on aninvestigation of the graphene raw material quality from the suppliers, and friction,wear and resistance analysis of the composites. This is done by using Ramanspectroscopy, SEM with EDS, LOM, tribometer tests and resistivity analysis. Raman and SEM analyses show that none of the supplied LEG materials are ofhigh-quality G (single or bilayer), but rather multi-layer graphene or even graphite.Small amounts of graphene added to Ag gave extremly low friction (μ<0.2 vs. pureAg μ~1.3, 5 N load and 5 cm/s speed). The composite manufacturing process hadcritical steps, which have to be optimized, to obtain low values of friction. Severedegassing of the composites was observed for some sampes, but the samples stillmaintained good friction values. SEM and EDS analyses of 2dfab’s wear track show abuild-up thin carbon-containing tribofilm on the Ag surface. Indicating that G ispresent, and works as a lubricant, creating good tribological properties. The resultsfrom this project may for sure be of importance for future ABB products in specificindustrial applications.
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Caractérisation et modélisation du comportement mécanique d'éléments d'étanchéité par presse garniture / Characterization of the mechanical behaviour and modelling of sealing elements by stuffing-boxViéville, Émilie 02 February 2018 (has links)
L'impact des émissions fugitives sur l'environnement est un enjeu capital pour les industries. Ainsi, de nombreuses réglementations et normes sont établies afin de prévenir des risques et limiter leurs impacts. L'une des sources majeures de ces émissions provient de la robinetterie industrielle. Dans ce domaine, l'un des systèmes les plus communs est le presse-garniture. Dans le secteur de l'Energie, l'étanchéité peut être garantie sur les éléments mobiles par un empilement de bagues en Graphite Expansé Matricé (GEM); matériau relativement souple, plébiscité pour ses caractéristiques et ayant une structure macroscopique particulière. Ces travaux de thèse s'intéressent à la compréhension du comportement mécanique complexe des solutions d'étanchéité de type GEM. L'objectif est de déterminer le comportement mécanique de ces garnitures afin de prédire leur étanchéité. Dans le but de caractériser ce comportement, diverses campagnes d'essais sont menées sur des joints en situation. Ainsi, sur la base d'un montage existant et d'un dispositif développé spécifiquement pour cette étude, la caractérisation de ce type de joints est effectuée via des essais de compression charge-décharge et cyclique. La base de données qui en résulte permet le développement d'un modèle numérique apte à décrire le comportement complexe de ces systèmes presse-garnitures. Ce modèle phénoménologique de type Hyperélasto-Hystérésis (HH) correspond à une loi additive en contrainte avec une contribution hyperélastique et une contribution hystérétique. La comparaison des réponses expérimentales et numériques du joint, dans le cadre de l'étude d'un seul joint mais également pour des empilements, est discutée. / The impact of fugitive emissions leakage rate on the environment is an essential issue for industries. Therefore, many regulations and standards are created to prevent risks and to limit their impacts. One of these major sources of fugitive emissions comes from industrial valves. In the Valve Industrie, the tightness of stem are often ensured by stuffing box seal. In the energy sector, the tightness could be ensure with compression packing which is manufactured in exfoliated graphite; which is a relatively flexible material, endorsed for its characteristics and having a particular macroscopic structure. The aim of this study is to improve the knowledge of the complex mechanical behaviour of compression packing in exfoliated graphite. The aim is to determinate the mechanical behaviour of these packings in order to predict their tightness. To characterize this behaviour, various test campaigns are conducted on seals in situation. Thus, based on an existing apparatus and a device developed specifically for this study, the characterization of this kind of packing is performed through loading-unloading and cyclic compression tests. A numerical model which is able to describe a complexe mechanical behaviour of compression packing, is performed thanks to resulting database. This Hyperelasto-Hysteresis phenomenological model corresponds to an additive decomposition in stress with an hyperelastic contribution and an hysteretic contribution. The comparison of the experimental and numerical responses of the seal, as part of the study a single seal but also of a packing, is discussed.
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