Two different research projects were investigated for this thesis, which has consequently been presented in two parts. PART 1 An attempt has been made to improve the high temperature performance of phenol-formaldehyde thermosets by modification of their structure with inorganic phosphate groups. Transesterification of tri-phenyl phosphate with resorcinol has given a resorcinol phosphate resin, which cured with hexamethylenetetramine. A pilot scale batch of this resin has been made and used in high temperature stability studies. Post-cured resorcinol phosphate resin-chrysotile asbestos (30: 70) moulded bars retained 59.5% of their flexural strength after ageing at 523K for 1000 hr in air. Similar phenol-formaldehyde composite bars aged under identical conditions retained only 5.3% of their initial flexural strength. The utility of the resorcinol phosphate resin composite as a commercial product is limited, since the bars had a much lower initial flexural strength (30.85 MNm-2) than the phenol-formaldehyde resin composite bars (108.5 MNm-2). Thermogravimetry and isothermal heating studies have indicated that the degradation of resorcinol phosphate resin was greatly accelerated by chrysotile asbestos, which may catalyse a bond re-organisation process that has been tentatively proposed as a mechanism for the fragmentation of the resin. PART 2 Recently an ionomer dental cement (ASPA), prepared from aqueous poly(acrylic acid) and an ion-leachable aluminosilicate glass, has been developed. The system has been extended by studying other aqueous polymers. The factors influencing the gelation and the properties of the set cements have been examined. Poly(carboxylic acids) with hydrophobic, or no pendant substituents were found to be the most satisfactory polymers for preparing water stable cements. To study the influence of the nature of the cation and polymer structure on the gelation and water stability of ionomer cements, a wide range of metal oxide-polyacid products have been studied. The formation of water stable cements depended markedly on the type of oxide and polyacid employed and appeared to involve factors such as the co-ordination geometry and radius of the cation and the nature of the cation-polyanion bonding in the matrix. A comparison between the water stabilities of ASPA cement and poly(acrylic acid)-CaO, Al2O3, or Al(OH)3 cements has shown that the chemistry of ASPA cement is more complex than has been hitherto reported. Stability constants have been determined for Ca 2+ and Cd 2+ with poly(acrylic acid) and ethyl ethylene-maleic acid copolymer by a potentiometric titration method developed by Gregor and modified by Mandel and Leyte. The stability constants obtained in 1.0M NaNO3 at 298.2 ± 0.2K were: for poly(acrylic acid), with Cat2+, log b1 Ca2+ PAA ~ -3.35 with Cd2+, log Bav Cd2+ PAA = -2.30 for ethylene-maleic acid copolymer, with Cat2+, log b1 CA2+ EMA ~ -4.05 with Cd2+, log Bav Cd2+ EMA = -1.95 The log b1 values probably had little precise meaning, although to a first approximation, log b1 Ca2+ PAA > log b1 Ca2+ EMA The determined stability constants have been used with limited success in predicting the water stabilities of the corresponding metal oxide-polyacid cements.

With the rapid development in electronic packaging due to product miniaturisation, the size of solder joints is decreasing considerably, thus the failure of solder interconnects induced by electro-migration (EM) and thermo-migration (TM) became a reliability concern. The incorporation of foreign reinforcement can effectively improve properties of the solder alloys. However, this presents an imperative need for a further investigation to elaborate the underlying fundamentals associated with the reliability of reinforced solders. In this study, the Sn-Ag-Cu (SAC) based solder alloy powders as matrix were incorporated with Fullerene (FNS), TiC and Ni-coated graphene (NG) reinforcements to form composite solders through powder metallurgical method. These composite solders were then characterised in terms of their microstructure, physical property, solderability, followed by a systematic investigation of their performance under isothermal ageing, current stressing and large thermal gradient, respectively. The results showed that three types of reinforcements were successfully incorporated into the solder matrix; with all reinforcements added being embedded in the solder matrix or around the intermetallic compounds (IMC). The average loss of FNS and TiC particles in the solders was approximately 80% after the initial reflow, while this was only 40% for NG particles. It has been observed that β-Sn and Ag3Sn in the SAC solder alloys can be refined by adding appropriate amount of FNS and TiC, which is beneficial to the wettability with a reduced coefficient of thermal expansion (CTE) with the minimal influence on the melting point and electrical resistivity of solder alloys. For the SAC alloys without reinforcements, obvious extrusion of interfacial IMC at the anode was present after 360 hours of current (1.5×104 A/cm2) stressing, while the changes of surface profiles of all reinforced solders were unnoticeable. Under the current stressing regimes, a continuous increase of interfacial IMCs at the anode of the original SAC alloys was observed, but decreased at the cathode with stressing time. For the composite solders, both anode and cathode showed a continuous growth of interfacial IMCs; the growth rates of IMCs at the anode were greater than that at cathode. In addition, NG and TiC were found to be most effective to retard the growth of Cu3Sn IMC under current stressing. A gradient in hardness across the stressed SAC joints was present, where it was harder at anode. However, no such obvious gradient was found in SAC/FNS and SAC/NG solder joints. FNS and NG were proven to be beneficial to prolong the service life of solder joints up to approximately 7.6% and 10.4% improvements, respectively. Thermal stressing made the interfacial IMC in the original SAC joints to grow at the cold end considerably; causing serious damage at the hot end after 600 hours under temperature gradient of 1240K/cm stressing; a large number of IMCs, cracks and voids appeared in the SAC solder joints. However, a uniform increase of IMCs at both sides in the composite solders was observed without apparent damages at the interfaces under the same thermal stressing conditions, indicating an effective reduction of the elemental migration in the reinforced solders. Although there were also some voids and IMCs formed in the composite solder joints after a long-term thermal stressing, the integrity of the composite solder joints was enhanced compared with the SAC alloys. During thermal stressing, the dissolution rate of Cu atom into the SAC solder joints was estimated to be 3.1×10-6 g/h, while the values for SAC/FNS, SAC/NG and SAC/TiC were only 1.22×10-6 g/h, 1.09×10-6 g/h and 1.67×10-6 g/h, respectively.

Orientador: José de Alencar Simoni / Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Química / Made available in DSpace on 2018-08-26T20:46:57Z (GMT). No. of bitstreams: 1 Curti_GabrielJeronymo_D.pdf: 2740453 bytes, checksum: e587cb4af6da5b69a349e04e62b2a63c (MD5) Previous issue date: 2014 / Resumo: Sabe-se que na agricultura a qualidade de um solo é dependente do tipo de manejo. No presente trabalho foi aplicada a microcalorimetria isotérmica para se investigar a influência do herbicida atrazina na atividade microbiana de um solo envelhecido de mata nativa, mantido a aproximadamente 4 °C, durante três anos. Além da utilização da microcalorimetria isotérmica, foram realizadas as análises de DSC e TG com a finalidade de se avaliar a quantidade de matéria orgânica presente no solo estudado, cujo valor quantificado foi de (3,5 ± 0,2)% g/g. Também foi realizado o cálculo da humidade do solo e as análises elementares [CHN e EDS (Energy Dispersive X-Ray Detector) acoplado ao MEV (Microscópio Eletrônico de Varredura)]. As amostras de solo utilizadas na análise microcalorimétrica foram previamente incubadas com acetonitrila e com soluções de atrazina em acetonitrila nas concentrações de 1000 e 2000 ppm, durante aproximadamente 48 horas. Em seguida, foi descoberto com o emprego da microcalorimetria isotérmica que a acetonitrila ainda permanecia no solo após o período de incubação, além do fato de que o efeito da atrazina sobre os microrganismos do solo não era detectável, uma vez que os valores para o calor gerado durante a incubação com aquele solvente e com as soluções de atrazina em acetonitrila nas concentrações de 1000 e 2000 ppm, respectivamente, eram iguais a: (-12,8 ± 0,8), (-12,9 ± 0,9) e (-13,5 ± 0,6) J, enquanto que os valores da constante do crescimento microbiano eram iguais a: (5,9 ± 1,4), (6,8 ± 1,6) e 6,37 min-1. A análise microbiológica também indicou que a atrazina não estaria influenciando os microrganismos, diferentemente do caso da acetonitrila, a qual foi responsável por uma redução nas quantidades dos microrganismos. No presente trabalho também foi investigada a influência do herbicida nicosulfuron sobre as atividades microbianas nos solos de mata nativa ou floresta e de cultivos do milho e do café. Foram empregadas as mesmas técnicas analíticas como no caso da atrazina, sendo que para se estudar o nicosulfuron foram investigadas as seguintes condições de incubação (durante 48 h) para cada tipo de solo: aplicação de acetonitrila, aplicação de uma solução de nicosulfuron em acetonitrila com uma concentração igual a 64 ppm e aplicação de uma solução com a mesma natureza, mas com uma concentração igual a 120 ppm. Os resultados indicaram que o solo de floresta era o mais rico em termos de matéria orgânica (4,0 ± 0,1)%, enquanto que o solo de cultivo do café era o mais rico em termos de humidade (21 %). Preliminarmente, as análises térmicas realizadas com o auxílio da microcalorimetria isotérmica indicaram que a acetonitrila foi novamente a espécie mais biodegradada, ao passo que nos casos das condições em que havia adição de água ao invés da solução de glicose pôde ser concluído que o solo cultivado com café foi aquele que mais sofreu influência do nicosulfuron do que nos casos dos outros solos, uma vez que para o valor de concentração mais elevado, i.e., 120 ppm, o valor da energia dissipada (calor; Q) foi estatisticamente superior (-6,6±0,3)J do que no caso da solução da mesma natureza com concentração igual a 64 ppm (-4,8±0,9)J. Para os solos de floresta ou mata nativa e de cultivo do milho o nicosulfuron não exerceu influência detectável. As análises microbiológicas para os solos de cultivo do café e do milho não indicam que ocorram diferenças estatisticamente significativas para algumas das condições estudadas, de tal maneira que para o estudo com o nicosulfuron podemos concluir que a microcalorimetria isotérmica se mostra uma técnica promissora que pode permitir estudos com xenobióticos como os pesticidas / Abstract: It is known in agriculture that soil quality does dependent on the kind of soil management. In the present work was applied the isothermal microcalorimetry to investigate the influence of the herbicide atrazine on the microbial activity of a forest soil that was aged (resting along 3 years under about 4°C). Besides the application of isothermal microcalorimetry it were performed the DSC and TG analyses with the purpose to evaluated the amount of organic matter present in the soil whose value was equal to (3.5±0.2) % to the studied soil. It were also performed the calculation of humidity in the soil and the elemental analyses [CHN and EDS (Energy Dispersive X-Ray Detector) coupled to SEM (Scanning Electron Microscopy)]. The soil samples used for the microcalorimetric analysis were previously incubated with acetonitrile and atrazine solutions in acetonitrile (1000 ppm and 2000 ppm), during approximately 48 hours. Afterwards, with the aid of the Isothermal Microcalorimetry it was discovered that actually the acetonitrile was remaining in the soil, even after the incubation period and that the effect of atrazine on the soil microorganisms was undetectable, once the heat generated for the incubation with acetonitrile and with atrazine solutions in acetonitrile of 1000 and 2000 ppm were equal respectively to: (-12.8 ± 0.8); (-12.9 ± 0.9) and (-13.5 ± 0.6) J, whilst that the values of the microbial growth constant were equal to: (5.9±1.4); (6.8±1.6) and 6.37 min-1. The microbiological analysis also indicated that the atrazine was not influencing the microorganisms, differently for the case of acetonitrile that was responsible for a decrease on the amounts of them. It was also investigated in that work the influence of the herbicide nicosulfuron on the microbial activities of soils under forest, and under maize and coffe tree crops. The same kind of analyses were performed as for the case of atrazine, but the investigations occured after a previous period of incubation along 48 h, and the conditions evaluated were: application of acetonitrile, application of nicosulfuron solution in acetonitrile with concentration equal to 64 ppm and application of a solution with the same nature but with concentration equal to 120 ppm. The results indicated that the forest soil was the richest one in terms of organic matter ( 4.0 ± 0.1) % , whilst the soil that lies under a coffe tree crop was the richest one in terms of humidity (21 % ). The thermal analyses with the aid of the Isothermal Microcalorimetry indicated preliminary that again acetonitrile was biodegradated mostly. However, for the soil tilled under coffe tree crop, considering the same conditions discussed previously for nicosulfuron but with the addition of deionized water after 48 h, the microbial activity was more stimulated by the nicosulfuron than respect to the other conditions, once with the solution of nicosulfuron with the highest concentration, i. e., 120 ppm, the value for the heat dissipated (Q) was statistically higher (-6.6±0.3) than for the concentration equal to 64 ppm (- 4.8 ± 0.9), while that in the forest soil and for the soil tilled with maize crop its influence was undetectable. The microbiological analysis for the forest soil and for the soil under maize crop shown that there are no differences that are statistically significant for some conditions studied, in such a way that for the study with nicosulfuron we can conclude that the Isothermal Microcalorimetry shows itself a promising technique that can allow studies with xenobiotics as the pesticides / Doutorado / Físico-Química / Doutor em Ciências

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This research explores Isothermal Titration Calorimetry as a method for measuring beta-galactosidase activity directly and continuously in milk, sweet whey, sweet whey permeate, acid whey, and acid whey permeate. Beta-galactosidase in various concentrations was injected into each of the liquid dairy products spiked with lactose to verify if the heat rate from the enzymatic reaction could be observed. In addition, a consistent concentration of beta-galactosidase was injected into various concentrations of lactose in the products, to observe the heat rates from the enzymatic reaction. There was exothermic activity that never returned to baseline demonstrated in milk, sweet whey, and sweet whey permeate with beta-galactosidase from Kluyveromyces lactis in runs done in the isothermal titration calorimeter. The baseline was approximately 3-9 uJ/s above the control's baseline at the end of the runs. The exothermic activity ranged from approximately 2-10 uJ/s and did not return to baseline when beta-galactosidase concentrations were varied and lactose concentrations remained the same. The exothermic heat rate was approximately 3-7 uJ/s when lactose concentrations were varied and enzyme concentrations remained the same. With runs with increasing lactose concentrations, there was no corresponding increase in the exothermal reaction indicating saturation of the enzyme. There was a short exothermic reaction(s), ranging from approximately 3-26 uJ/s, demonstrated when varying concentrations of beta-galactosidase from Aspergillus oryzae in acid whey and acid whey permeate were injected into a consistent concentration of lactose in acid whey and acid whey permeate. There was a pattern of increasing heat with increasing concentrations of enzyme, with some of these differences being statistically significant. There was also a short exothermic reaction(s), ranging from approximately 2-17 uJ/s, demonstrated when a consistent concentration of beta-galactosidase from Aspergillus oryzae was injected into varying concentrations of lactose. There was a pattern of increasing heat rate with increasing concentrations of lactose, with some of these differences being statistically significant. This research demonstrates that ITC is a useful method for measuring residual beta-galactosidase and/or residual lactose in liquid dairy products. This research leads to further understanding of how enzymes and substrates interact directly in the food matrix, rather than in an isolated environment.

Preventing the spread of blood-borne infectious diseases is vital to improving global health outcomes, particularly for low- and middle-income countries (LMICs). Sensitive and accurate diagnosis of infections is vital to this effort. Nucleic acid amplification tests (NAATs), which amplify pathogen nucleic acids, are gold-standard techniques for detection and quantification of pathogen levels. However, standard NAATs such as polymerase chain reaction (PCR) require expensive equipment for blood sample processing and DNA/RNA amplification, making them challenging to implement in resource-limited areas of LMICs. In this work, I developed two methods to simplify sample processing and amplification to make NAATs more accessible for use at the point of care in resource-limited areas of LMICs. The first method enables instrument-free nucleic acid extraction from whole blood. A room temperature lysis chemistry and a paper-and-plastic sample capture device were developed to isolate, purify, and store pathogen DNA and RNA on a paper capture membrane. Extracted nucleic acids can be eluted and used in standard NAATs or in developmental amplification assays. I demonstrated successful isolation of HIV virion RNA and P. falciparum parasite DNA from whole blood samples over several concentrations with >60% recovery. Extracted RNA remains stable on the capture membrane for two weeks at room temperature and 37°C, alleviating the need for cold storage after sample collection. These results are a promising step toward using this method for simplified sample extraction and storage in low-resource settings in LMICs. The second method I developed is a novel isothermal amplification technique for P. falciparum DNA. Sensitive diagnosis of P. falciparum infection is vital to identify and treat low-density, asymptomatic infections and move closer to eliminating malaria. Highly sensitive PCR assays are difficult to deploy in resource-limited areas of LMICs and existing isothermal methods require complex assay design and are often not sensitive enough to diagnose asymptomatic infections. Here, I developed a novel isothermal technique which amplifies multiple regions of the P. falciparum genome, generating a large amount of DNA for better analytical sensitivity. The assay achieves a lower limit of detection of ~23.4 fg P. falciparum gDNA/µL (~1 parasite/µL) in 30 minutes, similar gold-standard PCR assay while using a fraction of the resources required for PCR. Lastly, I adapted the assay for implementation at the point of care. I showed that the assay directly amplifies P. falciparum parasite DNA captured on paper with the paper-and-plastic device previously developed. I also incorporated visual assay readout with lateral flow strips, eliminating the need for specialized equipment to detect amplified DNA. I explored methods to eliminate cold storage of reagents by stabilizing amplification enzymes at room temperature. The work described in this thesis represents two enhanced methods for point of care detection of blood borne pathogens. By simplifying sample extraction, amplification, and detection, the methods described here make NAATs more accessible to low-resource areas of LMICs. The whole blood nucleic acid extraction device and isothermal assay described in this work can be used together for sensitive diagnosis of P. falciparum malaria. The methods can also be used independently, or in combination with other techniques routinely used in the field. The flexibility built in to these methods enables easier integration into existing workflows in LMICs. / 2021-05-18T00:00:00Z

This work was dedicated to quantify and distinguish the radio- and chemitoxic effects of environmentally relevant low doses of uranium on the metabolism of microorganisms and multicellular organisms by a modern and highly sensitive microcalorimetry. In such low-dose regime, lethality is low or absent. Therefore, quantitative assays based on survival curves cannot be employed, particularly for multicellular organisms. Even in the case of microbial growth, where individual cells may be killed by particle radiation, classical toxicity assessments based on colony counting are not only extremely time-consuming but also highly error-prone. Therefore, measuring the metabolic activity of the organism under such kinds of conditions would give an extremely valuable quantitative measure of viability that is based on life cell monitoring, rather than determining lethality at higher doses and extrapolating it to the low dose regime. The basic concept is simple as it relies on the metabolic heat produced by an organism during development, growth or replication as an inevitable byproduct of all biochemical processes. A metabolic effect in this concept is defined as a change in heat production over time in the presence of a stressor, such as a heavy metal. This approach appeared to be particular versatile for the low dose regime. Thus, the thesis attempted in this case to measure the enthalpy production of a bacterial population as a whole to derive novel toxicity concepts. In the following chapters, an introduction about the properties of ionizing radiation will be briefly presented, in addition to a review about the isothermal calorimetry and its application in studying the bacterial growth. Later in chapter 2, the effect of uranium on the metabolic activity of three different bacterial strains isolated form a uranium mining waste pile together with a reference strain that is genetically related to them will be investigated. Due to the lack of published dedicated calibration techniques for the interpretation of heat production of bacterial cells under the conditions of calorimetric recordings, additional experiments, thorough investigations of the effects of experimental conditions, have been carried out in order to guide the interpretation of calorimetric results. In chapter 3, the differentiation between chemi- and radiotoxicity of uranium has been addressed by isotope exchange, which was a key effort in this thesis as it opens new experimental approaches in radioecology. In chapter 4, through investigating the role of the tripeptide glutathione (GSH) in detoxifying uranium, it will be shown to which degree the intrinsically unspecific signal provided by metabolic heat can be related to highly specific metabolic pathways of an organism, when combined with genetic engineering. The demonstration of gaining molecule-specific information by life metabolic monitoring was another experimental challenge of this thesis and provides proof of principle that can be extended to many organisms. Finally in chapter 5, an attempt has been undertaken to establish a minimal food chain, in order to study the effects of the exposure of a multicellular organism to uranium through its diet.

The most widely used titanium alloy in the hot sections of a jet engine is Ti-6Al-2Sn-4Zr-2Mo (Ti-6242) and with the technological advancements additive manufacturing (AM) of Ti-6242 is of great interest. Although, there is not much published related to additively manufactured Ti-6242. The project aimed to provide an experimental input for simulations of additively manufactured,laser metal deposited–wire (LMD-w) of Ti-6242. The main part of this project has been to experimentally study the effect of isothermal temperatures and holding times on the microstructural changes in as-built Ti-6242 on Ti-64 base-plate. The evaluation of micro-structural changes with isothermal temperature, holding time and cooling rates on Ti-6242 are quantified in terms of alpha laths, phase fraction by using MIPAR (image analysis software) and preliminary determine mechanical properties by performing hardness tests.The microstructures obtained through a process are highly dependent on the thermal history is it exposed to and the mechanical properties are determined by the microstructures present. In this thesis work the alpha lath thickness and the hardness of the material increases with increasing isothermal temperature. From the phase fractions obtained forthe heat treated samples an equilibrium phase diagram and a TTT diagram is plotted for as-built microstructure.

This thesis presents Monte Carlo methods for simulations of phase behaviors of Lennard-Jones fluids. The isobaric-isothermal (NPT) ensemble and Gibbs-NPT ensemble are introduced in detail. NPT ensemble is employed to determine the phase diagram of pure component. The reduced simulation results are verified by comparison with the equation of state by by Johnson et al. and results with L-J parameters of methane agree considerably with the experiment measurements. We adopt the blocking method for variance estimation and error analysis of the simulation results. The relationship between variance and number of Monte Carlo cycles, error propagation and Random Number Generator performance are also investigated. We review the Gibbs-NPT ensemble employed for phase equilibrium of binary mixture. The phase equilibrium is achieved by performing three types of trial move: particle displacement, volume rearrangement and particle transfer. The simulation models and the simulation details are introduced. The simulation results of phase coexistence for methane and ethane are reported with comparison of the experimental data. Good agreement is found for a wide range of pressures. The contribution of this thesis work lies in the study of the error analysis with respect to the Monte Carlo cycles and number of particles in some interesting aspects.