The aerospace industry strives to develop new methods of refining gas turbine engines by increasing power and thermal efficiencies while simultaneously reducing cost. Turbine engines operate under high temperatures and therefore thermal barrier coatings (TBCs) composed of yttria-stabilized zirconia (YSZ) play an important role in improving the performance of the components that make up the engine. Failure of the TBC could lead to catastrophic events, thus requiring consistent and accurate characterization for supplier qualification and production quality assurance. However, due to porosity and the anisotropic behavior of the coating and variability in processing of TBCs, consistent characterization has proven to be extremely challenging. One of the reoccurring issues is the inconsistency in measuring percent porosity, which stems from the difficulty in distinguishing filled pores from damaged, unfilled voids. Sample preparation of TBCs involves sectioning, mounting, grinding, polishing, and characterization. Eliminating variability in characterization begins with mounting which is a critical step to protect the surface integrity and edge retention of the coating during grinding and polishing. The curing kinetics of a slow cure two part epoxy was investigated and the TBC samples were mounted and cured at heating rates of 2, 5, and 10°C/min to 55°C and 70°C. Grinding and polishing procedures simulated industry practices followed by characterization with optical microscopy. Results showed that heating rates of 2°C/min to 55°C and 70°C have the best impregnation properties while uncontrolled or high heating rates of 10°C/min had an increase in the amount of pullouts and lack of infiltration from the epoxy. The curing kinetics of the epoxy needs to be controlled to eliminate the ambiguity of filled and unfilled pores. / Master of Science

Research has shown that acreage restrictions in flue-cured tobacco production have resulted in the capitalization of a portion of the future benefits of the price-support program into land values. Higher net income for farmers, the primary objective of the program, is therefore defeated through higher land cost and increased rents. The objective of this study was to derive empirical estimates of the capitalized value of an acre of tobacco during 1958-1961 in Pittsylvania County. The estimates were compared with those obtained in a previous study for the years 1954-1957. In addition, some analysis was made of factors which influence the price of farmland but which were difficult, if not impossible, to quantify as continuous variables for statistical measurement. Data on sale value of farms and factors thought to influence sale value were secured from public records. These data were analyzed by a multiple linear regression statistical technique to measure the value of an acre of tobacco allotment as a right to produce tobacco. Partial regression coefficients indicated that an acre of allotment was worth $833, $1,216, $1,453, and $1,460 for the four years, 1958-1961, respectively and $1,345 for the four years combined. Questionnaire data secured from buyers indicated that there were several distinct types of buyers on the land market and that the type of buyer influenced the type of farm purchased. Further, some differences in type of sale, number of buyers competing for a farm, variation in reason for purchase, and buyers' knowledge of market affected the sale price of tobacco farms. / M.S.

Yes / Considering the continuous development of sustainable development, energy saving, and emission reduction concepts, it is very important to reduce concrete's cement content in order to improve its environmental impact. Using a reactive admixture to replace part of the cement in ultra-high-performance concrete (UHPC) can effectively improve the overall performance of the concrete and reduce carbon dioxide emissions, which is an important aspect of environmental protection. Here, industrial waste residue (fly ash and slag), sea sand (SS), and manufactured sand (MS) were used to produce UHPC under standard curing conditions to reduce the material cost and make it more environmentally friendly and sustainable. The effects of water-binder ratio, contents of cementitious materials, types of sands, and content of steel fibers on the mechanical performance of UHPC under standard curing were investigated experimentally. In addition, evaluations of the impermeability, chloride, and freeze-thaw resistance of various UHPCs produced were conducted by investigating the effects of various factors on the depth under hydraulic pressure and electric flux of UHPC, as well as the mass loss, relative dynamic modulus of elasticity, flexural strength, and compressive strength of UHPC specimens after freeze-thaw cycles. The obtained experimental results show that the SS-UHPC and MS-UHPC prepared by standard curing exhibit high strength, excellent impermeability, and chloride resistance. The frost-resistant grade of all groups of UHPCs prepared by standard curing was greater than F500 and had excellent freeze-thaw resistance, including those produced with local tap water or artificial seawater. The investigation presented in this paper could contribute to the production of new low-cost and environmentally friendly UHPCs and accelerate the application of UHPC in engineering structures.

Yes / This study aims to provide a thorough evaluation for the changes in the microstructure and evolution of strength of highly reactive clays that were treated with 7 % lime over a period of curing time as a function of the mixing moisture content. Three series of testing were carried out on specimens with 100 %, 85 % and 75 % of bentonite content and prepared with different moisture content of 10, 20, 30 and 40 % above the corresponding optimum moisture content. Specimens of 100 % bentonite were treated with 7 % of lime, compacted to achieve a predetermined dry unit weight and cured at temperatures of 20 OC and 40 OC for up to 28 days whereas the specimens with 85 % and 75 % of bentonite content were prepared by the addition of sand and were cured at 20 oC for up to 7 days. Unconfined Compressive Strength tests and Scanning Electron Microscopy were conducted to observe the strength and the microstructural changes resulting from increasing mixing moisture content. California Bearing Ratio and Resilient Modulus were correspondingly determined based on correlations with the Unconfined Compressive Strength. The failure pattern was also studied to better understand the ultimate behaviour of lime stabilised clays. The results revealed that the strength of treated bentonite increased with the increase in the moisture content up to 30 % above the corresponding optimum moisture content and with increasing the curing time and temperature. Nevertheless, substituting bentonite with sand on the specimen resulted in a significant reduction on the attained strength. Furthermore, the results of California Bearing Ratio and Resilient Modulus showed that values for both parameters are significantly enhanced with lime treatment. The microstructural analysis provided visual evidence to the improved strength in which the pozzolanic reaction was found to be significantly affected by the amount of moisture in the mixture. The results suggested that compacting lime treated expansive clays with moisture content moderately higher than the optimum moisture content would result in a significant enhancement to the attained strength over the period of curing.

<p>This thesis describes the synthesis and characterization ofbranched semi-crystalline polymers. Included in this work isthe SEC characterization of a series of dendrimers. Thebranched semi-crystalline polymers were synthesized in order toinvestigate the concept of their use as powder coatings resins.This concept being that the use of branched semi-crystallinepolymers in a UV-cured powder coating system may offer a lowertemperature alternative thus allowing the use of heat sensitivesubstrates and the added benefit of a reduced viscositycompared to linear polymers.</p><p>A series of branched poly(ε-caprolactone)’s (PCL)(degree of polymerization: 5-200) initiated from hydroxylfunctional initiators were synthesized. The final architectureswere controlled by the choice of initiator structure;specifically the dendritic initiators yielded starbranchedPCL’s while the linear initiator yielded comb-branchedPCL’s. The dendritic initiators utilized were: (1) a3rd-generation Boltorn H-30, commercially availablehyperbranched polyester with approximately 32 hydroxyl groups,(2) a 3rd-generation dendrimer with 24 hydroxyl groups, and (3)a 3rd-generation dendron with 8 hydroxyl groups. Linear PCL wassynthesized for comparison. All dendritic initiators are basedon 2,2- bis(methylol) propionic acid. The comb-branchedpolymers were initiated from a modified peroxide functionalpolyacrylate. The resins were end-capped withmethylmethacrylate in order to produce a cross-linkable system.The polymers and films were characterized using 1H NMR, 13CNMR, SEC, DMTA, DSC, FT-IR, FT-Raman, rheometry and a rheometercoupled to a UV-lamp to measure cure behavior.</p><p>The star-branched PCL’s exhibited considerably lowerviscosities than their linear counterparts with the samemolecular weight for the molecular region investigated (2-550kg mol-1). It was also found that the zero shear viscosityincreased roughly exponentially with M.</p><p>The PCL star-branched resins are semi-crystalline and theirmelting points (Tm) range from 34-50°C; films can beformed and cured below 80°C. The viscoelastic behaviourduring the cure showed that the time to reach the gel point, afew seconds, increased linearly with molecular weight. Thecrossover of G’and G’’was used as the gelpoint. Measurement of mechanical properties of films showedthat the low molecular weight polymers were amorphous whilethose with high molecular weight were crystalline after cure.The polymerization of 5,5-dimethyl-1,3-dioxane-2-one (NPC) fromoligo- and multifunctional initiators was evaluated utilizingcoordination and cationic polymerization. Two tin basedcatalysts, stannous(II) 2-ethylhexanoate and stannous(II)trifluoromethane sulfonate, were compared with fumaric acid.Fumaric acid under bulk conditions resulted in lowerpolydispersity and less chance of gelling. The synthesis ofstar-branched polymers was confirmed by SEC data. The starpolymers exhibited a Tg at 20-30°C and a Tm at about100°C.</p><p>All semi-crystalline resins exhibited a fast decrease inviscosity at Tm. Blends of combbranched semi-crystalline resinsand amorphous resins exhibited a transition behavior inbetweenthat of pure semi-crystalline resins and that of amorphousresins.</p><p>The SEC characterization of a series of dendrimers withdifferent cores and terminal groups showed that the core had animpact on the viscosimetric radius of the core while theterminal groups appeared to have no effect.</p><p><b>Keywords:</b>star-branched, semi-crystalline,comb-branched, ring-opening polymerization,poly(ε-caprolactone), dendritic, thermoset, lowtemperature curing, powder coating, UVcuring,poly(5,5-dimethyl-1,3-dioxane-2-one), size exclusionchromatography, rheology, dendritic aliphatic polyester</p>

This thesis describes the synthesis and characterization ofbranched semi-crystalline polymers. Included in this work isthe SEC characterization of a series of dendrimers. Thebranched semi-crystalline polymers were synthesized in order toinvestigate the concept of their use as powder coatings resins.This concept being that the use of branched semi-crystallinepolymers in a UV-cured powder coating system may offer a lowertemperature alternative thus allowing the use of heat sensitivesubstrates and the added benefit of a reduced viscositycompared to linear polymers. A series of branched poly(ε-caprolactone)’s (PCL)(degree of polymerization: 5-200) initiated from hydroxylfunctional initiators were synthesized. The final architectureswere controlled by the choice of initiator structure;specifically the dendritic initiators yielded starbranchedPCL’s while the linear initiator yielded comb-branchedPCL’s. The dendritic initiators utilized were: (1) a3rd-generation Boltorn H-30, commercially availablehyperbranched polyester with approximately 32 hydroxyl groups,(2) a 3rd-generation dendrimer with 24 hydroxyl groups, and (3)a 3rd-generation dendron with 8 hydroxyl groups. Linear PCL wassynthesized for comparison. All dendritic initiators are basedon 2,2- bis(methylol) propionic acid. The comb-branchedpolymers were initiated from a modified peroxide functionalpolyacrylate. The resins were end-capped withmethylmethacrylate in order to produce a cross-linkable system.The polymers and films were characterized using 1H NMR, 13CNMR, SEC, DMTA, DSC, FT-IR, FT-Raman, rheometry and a rheometercoupled to a UV-lamp to measure cure behavior. The star-branched PCL’s exhibited considerably lowerviscosities than their linear counterparts with the samemolecular weight for the molecular region investigated (2-550kg mol-1). It was also found that the zero shear viscosityincreased roughly exponentially with M. The PCL star-branched resins are semi-crystalline and theirmelting points (Tm) range from 34-50°C; films can beformed and cured below 80°C. The viscoelastic behaviourduring the cure showed that the time to reach the gel point, afew seconds, increased linearly with molecular weight. Thecrossover of G’and G’’was used as the gelpoint. Measurement of mechanical properties of films showedthat the low molecular weight polymers were amorphous whilethose with high molecular weight were crystalline after cure.The polymerization of 5,5-dimethyl-1,3-dioxane-2-one (NPC) fromoligo- and multifunctional initiators was evaluated utilizingcoordination and cationic polymerization. Two tin basedcatalysts, stannous(II) 2-ethylhexanoate and stannous(II)trifluoromethane sulfonate, were compared with fumaric acid.Fumaric acid under bulk conditions resulted in lowerpolydispersity and less chance of gelling. The synthesis ofstar-branched polymers was confirmed by SEC data. The starpolymers exhibited a Tg at 20-30°C and a Tm at about100°C. All semi-crystalline resins exhibited a fast decrease inviscosity at Tm. Blends of combbranched semi-crystalline resinsand amorphous resins exhibited a transition behavior inbetweenthat of pure semi-crystalline resins and that of amorphousresins. The SEC characterization of a series of dendrimers withdifferent cores and terminal groups showed that the core had animpact on the viscosimetric radius of the core while theterminal groups appeared to have no effect. Keywords:star-branched, semi-crystalline,comb-branched, ring-opening polymerization,poly(ε-caprolactone), dendritic, thermoset, lowtemperature curing, powder coating, UVcuring,poly(5,5-dimethyl-1,3-dioxane-2-one), size exclusionchromatography, rheology, dendritic aliphatic polyester / <p>NR 20140805</p>

The eco-friendly alternatives use is increasing momentum in a conscious effort towards sustainability. In this regards, the relevance and the economic value of using copper slag as a concrete aggregate are explored in this study in order to contribute towards metallurgical waste recycling. Emphasis is placed on the evaluation of the concretes strengthening prepared with copper slag contents and produced under four curing methods: water immersion, water spraying, plastic sheet covering and air-drying. In each curing case excluding for water immersion, was duplicated in indoors (i.e. in the laboratory) and outdoor exposure (so was prone to varying environmental conditions). This was specifically aimed at capturing the effects of tropical weather conditions typical of the Lualaba province in the Democratic Republic of Congo. The control mix was designed to reach 25 MPa of compressive strength. Copper slag was successively incorporated as sand replacement at the following mass fractions: 20 %, 40 % and 60 %. Freshly mixed concrete samples were evaluated for workability. Cube specimens were cast accordingly, cured for 28 days and then tested for density and compressive strength. Results indicated an increase in strength up to 20 % of replacement rate for all the curing methods. Further additions resulted in reduction in the strength, but the rate of reduction depended on curing conditions. The increase in strength was mainly credited to the physical properties of copper slag that could have contributed to the cohesion of the concrete matrix. It has been found that appropriate ways of curing can still achieve greater results than that of the control mix since 80 % of humidity is ensure. The two-way ANOVA test performed on the 28-days compressive strength values confirmed the significant influence of the curing methods, of copper slag content and the interaction between them. It has been found that considerable influence is attributed to copper slag content and that warm environmental conditions further extend the concrete strengthening. / College of Engineering, Science and Technology / M. Tech. (Chemical Engineering)

The aim of the work reported here was to determine the influence of an amine curing agent, and postcure cycle on the mechanical and thermal properties of diglycidyl ether of bisphenol A (DGEBA) epoxy resin. The results of this initial study were then used as the basis for selecting material to obtain optimum toughness in epoxy/glass fibre systems. These basic materials were further used to make comparisons with the properties of modified resin systems which contained commercial elastomers. Differential Scanning Calorimetry (DSC), Dynamic Mechanical Thermal Analysis (DMTA), Fourier Transform Infrared Spectroscopy (FTIR), flexural and interlaminar shear tests, Instrumented Falling Weight Impact (IFWI), visual observation, Scanning Electron Microscopy (SEM), and Transmission Electron Microscopy (TEM) were all used to investigate various properties and the structures which gave rise to them. The properties of cured products were found to be affected by the amounts of curing agent, curing times and temperatures, and the structure of the elastomers. Not surprisingly the maximum thermal and mechanical properties tended to be found in the stoichiometric (standard) mix systems. However, postcuring at higher than room temperature, which was used as the basic curing temperature, led to more conversion. This effect improved the thermal and mechanical properties of both the unmodified and modified resin systems. The maximum flexural strength of 104 MPa of the unreinforced resins was found in the stoichiometric mix ratio after postcure at 150°C for 4 hr. However, the maximum flexural modulus and glass transition temperature (Tg) were found after postcuring at the same temperature for 48 hr. This was believed to be due to increased crosslinking, but unfortunately the longer curing time led to degradation of the resins. In the systems modified with -20 phr of polyetheramine elastomers, the one modified with the lowest molecular weight (2000) was found to have the highest flexural strength (85.8 MPa) and modulus (2.5 GPa). The impact properties of all the composites with modified resin matrices were found to be higher than the unmodified resin matrix composites. The best impact properties were, however, obtained with the elastomer modifier with a molecular weight of 4000. The impact energy at maximum force increased from 11.9 to 16.4 J, and energy at failure increased from 18.7 to 21.6 J. This increase in impact properties was due to the increase in areas of phase separated elastomer particles over similar systems with lower molecular weight modifier.

O objetivo deste estudo ex vivo foi avaliar, por meio de teste de pull out, a influência de diferentes potências de fotoativação, associadas a diferentes técnicas de inserção, na retenção da restauração de resina composta em raízes fragilizadas. Foram utilizadas quarenta raízes de caninos superiores humanos padronizadas em 15 mm de comprimento, que foram submetidas à fragilização por meio de brocas 718PM; 730PM e 720PM, com auxílio de paralelômetro numa extensão de 8 mm. O tratamento endodôntico foi realizado por meio de instrumentos manuais tipo K, apenas no remanescente radicular não tocado pela fragilização. A obturação foi realizada pela técnica de condensação lateral com cimento AH Plus, seguida de corte dos cones, no comprimento correspondente à área da fragilização, e toalete da cavidade. Os espécimes foram distribuídos em quatro grupos (n= 10) de acordo com a técnica de inserção e a potência de fotoativação: Grupo I, resina composta inserida em incremento único; Grupo II, resina composta inserida em dois incrementos. Estes grupos foram fotoativados em baixa potência (500 mW/cm²); Grupo III, resina composta inserida em incremento único; Grupo IV, resina composta inserida em dois incrementos. Estes grupos foram fotoativados em alta potência (1200 mW/cm²). Em todos os grupos as raízes foram restauradas internamente com resina composta fotopolimerizável Z100, com fotoativação auxiliada por pinos plásticos fototransmissores, no comprimento de 8 mm, removidos após a polimerização, para a cimentação dos pinos metálicos pré-fabricados Reforpost com cimento resinoso Relyx ARC, o que proporcionou a obtenção do reforço radicular (resina composta + pino metálico). As raízes foram submetidas ao teste de pull out numa máquina universal de ensaios (Intron 3345) à velocidade de 1mm/min até deslocamento do reforço radicular. Os valores de resistência à tração foram expressos em MPa e submetidos à Análise de Variância dois fatores (&alpha;=0,05). A resistência à tração foi influenciada pela potência de fotoativação (P<0,05), mas não pela técnica de inserção da resina composta e nem pela interação dos fatores em estudo (P>0,05). A fotoativação em alta potência apresentou altos valores de resistência à tração (4,38±1,57) em comparação com a fotoativação em baixa potência (2,19±0,82), enquanto que a técnica de inserção em incremento único (3,62±1,60) ou dois incrementos (2,95±1,70) apresentou valores estatisticamente semelhantes. Concluiu-se que o aumento da potência de fotoativação influenciou positivamente na retenção da resina composta utilizada na restauração de raízes fragilizadas, independente da quantidade de incrementos utilizados / The aim of this ex vivo study was to evaluate by pull out test the influence of different curing light intensities, associated to different insertion techniques on the composite resin restoration retention of weakened roots. For this purpose forty maxillary human roots were used. The minimum length was standardized at 15 mm. The roots were weakened using 718PM; 730PM e 720PM drills with the aid of a parallelometer up to a depth of 8mm. Endodontic treatment was performed with K-type hand files only in the root section unreached by the weakening. Root canal filling was performed according to the lateral condensation technique using AHPlus sealer. Then cones were cut up to weakening length and cavity was cleaned.. The samples were assigned to four groups (n= 10) according to the insertion technique and curing light intensity: Group I, composite resin placed in bulk placement; Group II, composite resin placed in two increments. These groups were photoactivated with low intensity curing light (500 mW/cm²); Group III, composite resin placed in bulk placement; Group IV, composite resin placed in two increments. These groups were photoactivated with higth intensity curing light (1200 mW/cm²). In all groups the roots were restored internally with Z100 light-cured composite resin and photoactivated using light-transmitting plastic posts up to a depth of 8 mm. After polymerization the light-transmitting posts were removed. Then prefabricated metal posts were cemented with Relyx ARC resin-based cement, which provided the achieviment of root reinforcement (composite resin + metal post). The roots were subjected to pull out test by a universal testing machine (Intron 3345) at a speed of 1 mm/min until the root reinforcement was dislodged. Resistance values were expressed in Mpa and were subjected by 2-way Analysis of Variance (&alpha;=0,05). Curing light intensity influenced the tensile strength (p<0,05), however for composite resin insertion technique and for interaction between factors under study (P>0,05) no influence was found. Higth intensity curing light showed high tensile strength values (4,38±1,57) compared with low intensity curing light (2,19±0,82) whereas composite resin insertion technique using bulk placement (3,62±1,60) or two increments (2,95±1,70) showed similar values. Increasing the curing light intensity had positive influences on composite resin restoration retention in weakened roots, regardless of the amount of increments used.

De modo geral, os ciclos de cura para resina epóxi demandam algumas horas e elevadas temperaturas. Em busca de novas soluções para a otimização de processos sem perda de qualidade, bem como a economia de energia, diversos processos de cura de resina epóxi não convencionais foram desenvolvidos ao longo dos anos. O uso de irradiação de micro-ondas teve início após a Segunda Guerra Mundial, com a invenção do RADAR. A radiação de micro-ondas é uma radiação não-ionizante, com bom poder de penetração e boa transferência de calor em materiais absorvedores, ou materiais com cargas absorvedoras. A frequência usualmente utilizada em trabalhos de pesquisa e desenvolvimento é de 2,45GHz, a mesma disponível nos equipamentos comerciais e industriais existentes. Para a cura de resinas epóxi não são necessárias alterações no sistema reativo, com iniciadores específicos sensíveis a micro-ondas. O \"efeito micro-ondas\" proporciona um aumento da velocidade de colisão entre os reagentes que, associada à energia absorvida pelo sistema reacional, acelera a reação de cura, possibilitando a cura de resinas de tempo de uso longo (superior a 24 horas, em temperatura ambiente) em questão de minutos. Neste estudo foi utilizado inicialmente um sistema epóxi do tipo DGEBA, com endurecedor à base de anidrido e acelerador à base de amina, nas mesmas condições comerciais indicadas pelo fabricante. Testes iniciais com os fornos de micro-ondas selecionados foram realizados previamente a operação com sistemas epóxi. A cura do sistema já catalisado foi realizada em dois diferentes fornos de micro-ondas adaptados para uso em laboratório. A temperatura de degradação, e a temperatura de transição vítrea, foram avaliadas por técnicas de análise térmica. Cargas, pigmentos e aditivos também foram avaliados, no sentido de determinar suas influências em misturas com o sistema epóxi escolhido. Após estudos preliminares com o sistema epóxi puro, foram realizados testes em compósitos reforçados com fibra de vidro. Os resultados indicam que o processo é promissor, correspondendo ao observado em diversos artigos na literatura. / Generally, the cure cycles epoxy resin demand for few hours, and elevated temperatures. In search of new solutions for process optimization without loss of quality as well as energy saving, various processes of curing epoxy resin unconventional were developed over the years. The use of microwave irradiation began after World War II, with the invention of RADAR. The microwave radiation is non-ionizing radiation, with good power of penetration and good heat transfer in absorbing materials, or materials with absorbing fillers. The frequency usually used in research and development is of 2.45 GHz, the same is available in commercial equipment. For curing epoxy resins are not necessary changes in the system reactive with specific initiators sensitive to microwaves. The \"microwave effect\" provides increased on collision velocity between the reactants, which combined with energy absorbed by the reaction system, its accelerates the reaction curing, allowing the resin to cure long pot-life (times greater than 24 hours) in minutes. In this study, a DGEBA epoxy resin with an anhydride based hardener, and an initiator based on amine was used under the same conditions indicated by the manufacturer. Preliminary tests with the microwave ovens selected were executed before the operation with epoxy systems. The curing of the catalyzed system was performed in two different adapted microwave ovens for use in laboratory. The degradation temperature and the glass transition temperature were evaluated by thermal analysis techniques. Fillers, pigments and additives also were evaluated to determinate the influences with and without the epoxy system. After previous tests with the epoxy system alone, it was realized tests in composites form with glass fiber. The initial results indicate that the curing process by microwave irradiation is promising, and corresponding with the literature.