The first paper, “Dye Penetrant Induced Microcracking in High-Performance Thermoplastic Polyimide Composites”, studied the possibility of spurious microcracking in three high-performance thermoplastic polyimide composite materials due to zinc iodine dye penetrant. The material systems were IM7/LaRC™-IAX, IM7/LaRC™-IAX2, and IM7/LaRC™-8515. Specimens from each material system were subjected to one of three immersion tests. The first immersion test involved soaking composite specimens previously prepared with different polishing techniques in dye penetrant. In the second test, specimens were immersed in the individual components of the dye penetrant. The final test involved exposure of specimens to one of six solvents followed by exposure to dye penetrant. Results showed that the composite materials have sufficiently high thermal residual stresses to drive microcracking in the presence of dye penetrant without external mechanical loading. There was no evidence that the different polishing techniques had an effect on dye penetrant-induced stress cracking. The dye penetrant components did not produce microcracks in the composites. Some combination of the components must be present to induce microcracking. Observations also revealed that polishing had an effect on the microcracking process of the composites that were initially exposed to solvents then dye penetrant. The second paper, “The Effect of Environmental Stress Cracking on High-Performance Polymeric Composites”, studied solvent stress cracking and solvent-induced strength degradation on four polyimide matrix materials developed at NASA-Langley Research Center. These materials are LaRC™-IAX, LaRC™-IAX2, LaRC™-8515, and LaRC™-PETI-5. Cross-ply specimens were used to characterize solvent stress cracking in composites. Matrix cracking due to solvent exposure was observed in all of the materials. The solvent exposure time of the materials ranged from 1 minute to 96 hours. The results show that residual thermal stresses due to processing in the cross-ply composite specimens are sufficient to drive solvent stress cracking in the matrix. Solvent application lowers the microcracking toughness, G_mc ,values such that the available strain energy, G_m, within the transverse ply groups is sufficient to initiate microcracking. In the absence of a solvent, the same G_m value would not induce microcracking. Transverse flexure tests were performed on unidirectional specimens to determine the effects of the solvents on the material strengths. The presence of certain solvents severely degraded the materials. The manner in which the solvents were applied to the materials determined the degree of material degradation. The results revealed a synergistic effect between stress and solvent. The tests showed that diglyme, MEK, and acetone produced the most severe damage to the materials. The most solvent resistant material was LaRC™-PETI-5. This is followed by LaRC™-8515, LaRC™-IAX2, and LaRC™-IAX respectively. LaRC™- PETI-5 is a thermoset whereas the remaining materials are thermoplastics. / Master of Science

Road administrators have to make decisions regarding the maintenance and rehabilitation of many existing jointed Portland Cement Concrete (PCC) pavements in the road network. Since these pavements are in general expensive to rehabilitate, agencies often opt for overlaying the deteriorated PCC pavement with Hot Mix Asphalt (HMA), resulting in a composite pavement. Unfortunately, the tensile stresses and strains at the bottom of the overlay developed from the movement of the joints, which are caused by the traffic and the changes in temperature, will create cracks on the surface known as reflective cracking. Reflective cracking can reduce the life of a pavement by allowing water or other particles to get into the underlying layers, which causes the pavement structure to lose strength. To improve the performance of the composite pavement, road agencies have studied mitigations techniques to delay the initiation and propagation of those cracks reflected from the PCC joints and cracks. Traditionally, these studies have relied only on laboratory testing or nondestructive tests. This dissertation expands the traditional approach by adding full-scale Accelerate Pavement Testing (APT) to a laboratory effort to investigate enhanced asphalt overlays that delay the initiation and propagation of cracks reflected from the PCC joints. The study was organized into three complementary experiments. The first experiment included the first reflective cracking study of hot-mix asphalt (HMA) overlays over jointed Portland cement concrete pavements (PCCP) conducted at the Virginia APT facility. A Heavy Vehicle Simulator (HVS) was used to compare the reflective cracking performance of a Stone Matrix Asphalt (SMA) control mix with a modified mix with a synthetic fiber. The discussion includes the characterization of the asphalt mixes, the pavement structure, construction layout, the equipment used, the instrumentation installed, and lessons learned. Results showed that the fiber-modified mix had a higher resistance to fracture, which increases the pavement life by approximately 50%. The second experiment compared the cracking resistance of the same control and modified mixes in the laboratory. Four cracking resistance tests were performed on each mix. These four tests are: (1) Indirect Tensile Asphalt Cracking Test (IDEAL-CT), which measures the Cracking Test index (CTindex); (2) Semicircular Bend Test-Illinois (SCB-IL), which measures the critical strain energy release rate (Jc); (3) Semicircular Bend-Louisiana Transportation Research Center (SCB-LTRC), which measures the Flexibility Index (FI); and (4) Overlay Test (OT), which measures the Cracking Propagation Rate (CPR). The results from the four tests showed that the fiber-modified mix had a better resistance to cracking, confirming the APT test results. The laboratory assessment also suggested that the IDEAL-CT and SCB-IL test appear to be the most practical for implementation. The third phase evaluated the performance of mixes designed with a high content of Reclaimed Asphalt Pavement (RAP) and an enhanced asphalt-rubber extender, which comprises three primary components: plain soft bitumen, fine crumb rubber and an Activated Mineral Binder Stabilizer (AMBS). The experiment evaluated the fracture resistance of nine mixes designed with different rates of recycled asphalt pavement (RAP) and asphalt-rubber, compare them with a traditional mix, and propose an optimized mixture for use in overlays of concrete pavements. The mixes were designed with different rates of RAP (15, 30, 45%) and asphalt-rubber extender (0, 30, and 45%) following generally, the design requirements for an SMA mix in Virginia. The laboratory test recommended in the second experiment, IDEAL-CT and SCB-IL, were used to determine the fracture resistance of the mixes. The results showed that the addition of RAP decreases fracture resistance, but the asphalt-rubber extender improves it. A mix designed that replaced 30% of the binder with asphalt-rubber extender and 15% RAP had the highest resistance to fracture according to both. Also, as expected, all the mixed had a low susceptibility to rutting. / Doctor of Philosophy / Reflective cracking can reduce the life of a pavement by allowing water or other particles to get into the underlying layers, which causes the pavement structure to lose strength. To improve the performance of the composite pavement, road agencies have studied mitigations techniques that will delay the initiation and propagation of those cracks reflected from the PCC joints. Traditionally, these studies rely only on laboratory testing or nondestructive tests that will assist in the decision-making stage in a short time manner. This dissertation focusses on a reflective cracking study conducted through Accelerate Pavement Testing (APT) using a Heavy Vehicle Simulator (HVS) and laboratory testing. The first task used an HVS to evaluate reflective cracking of a Stone Matrix Asphalt (SMA) control mix and a modified mix with synthetic fiber. One lane was constructed with two layers of 1.5-inches of a control Stone Matrix Asphalt (SMA) mix and the second lane with an SMA mix modified with the synthetic fiber. Results from APT demonstrated that the modified SMA has a higher resistance to fracture which increases the pavement life by approximately 50%. The second task estimated the fracture resistance of the mixes studied in task one following the laboratory test: Indirect Tension Asphalt Cracking Test (IDEAL-CT), Texas Overlay Test (OT), Semi-Circular Bend-Louisiana Transportation Research Center (SCB-LTRC) and Semi-Circular Bend-Illinois (SCB-IL) to estimate the Cracking Test Index (CTindex), Cracking Propagation Rate (CPR), critical strain energy release rate (Jc) and Flexibility Index (FI), respectively. Results showed that the modified mix had a better resistance to cracking, confirming the APT test results. Specifically, CTindex results showed that the modified mix is more resistant than the control, with indices of 268.72 and 67.86. The estimated Jc indicated that less energy is required to initiate a crack for the control mix that achieved 0.48 kJ/m2 compared to the modified mix with synthetic fibers 0.54 kJ/m2. FI results for the control and fibers were 2.16 and 10.71, respectively. The calculated CPR showed that the control mix propagates a crack at a higher rate of 0.188 compared to the modified mix with a CPR of 0.152. The third phase evaluated the performance of mixes designed with a high content of Reclaimed Asphalt Pavement (RAP) and an enhanced asphalt-rubber extender, which comprises three primary components: plain soft bitumen, fine crumb rubber and an Activated Mineral Binder Stabilizer (AMBS). The experiment evaluated the fracture resistance of nine mixes designed with different rates of recycled asphalt pavement (RAP) and asphalt-rubber, compare them with a traditional mix, and propose an optimized mixture for use in overlays of concrete pavements. The mixes were designed with different rates of RAP (15, 30, 45%) and asphalt-rubber extender (0, 30, and 45%) following generally, the design requirements for an SMA mix in Virginia. The laboratory test recommended in the second experiment, IDEAL-CT and SCB-IL, were used to determine the fracture resistance of the mixes. The results showed that the addition of RAP decreases fracture resistance, but the asphalt-rubber extender improves it. A mix designed that replaced 30% of the binder with asphalt-rubber extender and 15% RAP had the highest resistance to fracture according to both. Also, as expected, all the mixed had a low susceptibility to rutting.

No description available.

No description available.

No description available.

Thesis (MSc (Chemistry and Polymer Science))--University of Stellenbosch, 2006. / This study concerns the phenomenon of environmental stress cracking resistance (ESCR) in three impact polypropylene copolymers (IPPCs). The main purpose was to correlate the ESCR with their properties such as microstructure, molecular weight (MW), molecular weight distribution (MWD), crystallinity and morphology. Initially the selection of a suitable test method and an active stress cracking agent (SCA) were the preliminary concerns. The Bell telephone test was used to evaluate SCAs, while a published procedure for determining ESCR of ethylene based plastics was adapted for the purpose of this study. Isopropanol was selected as SCA. Polymers were fully characterized by FTIR, 13C NMR, DSC and high temperature GPC. Optical microscopy was used to investigate craze formation and crack growth, and scanning electron microscopy (SEM) was used to study the morphology of the polymers. Since IPPCs are known to have multi-fraction copolymeric structures and each of these fractions has significantly different average properties, fractions were selectively removed from the materials, either by solvent extraction at room temperature, or by TREF fractionation. The effect of removing these fractions on the ESCR was determined. The effect of the molecular composition of the three IPPCs on the ESCR of these materials, as well as the effect of the removal of the selected molecular fractions on the ESCR, morphology and molecular characteristics are discussed and compared. Conclusions are drawn as to the factors controlling ESCR in these materials.

L'EU-1 et la MCM-22 sont deux zéolithes à taille de pores intermédiaire, utilisées respectivement pour l'isomérisation de la coupe C8 aromatique et l'alkylation du benzène par des oléfines légères. Leurs propriétés catalytiques originales sont dues à une contribution très importante des sites acides localisés sur leur surface externe. Au cours de ce travail, différentes approches ont été envisagées pour augmenter la quantité ou la proportion de ces sites aux dépends des sites internes. Tout d'abord, une série de zéolithes H-EU-1 partiellement échangées par du sodium a été préparée et caractérisée par voie physicochimique et par des réactions modèles. Comme attendu, l'échange s'accompagne d'une diminution de la concentration en sites acides de Brönsted. Toutefois, une augmentation importante de la quantité de sites acides très forts a été observée pour des taux d'échange de 26 à 35 % et corrélée à l'augmentation de l'activité en craquage du méthylcyclohexane. Par ailleurs, les conversions du m-xylène et du 1,3,5-triméthylbenzène diminuent rapidement pour de faibles taux d'échange, ce qui pourrait s'expliquer par un échange préférentiel des sites acides externes, également mis en évidence dans le cas de zéolithes MCM-22. Enfin, une nouvelle zéolithe de la famille MWW a été synthétisée et caractérisée. Cette zéolithe possède une acidité totale similaire à celle de la MCM-22, mais une proportion de sites acides externes beaucoup plus importante, conduisant à une activité beaucoup plus grande en transformation du m-xylène et du 1,3,5-triméthylbenzène. Cette nouvelle zéolithe pourrait donc constituer une alternative intéressante à la zéolithe MCM-22 en alkylation du benzène. / EU-1 and MCM-22 are two 10-ring zeolites used in petrochemical applications such as C8-aromatic cut isomerization and benzene alkylation with short olefins. In all these processes, the original catalytic behaviors of both zeolites are characterized by an important contribution of the acid sites located over the external surface of their crystals. In this work, different methods were investigated in order to increase the amount or the proportion of these acid sites at the expense of those located inside the pores. Firstly, a series of partially Na-exchanged H-EU-1 was prepared and fully characterized through physicochemical techniques and model reactions. As expected, the exchange led to a gradual decrease in the total Brönsted site concentration. Nevertheless, an increase of the concentration in very strong acid sites was obtained for exchange ratio between 26 and 35%, leading to a significant increase of the activity in methylcyclohexane transformation. On the other hand, m-xylene and 1,3,5-trimethylbenzene (135-TMB) conversions decreased rapidly at low exchange ratio, which was attributed to a preferential exchange of the external acid sites. This latter phenomenon was also observed over Na-exchanged H-MCM-22 zeolites. Secondly, a new zeolite belonging to the MWW family was synthesized and characterized. This zeolite was shown to possess the same acid site concentration than MCM-22 zeolite but with a much higher proportion of external sites. In consequence, it exhibited a very high catalytic activity in both m-xylene and 135-TMB transformations. This material could therefore be considered as an alternative to MCM-22 in the benzene alkylation process. / EU-1 e MCM-22 são dois zeólitos de poros intermédios utilizados, respetivamente, na isomerização do corte C8 aromático e na alquilação do benzeno com olefinas leves. As suas propriedades catalíticas originais devem-se a uma importante contribuição dos centros ácidos localizados nas superfície externa. Nesta tese, diferentes abordagens foram investigadas com o objetivo de aumentar a quantidade ou a proporção destes centros ácidos em detrimento dos centros internos. Primeiramente, uma série de zeólitos H-EU-1 parcialmente permutados com sódio foi preparada e caracterizada por via físico-química e por reações modelo. Como esperado, a permuta é acompanhada por uma diminuição da concentração em centros ácidos de Brönsted. Contudo, um importante aumento da quantidade de centros ácidos muito fortes foi obtido para taxas de permuta entre 26 e 35% e correlacionado com um aumento da atividade no cracking do metilciclohexano. Por outro lado, as conversões do m-xileno e do 1,3,5-trimetilbenzeno diminuem rapidamente para baixas taxas de permuta, o que pode ser explicado por uma permuta preferencial dos centros ácidos externos. Este último fenómeno foi igualmente observado no caso do zeólito H-MCM-22 permutado com sódio. Por fim, um novo zeólito pertencente à família MWW foi sintetizado e caracterizado. Este zeólito demonstrou possuir uma acidez total semelhante à do zeólito MCM-22, porém com uma muito maior proporção de centros ácidos externos, conduzindo a uma bastante superior atividade nas transformações do m-xileno e do 1,3,5-trimetilbenzeno. Este novozeólito poderá, portanto, representar uma alternativa interessante ao zeólito MCM-22 na alquilação do benzeno.

Made available in DSpace on 2014-12-17T15:42:09Z (GMT). No. of bitstreams: 1 AnaCRM_TESE.pdf: 3734770 bytes, checksum: 59720290841ee6807d60b116e21f2090 (MD5) Previous issue date: 2010-12-06 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior / Microporous materials zeolite type Beta and mesoporous type MCM-41 and AlMCM-41 were synthesized hydrothermally and characterized by methods of X-ray diffraction, Fourier transform infrared, scanning electron microscopy, surface acidity, nitrogen adsorption, thermal analysis TG / DTG. Also we performed a kinetic study of sunflower oil on micro and mesoporous catalysts. The microporous material zeolite beta showed a lower crystallinity due to the existence of smaller crystals and a larger number of structural defects. As for the mesoporous materials MCM-41 and AlMCM-41 samples showed formation of hexagonal one-dimensional structure. The study of kinetic behavior of sunflower oil with zeolite beta catalysts, AlMCM-41 and MCM-41 showed a lower activation energy in front of the energy of pure sunflower oil, mainly zeolite beta. In the thermal cracking and thermocatalytic of sunflower oil were obtained two liquid fractions containing an aqueous phase and another organic - organic liquid fraction (FLO). The FLO first collected in both the thermal cracking as the thermocatalytic, showed very high level of acidity, performed characterizations of physicochemical properties of the second fraction in accordance with the specifications of the ANP. The second FLO thermocatalytic collected in cracking of sunflower oil presented results in the range of diesel oil, introducing himself as a promising alternative for use as biofuel liquid similar to diesel, either instead or mixed with it / Os materiais microporosos tipo ze?lita beta e mesoporosos tipo MCM-41 e AlMCM-41 foram sintetizados hidrotermicamente e caracterizados pelos m?todos de difra??o de raios X, infravermelho por transformada de Fourier, microscopia eletr?nica de varredura, acidez superficial, adsor??o de nitrog?nio, an?lise t?rmica via TG/DTG. Ainda foi realizado um estudo do comportamento cin?tico termogravim?trico do ?leo de girassol sobre os catalisadores micro e mesoporosos citados. Usando curvas integrais da TG e o m?todo cin?tico de Vyazovkin, foram estimados a energia de ativa??o, as taxas de convers?o e o tempo degrada??o do ?leo em fun??o da temperatura. O material microporoso ze?lita beta apresentou menor cristalinidade, devido ? exist?ncia de cristais menores e um maior n?mero de defeitos estruturais. Quanto aos materiais mesoporosos MCM-41 e AlMCM-41 apresentaram amostras com forma??o da estrutura hexagonal unidimensional. O estudo do comportamento cin?tico do ?leo de girassol com os catalisadores ze?lita beta, AlMCM-41 e MCM-41, mostrou uma menor energia de ativa??o frente a energia do ?leo de girassol puro, principalmente a ze?lita beta. No craqueamento t?rmico e termocatal?tico do ?leo de girassol foram obtidas duas fra??es l?quidas contendo uma fase aquosa e outra org?nica fra??o l?quida org?nica (FLO). A primeira FLO coletada, tanto no craqueamento t?rmico quanto no termocatal?tico, apresentou ?ndice de acidez muito elevado, sendo assim foi realizada as caracteriza??es das propriedades f?sico-qu?micas da segunda fra??o de acordo com as especifica??es da ANP. As segundas FLOs coletadas no craqueamento termocatal?tico do ?leo de girassol apresentaram resultados na faixa adequada ao diesel de petr?leo, apresentando-se como uma alternativa promissora para utiliza??o como biocombust?vel l?quido similar ao diesel, seja em substitui??o, ou misturado a este

There has been an increase in the production of bio-fuels. Organosolv delignification, high temperature ethanol/water environments, can be used to separate lignin, cellulose, and hemicelluloses in the bio-mass for bio-fuel production. These environments have been shown to induce stress corrosion cracking (SCC) in 316L stainless steel. Previous research has been done in mixed solvent environments at room temperature to understand SCC for stainless steels, but little is known about the behavior in high temperature environments. Simulated organosolv delignification environments were studied, varying water content, temperature, pHe, and Cl- content to understand how these constituents impact SCC. In order for SCC to occur in 316L, there needs to be between 10 and 90 volume % water and the environment needs to be at a temperature around 200°C. Once these two conditions are met, the environment needs to either have pHe < 4 or have more than 10 ppm Cl-. These threshold conditions are based on the organosolv delignification simulated environments tested. SCC severity was seen to increase as water content, temperature, and Cl- content increased and as pHe decreased. To prevent failure of industrial vessels encountering organosolv delignification environments, care needs to be taken to monitor and adjust the constituents to prevent SCC.

Today, ethanol, as well as other biofuels, has been increasingly gaining popularity as a major alternative liquid fuel to replace conventional gasoline for road transportation. One of the key challenges for the future use of bioethanol is to increase its availability in the market via an efficient and economic way. However, one major concern in using the existing gas-pipelines to transport fuel-grade ethanol or blended fuel is the potential corrosion and stress corrosion cracking (SCC) susceptibility of carbon steel pipelines in these environments. Both phenomenological and mechanistic investigations have been carried out in order to address the possible degradation phenomena of X-65 pipeline carbon steel in simulated fuel-grade ethanol (SFGE). Firstly, the susceptibilities of stress corrosion cracking of this steel in SFGE were studied. Ethanol chemistry of SFGE was shown to have great impact on the stress corrosion crack initiation/propagation and the corrosion mode transition. Inclusions in the steel can increase local plastic strain and act as crack initiation sites. Secondly, the anodic behavior of carbon steel electrode was investigated in detail under different ethanol chemistry conditions. General corrosion and pitting susceptibility under unstressed condition were found to be sensitive to the ethanol chemistry. Low tendency to passivate and the sensitivity to ethanol chemistry are the major reasons which drive corrosion process in this system. Oxygen plays a critical role in controlling the passivity of carbon steel in ethanol. Thirdly, the detailed study was carried out to understand the SCC mechanism of carbon steel in SFGE. A film related anodic dissolution process was identified to be a major driving force during the crack propagation. Fourthly, more detailed electrochemical impedance spectroscopy (EIS) studies using phase angle analysis and transmission line simulation reveal a clearer physical picture of the stress corrosion cracking process in this environment. Fifthly, the cathodic reactions of carbon steel in SFGE were also investigated to understand the oxygen and hydrogen reactions. Hydrogen uptake into the pipeline steel and the conditions of the fractures related to hydrogen embrittlement were identified and studied.