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Freeze casting is a colloidal processing technique that shows great promise for development of nanostructured materials. A ceramic nanopowder is dispersed with a polymer in water, under carefully controlled pH. The suspension is cast into a suitable mold and frozen, then de-molded and exposed to a vacuum to sublimate and remove the water. Polymer adsorption and rheology were studied to optimize and characterize a colloidal suspension of a 38 nm Al2O3 powder. The dispersant, dispersant amount, pH and solids loading were examined to determine the best conditions for freeze casting. Based on adsorption and viscosity data, optimal conditions for freeze casting were found with Poly(acrylic acid) (PAA) dispersant, at 2.00 wt% (of Al2O3), pH of 9.5, and a solids loading of 40 vol%. Carbon nanotubes (CNTs) were added to that suspension in increments of 0.14, 0.28, 0.53, 1.30 and 2.60 vol%. The viscosity increased dramatically upon addition of 1.30 vol% CNTs. The colloidal CNT-Al2O3 suspension was successfully freeze cast and the microstructure showed a very smooth fracture surface. It was determined that upon resting, the suspension undergoes a physical change which must be completed to obtain advantageous microstructure. Freeze cast Al2O3 discs with and without CNTs were measured using a concentric ring test, with strengths on the order of one MPa. The freeze cast sample was successfully debinded, but the heating profile attempted was not effective in obtaining full density. / Master of Science

Yes / In this work, a novel concept in freeze desalination (FD) was introduced. Nowadays the total liquefied natural gas (LNG) production capacity has reached 290 Megatons per year. Its enormous cold energy released from re-gasification can be used in the freeze desalination process to minimize the overall energy consumption. A process of FD on flake ice maker utilizing LNG cold energy was designed and simulated by HYSYS software. An ice bucket on flake ice maker was chosen as seawater crystallizer mainly due to its continuous ice making and removing ice without heat source. A dynamic model of the freezing section has been developed and simulated through gPROMS software. The results show that the consumption of 1 kg equivalent LNG cold energy can obtain about 2 kg of ice melt water. In addition, it is shown that the power consumption of this LNG/FD hybrid process is negligible.

Submitted by Angela Maria de Oliveira (amolivei@uepg.br) on 2019-02-27T11:49:16Z No. of bitstreams: 2 license_rdf: 811 bytes, checksum: e39d27027a6cc9cb039ad269a5db8e34 (MD5) Gustavo Antoniacomi de Carvalho.pdf: 6310308 bytes, checksum: 8e1efd9d86bc5a1adf80b45bba2a3985 (MD5) / Made available in DSpace on 2019-02-27T11:49:16Z (GMT). No. of bitstreams: 2 license_rdf: 811 bytes, checksum: e39d27027a6cc9cb039ad269a5db8e34 (MD5) Gustavo Antoniacomi de Carvalho.pdf: 6310308 bytes, checksum: 8e1efd9d86bc5a1adf80b45bba2a3985 (MD5) Previous issue date: 2018-01-30 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Cerâmicas porosas vêm ganhando visibilidade devido a algumas aplicações tecnológicas interessantes, tais como a utilização em eletrólitos sólidos, ânodos de células a combustível, filtros cerâmicos e reposição óssea e dental. Dentre elas, há especial atenção ao estudo de materiais porosos com porosidade graduada, nos quais a quantidade de poros e a morfologia dos mesmos se alteram pelo volume do material. Nesse trabalho foi realizado o processamento e caracterização de materiais cerâmicos de alumina com porosidade graduada a partir das técnicas de freeze casting e colagem de barbotina, utilizando hidróxido de alumínio e amido de arroz como fases de sacrifício. Após a conformação das amostras por esses métodos, a porosidade foi caracterizada por microscopia eletrônica de varredura, pelas medidas de porosidade aparente feita pelo Princípio de Arquimedes e pela distribuição de tamanho de poros feita pela técnica de porosimetria de mercúrio. Foi avaliada também a resistência mecânica das amostras a partir de ensaio de compressão. Foi confirmada a relação entre as amostras processados isoladamente e suas respectivas camadas nas amostras graduadas. Foi observada também uma boa interação interfacial entre cada uma das camadas das amostras graduadas. A porosidade das amostras com porosidade graduada se manteve próxima do esperado, o valor esperado foi determinado a partir da média das amostras processadas isoladamente em relação às camadas do material com porosidade graduada. O ensaio mecânico demonstrou que não houve influência das interfaces dos materiais graduados na sua resistência à compressão. / Porous ceramics have been gaining visibility due to some interesting technological applications, such as its use as solid electrolytes, fuel cell anodes, ceramic filters and bone and dental reposition. Among them, there is special care in studying graded porosity materials, where the quantity of pores and pore morphology changes through the material volume. In this work the processing and characterization of alumina ceramic materials with functionally graded porosity by freeze casting and slip casting techniques using aluminum hydroxide and rice starch as sacrificial template was performed. After conformation, the porosity was characterized through electron scanning microscopy, apparent porosity through Archimedes method and median pore size through mercury porosimetry. The mechanical resistance was also obtained by compression testing. The analysis allowed to confirm the relation between each of the isolated samples’ microstructure and its respective layer in each of the graded materials, also, the graded materials shown good interfacial interaction between each of the layers. The porosity in graded materials kept close to the expected value, which was determined by the medium value of the porosities of the isolated samples respective to the graded material. Mechanical testing shown that there was no influence of the graded material interfaces in its compressive strength.

Le monoxyde d'azote est exclusivement synthétisé chez les mammifères par une famille d’hémoprotéines, les NO-Synthases. Le cœur de l’activité des NO-Synthases est l’activation de l’oxygène c'est-à-dire l’activation de l’intermédiaire réactionnel FeIIO2. Cette étape est contrôlée par la réactivité intrinsèque du fer, par les transferts de proton et les transferts d’électron. Elle doit être parfaitement maîtrisée car elle contrôle le chemin catalytique emprunté et la nature du produit final. Comprendre l’étape d’activation de l’oxygène est essentiel à la compréhension du rôle biologique et/ou pathologique de la NO-Synthase de mammifère. Cette question s'étend aux NO-Synthases bactériennes pour lesquelles on ne connait ni le mécanisme moléculaire ni la fonction biologique. Ce manuscrit propose une analyse approfondie de l’étape d’activation de l’oxygène de la NO-Synthase. Dans un premier temps, nous avons étudié l’influence de l’environnement proximal sur la réactivité intrinsèque du fer et l’activation de l’oxygène. Nous avons généré des protéines mutées qui modifient les propriétés électroniques de la liaison proximale de l’hème. Ces protéines mutées ont été caractérisées par différentes spectroscopies (résonance paramagnétique électronique, Raman de résonance). Dans un second temps nous avons directement étudié le complexe FeIIO2, en présence d’analogues de substrat, grâce à des analyses de cinétique rapide en flux continu et en flux arrêté (stopped-flow). Dans un troisième temps, le rôle du cofacteur tetrahydrobioptérine dans le transfert de proton et d’électron a été étudié par une méthode de piégeage à des temps très courts : le freeze-quench. L'ensemble de nos résultats montrent que l’activation de l’oxygène est régulée par les propriétés électro-donneuses du ligand proximal et par le réseau de liaisons H distal. Nous mettons en évidence des différences dans le rôle redox du cofacteur tetrahydrobioptérine entre la NO-Synthase de mammifère et la NO-Synthase bactérienne. La difficulté majeure pour comprendre l’étape d’activation de l’oxygène de la NO-Synthase réside dans la complexité et la rapidité de la réaction catalytique. Dans ce contexte, nous avons cherché à adapter une méthodologie qui a prouvé son efficacité dans le cas des cytochromes P450 : la cryo-réduction couplée à des sauts en température. / Nitric oxide is exclusively synthesized by NO-Synthases in mammals. The heart of the NO-synthase activity is oxygen activation, which corresponds to the activation of the FeIIO2 intermediate. This step depends on the heme electronic properties and on the electron and proton transfers. Oxygen activation has to be well mastered to control exactly the nature of the end-product. Understanding the oxygen activation step is necessary to better understand the biological/pathological role of the mammalian NO-Synthases. Furthermore, bacterial NO-Synthases function and oxygen activation mechanism are unknown. This PhD work proposes a deep analysis of the oxygen activation step in NO-Synthases. First, proximal environment has been studied with mutated proteins. These mutations impact the electronic properties of the heme proximal bond. Spectroscopic analyses of these mutants have been done by electron paramagnetic resonance and resonance Raman. Then, we have studied the FeIIO2 intermediate with substrate analogs which has necessitated continuous flow and stopped-flow analyses. Finally, the role of the tetrahydrobiopterin cofactor in the electron and proton transfer has been studied and clarified thanks to a very fast trapping method : the freeze-quench. Our results show that the oxygen activation step is elaborately controlled by the proximal bond electron donation and the distal H bond network. At the same time we show some differences between mammalian and bacterial NO-Synthases concerning the redox role of the tetrahydrobiopterin cofactor. The major obstacle to understand the oxygen activation step resides in the complexity of the active site chemistry and the rate of catalytic reactions. For this reason, we propose to adapt an already successful protocol to trap some intermediates in the cytochromes P450 mechanism : cryo-reduction coupled with temperature jumps.

<p>  </p> <p>With the recent growth in demand for biologics across the globe, it remains critical to manufacture these biologics in solid-state to improve stability as well as to increase the ease of transportation across the world. To meet these increased demands, it is of paramount importance to use various processing methods that have shorter processing times. It is also important to understand the impact of the processing methods and various formulation components on the stability of the proteins.  In Chapter 1, a review of the various processing methods that are used in the industry along with additional processing methods that are being investigated will be discussed. The common drying methods such as lyophilization and spray drying along with the novel techniques as well as specific examples of processing parameters to improve the processing conditions that better suit the protein formulations will be mentioned. </p> <p>The studies in Chapter 2 examined the effects of processing methods (freeze drying and spray freeze drying) and the excipients on the protein structure and physical stability. Protein solids containing one of two model proteins (lysozyme or myoglobin) were produced with or without excipients (sucrose or mannitol) using freeze drying or spray freeze drying (SFD). The protein powders were then characterized using solid-state Fourier transform infrared spectroscopy (ssFTIR), differential scanning calorimetry (DSC), circular dichroism spectrometry (CD), size exclusion chromatography (SEC), BET surface area measurements, and solid-state hydrogen-deuterium exchange with mass spectrometry (ssHDX-MS). ssFTIR and CD could identify little to no difference in the structure of the proteins in the formulation. ssHDX-MS was able to identify the population heterogeneity, which was undetectable by conventional characterization techniques of ssFTIR and CD. ssHDX-MS metrics such as Dmax and peak area showed a good correlation with the protein physical instability (loss of the monomeric peak area by size exclusion chromatography) in 90-day stability studies conducted at 40oC for lysozyme.  The higher specific surface area was associated with greater loss in monomer content for myoglobin-mannitol formulations as compared to myoglobin-only formulations. Spray freeze drying seems a viable manufacturing technique for protein solids with appropriate optimization of formulations. The differences observed within the formulations and between the processes using ssHDX-MS, BET surface area measurements, and SEC in this study provide an insight into the influence of drying methods and excipients on protein physical stability.</p> <p>Based on this work, it was identified that spray freeze drying can be a viable alternative to produce solid-state protein formulations with similar stability as the freeze drying process. However, due to the long processing times and scale-up issues involved in the spray freeze drying process, there is a necessity to explore additional drying processes. Chapter 3 focuses on using another novel technique known as electrostatic spray drying (ESD) to produce solid-state protein formulations at lower drying temperatures than conventional spray drying and its effect on protein stability. A mAb formulation was dried by either conventional spray drying or electrostatic spray drying with charge (ESD). The protein powders were then characterized using solid-state Fourier transform infrared spectroscopy (ssFTIR), differential scanning calorimetry (DSC), size exclusion chromatography (SEC), and solid-state hydrogen/deuterium exchange with mass spectrometry (ssHDX-MS). Particle characterizations such as BET surface area, particle size distribution, and particle morphology were also performed. Conventional spray drying of the mAb formulation at the inlet temperature of 70oC failed to generate dry powders due to poor drying efficiency; electrostatic spray drying at the same temperature at 5kV enabled the formation of powder formulation with satisfactory moisture contents. Deconvoluted peak areas of deuterated samples from the ssHDX-MS study showed a good correlation with the loss of the monomeric peak area measured by size exclusion chromatography in the 90-day accelerated stability study conducted at 40oC. Low-temperature (70oC inlet temperature) drying with an electrostatic charge (5kV) led to better protein physical stability as compared with the samples spray-dried at the high temperature (130oC inlet temperature) without charge.</p> <p>This study shows that electrostatic spray drying can produce solid monoclonal antibody formulation at a lower inlet temperature than traditional spray drying with better physical stability. While ESD can be a viable option for thermal-sensitive formulations, it is important to understand the impact of various formulation components on the stability of the proteins while using spray drying. Based on our previous studies, a good understanding of the effect of different sugars and the presence of surfactants on the spray-dried proteins has been established. However, the impact of the selection of buffer on protein stability has not been studied. In Chapter 4, the effect of buffer salts on the physical stability of spray dried and lyophilized formulations of a model protein, bovine serum albumin (BSA) were examined. BSA formulations with various buffers were dried by either lyophilization or spray drying. The protein powders were then characterized using solid-state Fourier transform infrared spectroscopy (ssFTIR), powder X-ray diffraction (PXRD), size exclusion chromatography (SEC), solid-state hydrogen/deuterium exchange with mass spectrometry (ssHDX-MS), and solid-state nuclear magnetic resonance spectroscopy (ssNMR). Particle characterizations such as BET surface area, particle size distribution, and particle morphology were also performed. Results from conventional techniques such as ssFTIR did not exhibit correlations with the physical stability of studied formulations. Deconvoluted peak areas of deuterated samples from the ssHDX-MS study showed a satisfactory correlation with the loss of the monomeric peak area measured by SEC (R2 of 0.8722 for spray-dried formulations and 0.8428 for lyophilized formulations) in the 90-day accelerated stability study conducted at 40oC. PXRD was unable to measure phase separation in the samples right after drying. In contrast, ssNMR successfully detected the occurrence of phase separation between the succinic buffer component and protein in the lyophilized formulation, which results in a distribution of microenvironmental acidity and the subsequent loss of long-term stability. In summary, this study demonstrated that buffer salts have less impact on physical stability for the spray-dried formulations than the lyophilized solids.</p> <p>The study in Chapter 5 looked at examining the physical stability of spray freeze dried (SFD) bovine serum albumin (BSA) solids produced using the radio frequency (RF)-assisted drying technique. BSA formulations were prepared with varying concentrations of trehalose and mannitol, with an excipient-free formulation as control. These formulations were produced using traditional spray freeze drying (SFD) or RF-assisted spray freeze drying (RFSFD). The dried formulations were then characterized using solid-state Fourier transform infrared spectroscopy (ssFTIR), Karl Fischer moisture content measurement, powder X-ray diffraction (PXRD), size exclusion chromatography (SEC), solid-state hydrogen/deuterium exchange with mass spectrometry (ssHDX-MS). Traditional characterization tools such as ssFTIR and moisture content did not have a good correlation with the physical stability of the formulations measured by SEC. ssHDX-MS metrics such as the maximum deuterium uptake (Dmax) (R2 = 0.791) and deconvoluted peak areas of the deuterated samples (R2 = 0.914) showed a satisfactory correlation with the SEC stability data. RFSFD improved the stability of formulations with 20 mg/ml of trehalose and no mannitol and had similar stability with all other formulations as compared to SFD. This study demonstrated that the RFSFD technique can significantly reduce the duration of primary drying cycle from 48 h to 27.5 h while maintaining or improving protein physical stability as compared to traditional lyophilization.</p> <p>Lastly, Chapter 6 consists of a summary of the conclusions formed from the work presented in this thesis. Furthermore, suggestions for future work are provided based on observations of results, less-explored areas of formulation and processing conditions as well as characterization tools to understand effects on protein physical stability.</p> <p><br></p>

Master of Science / Department of Civil Engineering / Kyle Riding / Corrosion of reinforcing steel is one of the most common and serious causes of reinforced concrete deterioration. While corrosion is normally inhibited by a passive layer that develops around the reinforcing steel due to the high pH environment of the surrounding concrete, chlorides will break down this protective layer, leading to reinforcement corrosion. Decreasing the diffusivity of the concrete would slow the ingress of chlorides into concrete, and is one of the most economical ways to increase the concrete service life. Optimized concrete mixtures blending portland cement and supplementary cementing materials (SCMs) have become popular throughout the construction industry as a method of improving both fresh and long-term concrete properties such as workability, strength and porosity. It has been shown that use of Class F fly ash, silica fume and ground granulated blast furnace slag (GGBFS) in binary concrete mixture blends can result in a significant reduction in concrete diffusivity. This study investigates the ability of Class C fly ash and ternary concrete mixture blends to also aid in diffusivity reduction. In order to study the effect of incorporation of SCMs into concrete, mixtures containing Class C and Class F fly ash, silica fume and GGBFS were tested following the ASTM C 1556 procedures to measure the concrete’s apparent chloride diffusivity. Structure life cycles were modeled using the measured apparent chloride diffusivities with two finite-difference based life-cycle analysis software packages. To determine whether a correlation between diffusivity and deterioration due to freezing and thawing exists, samples were also tested for their ability to resist deterioration from freezing and thawing cycles using a modified ASTM C 666 Procedure B test. Results show that the use of Class C fly ash yields some service life improvements as compared to the portland cement control mixtures, while ternary mixture blends performed significantly better than the control mixture and equal to or better than the binary SCM mixtures tested. Freeze-thaw tests showed all mixtures to be equally resistant to deterioration due to freezing and thawing.