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Dimethacrylate oligomers diluted with styrene reactive diluents (so-called vinyl ester resins) are becoming increasingly important for composites in applications such as transportation vehicles, printed wiring boards and civil infrastructure. This research has focused on the generation and comparative analysis of glassy dimethacrylate networks as a function of oligomer structure, the type of reactive diluent, composition and curing conditions. A novel cycloaliphatic dimethacrylate was synthesized and its networks were compared to oligomeric structures containing dimethacrylates derived from epoxy terminated oligomers (from bisphenol-A and epichlorohydrin). Both types of dimethacrylates co-cured with methyl methacrylate exhibited increases in Mc and fracture toughness as the concentration of methyl methacrylate was increased. By contrast, networks prepared with a styrene diluent displayed reduced toughness with increasing styrene and Mc. Due to the need for long-term composite environmental durability, the effects of moisture and exposure to sunlight are important. Thus, these materials were exposed to ultraviolet light on a rotating drum for 225 days and the exposure was carefully monitored. Initial results from this study suggest that both the networks comprising the aromatic dimethacrylate/styrene structures as well as the cycloaliphatic analogues cured with methyl methacrylate undergo reductions in rubbery moduli upon aging under these conditions. X-Ray photoelectron spectroscopy shows higher levels of oxidation on the bisphenol-A vinyl ester networks cured with styrene, especially those containing dimethylaniline and cobalt naphthenate as accelerators. Scanning electron microscopy indicates a smooth surface for the cycloaliphatic networks cured with methyl methacrylate and a pitted surface for the aromatic networks cured with styrene. Water absorption is also higher for the cycloaliphatic vinyl ester; however, curing with a longer alkyl chain methacrylate (butyl methacrylate) decreases the water absorption to levels comparable to those cured with styrene. / Ph. D.

High pre-harvest rainfall in 2006 caused significant pre-harvest sprouting (PHS) and weathering throughout the mid-Atlantic soft red winter wheat (SRWW) (Triticum aestivum L.) growing region. Sprouting and weathering caused decreased flour quality due to lowered dough viscosity and decreased ability to withstand mixing and processing for baked goods. Due to its decreased quality, severely sprouted grain is sold for feed, at a lower price per bushel. Pre-harvest sprouting negatively affects the chain of production from the field to baking operations. The purpose of this research was to evaluate the inherent dormancy and PHS resistance, of current SRWW cultivars and to assess the relationship between falling number and flour quality after grain weathering. Employing a weighted germination index (WGI), a large range in dormancy was observed across SRWW cultivars and seed production. Artificial weathering tests confirmed the use of WGI as a tool for screening for dormancy of SRWW cultivars. The WGI consistently identified cultivars with significantly higher or lower inherent dormancy. "Coker 9553" was highly dormant and resistant to PHS. This cultivar maintained an average falling number of 300 seconds even after receiving an average of 215 mm of rainfall, while the mean falling number for all SRWW cultivars after this amount of weathering was 131 seconds. After only moderate weathering, nine of 15 SRWW cultivars in the study exhibited severe sprouting, demonstrating the need for increased PHS resistance in SRWW wheat. Pre-harvest sprouting resistance groupings, based on average 2008 cultivar falling number were accurately predicted by WGI at both 10 (R2=0.79) and 30°C (R2=0.72) No consistent relationship was observed between head angle, glume tenacity or awn length and PHS resistance. Water absorption, dough stability, farinograph arrival and departure times, peak, and 20-minute drop were measured from grain samples with varying degrees of weathering. All parameters were negatively affected by weathering in 2008. Flour quality parameters were more affected by genotype than falling number suggesting that falling number should not be used as the sole indicator of flour quality after grain weathering. It is clear that there are vast differences in dormancy levels and PHS resistance among SRWW cultivars and stronger dormancy and higher resistance to PHS does not automatically ensure higher quality flour. / Master of Science

Applying sizing material (poly n-vinylpyrrolidone or PVP) around graphite fibers enhances the mechanical properties of carbon fiber reinforced epoxy composites. Understanding the influence of the interphase region between the carbon fiber and epoxy matrix is crucial in enhancing the performance of carbon fiber reinforced epoxy composite materials. In this work, simulated interphase regions, in the form of pure and modified epoxies were synthesized in the laboratory. Several characterization techniques were used to identify the properties of these modified epoxies. They were: 1) Tensile Tests: 2) Fracture Toughness Tests; 3) Thermogravimetric Analysis (TGA): 4) Differential Scanning Calorimetry (nSC); 5) Fourier Transform Infrared (FTIR) Spectrometry: and ()) Water Absorption. Young's modulus, yield stress, yield strain. ultimate tensile stress. ultimate tensile strain, tensile toughness, fracture toughness, and strain energy release rate were obtained from tensile and fracture tests. DSC and FTIR experiments were employed in this study to show the miscibility of PVP and epoxy resin. The pure and modified epoxy samples were immersed in water for about a month to determine their water absorptivity. Almost all epoxies remained unchanged in stiffness, with the exception of the sample 40 wt. % PVP. Only the pure epoxy and light PVP loading epoxies exhibited yield points. The ultimate properties worsened significantly with the increase of PVP loading. A decreasing trend was found in fracture toughness as PVP loading increased. All pure and modified epoxies exhibited sharp glass transition temperatures and the T_g's followed the Fox prediction. Downward frequencies shifting of carhonyl and hydroxyl groups were obtained from the PVP/epoxy blends by infrared study. This was believed to show evidence of hydrogen bond formation. All epoxy and modified epoxies were swollen in water absorption experiments. The samples reached equilibrium after about one month and water absorptivity was found to be a function of PVP content. These experiments sought to demonstrate the characteristics of the interphase region of the composites. / Master of Science

Water and CO adsorptions were studied over the stoichiometric and the oxygen-deficient Cu₂O(111) surfaces, using thermal desorption spectroscopy (TDS), ultraviolet photoelectron spectroscopy (UPS), and X-ray photoelectron spectroscopy (XPS). Water is the only desorbing species detected in TDS and the extent of dissociation is unaffected by the surface condition: ≃ 0.25 monolayers of water dissociate on Cu₂O(111) regardless of surface condition. The local defect environment around oxygen vacancies does not play a significant role in the activity of the Cu₂O(111) surface for the dissociation of water. CO is found to bind molecularly to the surface through the carbon atom and with a heat of adsorption of 22 kcal/mol, higher value than that of CO on Cu₂O(100) (16.7 kcal/mol). This suggests that the local geometry of adsorption sites may play an important role in the way CO binds to Cu₂O surfaces. Electronic changes upon CO adsorption and the higher heat of adsorption indicate an increased σ-donor character for CO, with some π-backbonding interactions. The local defect environment around oxygen vacancies does not appear to affect CO adsorption on Cu₂O(111) surfaces. / Master of Science

Thesis (PhD)--Stellenbosch University, 2011. / ENGLISH ABSTRACT: In this study, the use of surfactants, plate-like clays, organophilic molecules and side-chain crystallinity was investigated for their impact on the transport mechanisms of water vapour through polymer films. A model polymer latex, poly(styrene-co-butyl acrylate), was prepared using miniemulsion polymerization. Three different types of surfactants, sodium dodecyl benzene sulfonate (SDBS, an anionic surfactant), octyl phenol ethoxylate (OPE, a nonionic surfactant) and dodecyl ammonium- 3-butenoate (DA3B, a reactive surfactant) were used to stabilize the latex. Films were prepared from the resultant latices and their water vapour sorption behaviour determined across a water vapour partial pressure range of 0.1 to 0.9. Sigmoidal kinetic behaviour was seen for all three films, with the DA3B stabilized film exhibiting high diffusion coefficients compared to films stabilized with SDBS and OPE. The thermodynamic behaviour of the films differed and was dependent on the reactivity of the surfactant. SDBS and OPE stabilized films exhibited Flory- Huggins behaviour, while the DA3B stabilized film followed Henry’s Law. Despite significant differences in terms of these properties, the permeability coefficients were similar for the three films across the water vapour partial pressure range evaluated. The impact of sodium montmorillonite (Na-MMT) clay and an organophilic modifier, 2- acrylamido-2-methylpropanesulfonic acid (AMPS), on the water vapour sorption properties of poly(styrene-co-butyl acrylate) was evaluated. These polymer clay nanocomposites (PCNs) were synthesized using miniemulsion polymerization. The resultant latex films were characterized and used for water vapour sorption analyses. It was shown that complete exfoliation of the Na-MMT was necessary to minimize the equilibrium water vapour uptake. Even when Na-MMT was completely exfoliated, the amount of water vapour sorbed by the PCN was high and this was attributed to the hydrophilic nature of the clay. Using a least squares regression fit, good correlation was obtained between the experimental isotherms and the sorption behaviour predicted by the Dual Mode Sorption model which was originally developed for polymers in their glassy state. The impact of side chain crystallinity on the water vapour sorption properties of poly(methyl methacrylate-co-octadecyl acrylate) was evaluated. These random copolymers containing increasing amounts of octadecyl acrylate, and therefore increasing degrees of crystallinity, were synthesized using solvent polymerization. Although it could be expected that side chain crystallinity would be the main contributing factor resulting in a reduction in the diffusion coefficient, it was shown that the methyl group on the á- carbon of the vinyl group in the methacrylate reduced the diffusion to a greater extent through the increased stiffness of the polymer backbone. This was also reflected in poly(methyl methacrylate-co-octadecyl acrylate) having a greater activation energy for diffusion compared to polyoctadecyl acrylate. / AFRIKAANSE OPSOMMING: In hierdie studie is die gebruik van sepe, plaatagtige kleie, organofiliese molekules en sykettingkristalliniteit ondersoek ten opsigte van die impak op transportmeganismes van waterdamp deur polimeerfilms. ‘n Model polimeerlateks, polistireen-ko-butielakrilaat, is voorberei deur miniemulsiepolimerisasie. Drie verskillende tipes sepe, natriumdodekielbenseensulfonaat (NDBS, ‘n anioniese seep), oktielfenoletoksilaat (OFE, ‘n nie-ioniese seep) en dodekielammonium-3-butenoaat (DA3B, ‘n reaktiewe seep) is gebruik om die lateks te stabiliseer. Films is van die resultante lateks voorberei en hul waterdampsorpsie –eienskappe oor die parsiële waterdampdrukreeks van 0.1 tot 0.9 bepaal. Sigmodale kinetiese gedrag is vir al drie films waargeneem, met die DA3B gestabiliseerde film wat hoër diffusiekoëffisiënte toon in vergelyking met die films wat met NDBS en OFE gestabiliseer is. Die termodinamiese gedrag van die films het verskil en was afhanklik van die reaktiwiteit van die seep. NDBS en OFE gestabiliseerde films het Flory-Huggins gedrag getoon, terwyl die DA3B gestabiliseerde film Henry se Wet gevolg het. Ten spyte van die beduidende verskille ten opsigte van hierdie eienskappe was die permitiewe koëffisiënte soortgelyk vir die drie films regoor die parsiële waterdampdrukreeks wat vir die evaluasie gebruik is. Die impak van natriummontmorilloniet (Na-MMT) klei en ‘n organofiliese modifiseerder, 2- akrielamido-2-metielpropaansulfoonsuur (AMPS), op die waterdampsorpsie-eienskappe van polistireen-ko-butielakrilaat is geevalueer. Hierdie polimeer-klei-nanosaamgesteldemateriale (PKNe) is gesintetiseer deur van miniemulsiepolimerisasie gebruik te maak. Die resultante lateksfilms is gekarakteriseer en gebruik vir waterdampsorpsie analises. Daar is getoon dat algehele afskilfering van die Na-MMT nodig was om die ewewigswaterdampopname te minimaliseer. Selfs wanneer Na-MMT algeheel afgeskilfer was, was die hoeveelheid waterdamp gesorbeer deur die PKN hoog en kan dit toegeskryf word aan die hidrofiliese karakter van die klei. Deur ‘n kleinste-kwadrate-regressie passing te doen, is ‘n goeie korrelasie verkry tussen die eksperimentele isoterme en die sorpsie gedrag voorspel deur die Dubbelmodussorpsiemodel wat oorspronklik ontwikkel is vir polimere in hul glasagtige toestand. Die impak van sykettingkristalliniteit op die waterdampsorpsie-eienskappe van poli(metielmetakrilaat-ko-oktadekielakrilaat) is ondersoek. Hierdie ewekansige kopolimere wat toenemende hoeveelhede oktadekielakrilaat, en dus toenemende grade van kristalliniteit bevat, is gesintetiseer deur van oplossingspolimerisasie gebruik te maak. Alhoewel dit te wagte was dat sykettingkristalliniteit die hoofbydraende faktor is in die redusering van die diffusiekoeffisiente, is daar getoon dat die metielgroep aan die α-koolstof van die vinielgroep in die metakrilaat die diffusie tot 'n groter mate gereduseer het deur toenemende styfheid van die polimeerrugraat. Dit is ook gereflekteer deur poli(metielmetakrilaat-ko-oktadekielakrilaat) wat 'n groter aktiveringsenergie vir diffusie het in vergelyking met polioktadekielakrilaat.

No presente trabalho é proposto um método para estabelecer um critério de falha da camada polimérica externa dos cabos umbilicais usados em operações offshore. O método proposta baseia-se na determinação do incremento da quantidade de água absorvida pela camada polimérica externa do cabo devido à deterioração provocada pelos carregamentos cíclicos e o envelhecimento originados pelo meio marinho. Este método propõe a realização de um ensaio de fadiga à tração uniaxial no polímero que compõe a camada externa do cabo. O teste é feito simulando as solicitações a que é submetida a camada externa do umbilical durante os ensaios de fadiga feitos, segundo a norma API 17E, durante o processo de homologação do cabo. Além disso, se propõe fazer um ensaio de envelhecimento artificial no polímero da camada externa simulando as condições de serviço do cabo no meio marinho. Com o fim de avaliar a influência dos carregamentos cíclicos e o os agentes do meio marinho nas propriedades do polímero, são feitos ensaios de absorção de água segundo a norma ASTM D 570, ensaios de tração segundo a norma ASTM D 638, ensaios de dureza segundo a norma ASTM D 2240 e observações num microscópio eletrônico de varredura. Finalmente a partir do incremento de massa sofrido pelo polímero no ensaio de absorção de água foi estimado o dano no material da camada externa do cabo. Os resultados obtidos no trabalho mostraram que os carregamentos cíclicos e o meio marinho aceleraram o processo de degradação da camada polimérica externa do umbilical demonstrando assim a eficiência do método proposto. / In the present work is proposed a method to establish a failure criterion of the polymeric external layer of umbilical cables used in offshore operations. The proposed method is based on the determination of the increment of the quantity of absorbed water by the polymeric external layer of the cable due to deterioration caused by cyclic loads and the aging process originated by the marine environment. The method proposes to carry out a uniaxial fatigue test on the polymer that composes the external layer of the cable. This test is made simulating the cyclical deformation that the external layer is submitted in the umbilical during the fatigue test done, according to the API 17E standard, during the process of cable homologation. It is also intended to make an artificial aging test in the polymeric external layer simulating the service conditions of the cable in the marine environment. In order to evaluate of the cyclical loads and the sea set aging influence on the properties of the polymer, carry out water absorption test according to the ASTM D 570 standard, traction test according to the ASTM D 638 standard, hardness test according to the ASTM D 2240 standard and observations in an scanning electron microscopy. Finally starting from the mass increment suffered by the polymer in the water absorption test it was estimated the damage in the external layer material of the cable. The results obtained in this work showed that the cyclical loads and marine environment accelerated the degradation process of polymeric external layer of umbilical cable demonstrating the efficiency of the proposed method.

No presente trabalho é proposto um método para estabelecer um critério de falha da camada polimérica externa dos cabos umbilicais usados em operações offshore. O método proposta baseia-se na determinação do incremento da quantidade de água absorvida pela camada polimérica externa do cabo devido à deterioração provocada pelos carregamentos cíclicos e o envelhecimento originados pelo meio marinho. Este método propõe a realização de um ensaio de fadiga à tração uniaxial no polímero que compõe a camada externa do cabo. O teste é feito simulando as solicitações a que é submetida a camada externa do umbilical durante os ensaios de fadiga feitos, segundo a norma API 17E, durante o processo de homologação do cabo. Além disso, se propõe fazer um ensaio de envelhecimento artificial no polímero da camada externa simulando as condições de serviço do cabo no meio marinho. Com o fim de avaliar a influência dos carregamentos cíclicos e o os agentes do meio marinho nas propriedades do polímero, são feitos ensaios de absorção de água segundo a norma ASTM D 570, ensaios de tração segundo a norma ASTM D 638, ensaios de dureza segundo a norma ASTM D 2240 e observações num microscópio eletrônico de varredura. Finalmente a partir do incremento de massa sofrido pelo polímero no ensaio de absorção de água foi estimado o dano no material da camada externa do cabo. Os resultados obtidos no trabalho mostraram que os carregamentos cíclicos e o meio marinho aceleraram o processo de degradação da camada polimérica externa do umbilical demonstrando assim a eficiência do método proposto. / In the present work is proposed a method to establish a failure criterion of the polymeric external layer of umbilical cables used in offshore operations. The proposed method is based on the determination of the increment of the quantity of absorbed water by the polymeric external layer of the cable due to deterioration caused by cyclic loads and the aging process originated by the marine environment. The method proposes to carry out a uniaxial fatigue test on the polymer that composes the external layer of the cable. This test is made simulating the cyclical deformation that the external layer is submitted in the umbilical during the fatigue test done, according to the API 17E standard, during the process of cable homologation. It is also intended to make an artificial aging test in the polymeric external layer simulating the service conditions of the cable in the marine environment. In order to evaluate of the cyclical loads and the sea set aging influence on the properties of the polymer, carry out water absorption test according to the ASTM D 570 standard, traction test according to the ASTM D 638 standard, hardness test according to the ASTM D 2240 standard and observations in an scanning electron microscopy. Finally starting from the mass increment suffered by the polymer in the water absorption test it was estimated the damage in the external layer material of the cable. The results obtained in this work showed that the cyclical loads and marine environment accelerated the degradation process of polymeric external layer of umbilical cable demonstrating the efficiency of the proposed method.

<p>Coatings for exterior wood have two basic functions. One isto give an aesthetically acceptable surface appearance andcolour. The other is to provide protection against wooddegradation by microbiological or physical attack. Theseprotective properties, often called the barrier properties,play an important role in the selection of proper material forsupreme durability. The assessment of these barrier propertiesis of great importance. Within the CEN Technical Committee 139,Working Group 2, Coatings for exterior wood test methods andperformance specifications have been established. Forassessment of water protection efficiency a standard testprocedure, EN 927-5, has been launched. The present work hasfocused on its applicability in assessing water protectionefficiency in relation to the degradation of coatings duringexposure.</p><p>Assessments according to EN 927-5 is shown to givesignificant differences in water absorption values fordifferent types of coatings on wood. The proposed performancespecifications in ENV 927 - 2 for the water absorption valuesfor coatings to be used in different constructions seem to beset at acceptable levels. It has been shown that there is agood correlation between the level of water absorption andpractical experience of the performance of paints inScandinavia. However, it has also been shown that thecombination of a standard procedure for water absorptionmeasurement and an artificial weathering procedure gives moreinformation regarding expected durability and longtermperformance than a single measurement of water absorption onfresh, unweathered coated wood. A combination of waterabsorption measurement and artificial weathering could become auseful tool in product development as well as in benchmarking.Together with statistical tools, such as reliability-basedservice life prediction methodologies for predicting theservice life of coating systems a reduction in testing timesmay be achieved.</p><p>Surface-active substances in coatings have a negative effecton the coatings ability to prevent water ingress, which mostprobably is due to the hydrophilic character of thesesubstances. The presence of these substances, which are commonin waterborne coatings, alters the moisture sorptioncharacteristics of wood. Considering that these substancesoccur in waterborne coatings, may be mobilised during and afterfilm formation and accumulate at the coating/substrateinterface, there is a great probability that these substanceschange the moisture sorption characteristics of the woodsubstrate in an unfavourable way and create unexpected dynamicmoisture conditions at the coating/wood interface.</p><p>Computerized tomography has been found to be a valuable,non-destructive tool for visualising the spatial moisturedistribution of water and moisture in coated wood panels. Themethod is suitable for recurrent testing of a specimen exposedto a series of processes of wetting, drying. This thesis showsthat high moisture contents occur locally at and around cracks.In these areas there is an increased risk of internal tensionand stress resulting in crack initiation and propagation andthat high moisture contents may occur in the first fewmillimetres under waterborne coatings despite intact coatingfilms. Even with good barrier properties of the coating,moisture may accumulate by water-vapour absorption in air gapsbehind the cladding thus causing favourable conditions formicrobiological colonization.</p><p>The work that has been carried out regarding assessment ofthe water protection efficiency shows promising resultsregarding the possibility to use reliability-based service lifeprediction methodology for the assessment. The aim of futurework will be to establish more reliable techniques andprotocols for assessing service life expectancy and durability,especially for waterborne coatings with special focus ontendencies to early failure and robustness of the coatingsystems.</p><p><b>Keywords:</b>Coatings, surfactants, water absorption value,EN 927, paint, additives, moisture dynamics, absorption,desorption, artificial weathering, artificial exposure,computerized tomography, MRI.</p>

A norma brasileira NBR 7212 (ABNT, 1984), para execução de concreto dosado em central, estipula o tempo máximo para que o concreto seja descarregado (aplicado) completamente em 150 minutos. O tempo para utilização do concreto está vinculado às reações de hidratação do cimento e à perda de abatimento que ocorre com o concreto fresco, um fenômeno normal definido como sendo a perda de fluidez com o passar do tempo. Essa propriedade do concreto é particularmente importante no caso de concreto dosado em centrais, pelo fato do primeiro contato da água com o cimento ser na central enquanto que o lançamento/adensamento ocorrerá alguns minutos ou horas depois, quando o caminhão betoneira chegar ao canteiro de obras. Na prática, muitas vezes, ocorrem situações onde caminhões ficam carregados com concreto por 4 ou 5 horas, em função de atrasos no transporte ou na descarga, caracterizando um tempo bem acima do limite especificado pela norma. A dúvida de utilizar ou não o concreto nessas condições existe, pois não há conhecimento consolidado quanto às suas propriedades finais quando empregado com tempo de mistura que já tenham excedido o limite máximo especificado por norma. O objetivo desta pesquisa é investigar o comportamento de concretos do ponto de vista da resistência à compressão e absorção de água, quando utilizados com tempo de mistura de até 6 horas. Os concretos foram produzidos com dois tipos de cimento, CPIV e CPII, e o abatimento foi mantido ao longo das 6 horas em mistura com a incorporação de aditivo superplastificante à base policarboxilato. Nesse estudo adotaram-se três relações a/c e a produção dos concretos foi realizada em laboratório e em condição real numa central dosadora de concreto. As propriedades estudadas, resistência à compressão e absorção de água, foram analisadas aos 28 dias para vários tempos de mistura. O estudo mostrou que o tempo para utilização do concreto pode ser estendido acima do tempo especificado pela norma, sem que haja perda de sua resistência à compressão e alterações na absorção de água ao longo do tempo. / The Brazilian standard NBR 7212 (ABNT, 1984), for execution of ready-mixed concrete, specifies the maximum time for concrete to be discharged (used) completely in 150 minutes. The usage time of the concrete is due to reactions of the cement hydration and slump loss that occurs with fresh concrete, a normal phenomenon defined as the loss of fluidity along the time. This property of concrete is particularly important in the case of ready-mixed concrete plants, because the first contact of water with the cement is in the ready-mixed concrete plants while launching / densification occurs minutes or hours later, when the mixer truck arrives at the construction site. In fact, often, there are situations where trucks are loaded with concrete by 4 or 5 hours, due to delays in transportation or unloading, characterizing some time well above the limit specified by the standard. The question is to use or not use the concrete on these conditions, because there are no studies that confirm the final properties of the concrete when used with mixing time that have already exceeded the maximum limit specified by the standard. The aim of this study is to investigate the behavior of concrete from viewpoint of compressive strength and water absorption when used with mixing time up to 6 hours. The concretes were produced with two types of cement, CPIV and CPII, and slump was kept up to the six hours in a mixture with the incorporation of superplasticizer based polycarboxylate. In this study were adopted three relations w/c and the production of concrete was done in laboratory and real conditions in a ready-mixed concrete plants. The studied properties, compressive strength and water absorption were analyzed in 28 days for several mixing times. The study showed that the time of use from the concrete can be extended over the time specified by the standard, without loss of compressive strength and changes in the water absorption over time.