This thesis reports the development, synthesis and characterization of a ceramic-ceramic nanocomposite system for its possible application as structural and electronic biomaterial in the biomedical industry. The study selected and synthesized alumina-aluminum titanate-titania (Al2O3-Al2TiO5-TiO2) nanoceramic composite using a simple Sol-Gel technique, which can be easily reproduced. Aluminum propoxide and titanium propoxide were used as precursor chemicals. Propanol and 2- methoxy ethanol were used as solvent and stabilizer, respectively. Thermal analyses were performed for a systematic understanding of phase evolution from the synthesized gel. X-Ray diffraction technique was used to confirm the phase evolution, phase purity, crystallite size and crystal structure(s) of the phase(s). Calcination of the powder at low temperatures (700°C) leads to formation of Al2O3-TiO2 nanocomposite and at higher temperatures into Al2O3-Al2TiO5-TiO2 nanocomposite confirmed by XRD analysis. Electron microscopic techniques were used to investigate powder morphology, crystallite size and inter-planner spacing. High Resolution Transmission Electron Microscopy images of the calcined powder showed agglomerates of powder particles with particle size in 15-20 nm range. As-synthesized powder was uniaxially pressed into cylindrical pellets and sintered at elevated temperatures (1000-1400oC) to study the sintering behavior, densification characteristics, and measurement of mechanical and electrical properties and assessment of bioactivity. Phase transformation induced by the sintering process was analyzed by X-ray powder diffraction technique. The effects of nanosize of powder particles and multi-phases on densification, and mechanical and electrical properties were investigated. Vickers hardness and biaxial flexural strength tests were used to determine mechanical properties. Bioactivity of the nanocomposite was assessed in Simulated Body Fluid (SBF), which has the same ionic concentration as that of human plasma. Effects of biodegradation and change in mechanical properties of the composite when kept in SBF and maintained in a static condition were studied in terms of weight loss, change in the pH of the acellular solution and change in mechanical properties (hardness and biaxial strength). Scanning Electron Microscopy was used to observe the formation of apatite crystals on the surface of the nanocomposite specimens soaked in SBF. The results obtained throw light on biocompatibility and bioactivity of Al2TiO5 phase, which has not been reported so far in the literature to the best of our knowledge. Dielectric constant and dissipation factor of the sintered nanocomposite pellets were measured using HP 4284A impedance-capacitance-resistance meter and 16451 B dielectric test fixture at 1 MHz frequency. The effects of sintering time, temperature and phases present on the electrical properties were studied and are reported in the thesis.

High pressure processing (HPP) and gamma irradiation were applied to inactivate <i>Vibrio vulnificus</i> (MO624) and <i>Vibrio parahaemolyticus</i> (O3:K6 TX2103) in pure culture and in inoculated live oysters. <i>Vibrio</i> pure culture and inoculated oysters were exposed to pressures of 207 MPa (30 kpsi) to 552 MPa (80 kpsi) for 0 min to maximum of 20 min. More than 5.4 log reductions of <i>V. vulnificus</i> occurred at 345 MPa for 0 min in oysters; 345 MPa for 2 min can achieve 4 log reductions on <i>V. parahaemolyticus</i>. Dosage of 1 kGy gamma-irradiation was proved to be effective in producing <i>Vibrio</i> free oysters with comparable organoleptic quality to raw oysters. Thermal conductivity of shucked oysters was measured to be 0.58 to 0.68 W/m°C, as temperature increased from 0 to 50 °C, using a line heat source probe. The specific heat was measured by differential scanning calorimeter methods. It increased from 3.80 to 4.05 kJ/kg °C, when temperature rose from 10 to 50 °C. The thermal diffusivity was calculated employing the data of thermal conductivity, specific heat and density of shucked oysters. The results showed that, under the tested temperature range, thermal properties did not change significantly with temperature. The dielectric constant and loss factor of oysters were determined by an open-ended coaxial line probe connected to a network analyzer at frequency of 30 MHz to 3000 MHz from 1 to 55 °C. The penetration depth of dielectric heating was calculated to be 1.1 cm with the dielectric constant of 55 and loss factor of 14. A two-dimensional mathematical model was established to simulate the heat transfer of microwave heating using a fish gel. Finite difference method was utilized to solve partial differential heat transfer equations. The model was able to predict the temperature distribution in heated fish gel with an accuracy of ± 8°C. Applying the developed mathematical model, the lethality of <i>Vibrio</i> spp., artificially inoculated in live oysters, was estimated collectively by integrating the individual localized lethality of designated heating units. The predicted lethality was compared with microwave enumeration data on Vibrios in oysters. The observed maximum log reductions by microbial enumeration were 4.4 and 3.4 for <i>V. vulnificus</i> and <i>V. parahaemolyticus</i>, respectively. The lethality calculated by integrating temperature profiles was acceptable. The discrepancy between the estimated lethality and microbial test was attributed to the simplified model construction. The quality of processed oysters, including color, aroma and texture properties, was evaluated instrumentally by a digital image system, an electronic nose and universal testing machine. The performance of two electronic nose systems on their abilities to detect oyster aroma and classify the aroma data into distinct groups was evaluated using a trained sensory panel and microbial tests. Cyranose 320 system has demonstrated potential as a quality assessment tool due to its sound correlation with microbial quality data and sensory evaluation scores. According to the quality measurement results, high pressure processing conditions were recommended to be at 345 MPa for less than 3 min and 379 MPa for less than 1.5 min. Deterioration of the quality was distinct for oyster meats exposed to 60 °C or above by thermal processing. The critical thermal processing condition was identified to be 55 °C for 2 min. With careful control, microwave processing could be considered as a candidate for seafood processing to reduce potential bacterial hazard but still retain the quality of the product. / Ph. D.

No description available.

<p>Accurate knowledge of the frequency- and temperature-dependent dielectric properties of biological tissues is crucial in the development of ultra-wideband diagnostic and therapeutic technologies such as microwave breast cancer detection and hyperthermia treatments. This work examines the temperature dependence of the dielectric properties of the five tissue phantom-types developed by our group as well as porcine fat, muscle and liver tissues for the frequency range from 3 GHz to 10 GHz and for the temperature range from 5 °C to 45 °C. A systematic and simple measurement procedure is developed to measure the continuous temperature dependence of the dielectric properties of the various phantom and tissue types. The temperature trends of the dielectric properties of the different phantoms and tissues are investigated.</p> <p>Linear temperature coefficients at discrete frequencies are impractical and insufficient in ultra-wideband applications when realistic, non-linear numerical models of the dielectric properties are required. Therefore, a compact one-pole Cole-Cole model is used to model the frequency dependence of the dielectric properties of the measured samples at every temperature point. A second- or third-order polynomial is used to model the temperature dependence of the Cole-Cole parameters. The final model is a one-pole Cole-Cole model whose parameters are polynomial functions of temperature. This model enables the estimation of the relative permittivity and the conductivity of the measured phantom and tissue types at any temperature and frequency.</p> / Master of Applied Science (MASc)

Yes / Cerium (Ce3+) substituted Ni-Co ferrites with composition Ni0.3Co0.7CexFe2−xO4 (x = 0.0–0.20, with step size 0.05) were synthesized by sol-gel method. Face-centered cubic (FCC) spinel structure was revealed by X-ray analysis. The crystalline size was calculated ranging between 17.1 and 18.8 nm, lattice constant showed a decreasing trend with increase of Ce3+ contents, furthermore, X-ray density was calculated between 5.30 and 5.69 g/cm3. The two characteristic spinel ferrites absorption bands were seen around 550 (cm−1) and 415 (cm−1) in Fourier transform infra-red (FTIR) spectroscopy. The microstructural and elemental studies were carried out by field emission transmission electron microscopy (FE-TEM) and energy dispersive X-ray (EDX) respectively, the average particle size was calculated around 21.83 nm. Magnetic studies were per- formed by vibrating sample magnetometer (VSM), which showed that saturation magnetization Ms and remanence Mr decreased with substitution up to x = 0.10 due to small magnetic moment of Ce3+ than Fe3+. The coercivity Hc increased with substitution up to 908.93 Oe at x = 0.05, then it decreased following the trend of anisotropy constant. The dielectric studies exhibited decrease in dielectric parameters with fre- quency due to decreasing polarization in material. The dielectric loss was significantly decreased in material at high frequency. The Cole-Cole interpretation exhibited conduction mechanism being caused by grain boundary density. These attributes of Ce3+ substituted Ni-Co ferrites suggest their possible use in memory storage, switching and high frequency devices like antenna and satellite systems. / The authors would like to acknowledge the Researcher's Supporting Project Number (RSP-2021/269) King Saud University, Riyadh, Saudi Arabia, for their support in this work. / The full-text of this article will be released for public view at the end of the publisher embargo on 28 Dec 2023.

Aromatic polyimides have found widespread applicability which can be partially attributed to their thermal stability, chemical resistance, and high glass transition temperature. However, deficiencies in their processability, solubility, transparency, and relatively high dielectric constants do not always provide the optimum properties for many specialty microelectronics applications. The incorporation of aliphatic segments to form partially aliphatic polyimides, has been used to counteract these shortcomings. Many of the potential uses of partially aliphatic polyimides require them to adhere to ceramic substrates, a main topic of this research. Polyimides and copolyimides that varied in chemical composition by their aliphatic content were characterized by their molecular weight, glass transition temperature, thermal stability, coefficient of thermal expansion, refractive index, dielectric behavior, and mechanical properties. Structure-property relationships were established. The gamma and beta sub-Tg viscoelastic relaxations were investigated to understand their molecular origins. The adhesion performance of a selected series of partially aliphatic polyimides to SiO2/Si was examined using a shaft loaded blister test, which was designed and instrumented for use in a dynamic mechanical analysis instrument. The adhesion was studied at high and low percent relative humidities and for several temperatures to examine if adhesion strength is influenced by polymer chemical composition. The adhesion energy could not be quantified for the entire series of polyimides. It was possible to interpret the quantitative adhesive fracture energies along with the qualitative adhesion strength behaviors, the failure surface analyses, and to offer an understanding of the adhesive chemical structure-physical property relationships. These understandings provide a conclusion that the incorporation of aliphatic segments into the polyimide chemical structure improves the durability of the adhesive bond to SiO2/Si under high percent relative humidities. / Ph. D.

The research described in this dissertation mainly covers the development of novel technologies for co-crystallisation along with the discovering of plumbagin co-crystal and thermodynamic interrelationship between the co-crystal polymorphs. Co-crystallisation is a fast growing field in the area of crystal design and has shown potential advantages in the field of pharmaceutical. Currently, many research groups are working on the development of new technologies for the synthesis of pure and stoichiometrically controlled co-crystals. In present study, three novel technologies have been developed for co-crystallisation, which include microwave assisted co-crystallisation, spherical crystallisation and microwave assisted sub-critical water processing. The microwave assisted co-crystallisation is a slurry based technology where, effects of drug solubility and dielectric properties of the solvent were investigated using caffeine / maleic acid as a model co-crystal pair. The mechanism of co-crystallisation under microwave irradiation has been proposed. The co-crystals of plumbagin with improved solubility were obtained with the coformers such as hydroquinone, resorcinol and urea using microwave assisted co-crystallisation technique. The spherical crystallisation technology was developed for co-crystallisation of carbamazepine / saccharin co-crystal pair and demonstrated its application for polymorphic control and as a potential technique for the purification of desired crystal form through surface energetic based separation. The thermodynamic interrelationship between Form I and Form II of carbamazepine / saccharin co-crystal was studied using different thermodynamic tests. The results obtained suggest that the carbamazepine / saccharin co-crystal polymorphs are monotropic. Microwave assisted sub-critical water processing has been explored as a green technology for the synthesis of co-crystals. Carbamazepine / saccharin co-crystal pair has been used as a model pair and effects of processing variables on the resulting crystal form and degradation of an API have been studied.

Today, nanotechnology has added a new dimension to materials technology by creating opportunities to significantly enhance the properties of existing conventional materials. Polymer nanocomposites belong to one such class of materials and even though they show tremendous promise for dielectric/electrical insulation applications (“nanodielectrics” being the buzzword), the understanding related to these systems is very premature. Considering the desired research needs with respect to some of the dielectric properties of polymer nanocomposites, this study attempts to generate an understanding on some of the existing issues through a systematic and detailed experimental investigation coupled with a critical analysis of the data. An epoxy based nanocomposite system is chosen for this study along with four different choices of nano-fillers, viz. TiO2, Al2O3, ZnO and SiO2. The focus of this study is on the properties of nanocomposites at low filler loadings in the range of 0.1 - 5% by weight and the properties under investigation are the permittivity/tan delta behaviors, DC volume resistivity, AC dielectric strength and electrical discharge resistant characteristics. Significant efforts have also been directed towards addressing the interface interaction phenomena in epoxy nanocomposites and their subsequent influence on the dielectric properties of the material. The accurate characterization of the dielectric properties for polymer nanocomposites depends on the dispersion of nanoparticles in the polymer matrix and to achieve a good dispersion of nanoparticles in the epoxy matrix for the present study, a systematic design of experiments (DOE) is carried out involving two different processing methods. Consequently, a laboratory based epoxy nanocomposite processing methodology is proposed in this thesis and this process is found to be successful in dispersing nanoparticles effectively in the epoxy matrix, especially at filler concentrations lower than 5% by weight. Nanocomposite samples for the study are prepared using this method and a rigorous conditioning is performed before the dielectric measurements. The dielectric properties of epoxy nanocomposites obtained in the present study show interesting and intriguing characteristics when compared to those of unfilled epoxy and microcomposite systems and few of the results are unique and advantageous. In an unexpected observation, the addition of nanoparticles to epoxy is found to reduce the value of nanocomposite real permittivity below that of unfilled epoxy over a wide range of frequencies. Similarly, it has been observed that irrespective of the filler type, tan delta values in the case of nanocomposites are either same or lower than the value of unfilled epoxy up to a filler loading of 5% by weight, depending on the frequency and filler concentration. In fact, the nanocomposite real permittivities and tan delta values are also observed to be lower as compared to the corresponding microcomposites of the same constituent materials at the same filler loading. In another significant result, enhancements in the electrical discharge resistant characteristics of epoxy nanocomposites (with SiO2/Al2O3 nanoparticles) are observed when compared to unfilled epoxy, especially at longer durations of discharge exposures. Contrary to these encouragements observed for few of the dielectric properties, the trends of DC volume resistivity and AC dielectric breakdown strength characteristics in epoxy nanocomposites are found to be different. Irrespective of the type of filler in the epoxy matrix, it has been observed that the values of both AC dielectric strengths and DC volume resistivities are lower than that of unfilled epoxy for the filler loadings investigated. The results mentioned above seem to suggest that there has to be an interaction between the nanoparticles and the epoxy chains in the nanocomposite and therefore, glass transition temperature (Tg) measurements are performed to characterize the interaction phenomena, if any. The results of Tg for all the investigated nanocomposites also show interesting trends and they are observed to be lower than that of unfilled epoxy up to certain nanoparticle loadings. This lowering of the Tg in epoxy nanocomposites was not observed in the case of unfilled and microcomposite systems thereby strongly confirming the fact that there exists an interaction between the epoxy chains and nanoparticles in the nanocomposite. Considering the variations obtained for the nanocomposite real permittivity and Tg with respect to filler loading, a dual nanolayer interface model is utilized to explain the interaction dynamics and according to the model, interactions between epoxy chains and nanoparticles lead to the formation of two epoxy nanolayers around the nanoparticle. Analysis shows that the characteristics of the interface region have a strong influence on the dielectric behaviors of the nanocomposites and the suggested interface model seems to fit the characteristics obtained for the different dielectric/electrical insulation properties rather well. Further investigations are performed to understand the nature of interaction between nanoparticles and epoxy chains through FTIR studies and results show that there is probably an occurrence of hydrogen bonding between the epoxide groups of the epoxy resin and the free hydroxyl (OH) groups present on the nanoparticle surfaces. The results obtained for the dielectric properties of epoxy nanocomposites in this study have widened the scope of applications of these functional materials in the electrical sector. The occurrence of lower values of real permittivity for nanocomposites is definitely unique and unexpected and this result has huge potential in electronic component packaging applications. Further, the advantages related to tan delta and electrical discharge resistance for these materials carry lot of significance since, electrical insulating materials with enhanced electrical aging properties can be designed using nanocomposite technology. Although the characteristics of AC dielectric strengths and DC volume resistivities are not found to be strictly advantageous for epoxy nanocomposites at the investigated filler loadings, these properties can be optimized when designing insulation systems for practical applications. In spite of all these advantages, serious and systematic research efforts are still desired before these materials can be successfully utilized in electrical equipment.

Electroporation affects the dielectric properties of cells. Dielectric measurement techniques can provide a label-free and non-invasive modality to study this phenomenon. In this thesis we introduce a dielectrophoresis (DEP) based technique to study changes in the cytoplasm conductivity of single Chinese hamster ovary (CHO) cells immediately after electroporation. Using a microfluidic chip, we study changes in the DEP response of single CHO cells a few seconds after electroporation. First, in order to quantify our DEP measurement results and relate them to the cells internal conductivity, we introduce a dielectric model for CHO cells. This is achieved by measuring the DEP response of many individual cells in the β-dispersion frequency region and curve fitting to the measured data. Second, we present quantitative results for changes in the cytoplasm conductivity of single cells subjected to pulsed electric fields with various intensities. We observe that when electroporation is performed in media with lower ionic concentration than cells cytoplasm, their internal conductivity decreases after electroporation depending on the intensity of applied pulses. We also observe that with reversible electroporation there is a limit on the decrease in the cells’ internal conductivity. We hypothesize the reason is the presence of large and relatively immobile negative ions inside the cell which attract mobile positive ions (mainly sodium and potassium) to maintain cell electrical neutrality. We monitor the temporal response of cells after electroporation to measure the time constant of changes due to ion transport and observe this ranges from seconds to tens of seconds depending on the applied pulse intensity. This result can be used to infer information about the density and resealing time of very small pores (not measurable with conventional marker molecules). Lastly, we measure the electroporation of cells in media with different conductivities. Our results show that electroporation in very low conductivity media requires stronger pulses to achieve a similar poration extent as in high conductivity media. The outcome of this thesis can be used to improve our understanding of the dynamics of electroporation as well as its modelling in order to make more accurate predictions or optimize the process for specific applications. / February 2017

Ce travail concerne l’étude de l’effet des impuretés sur les phénomènes physico-chimiques apparaissant durant le frittage des kaolins entre 900 et 1600 °C et les propriétés physiques qui en découlent. Le kaolin est utilisé dans le domaine des céramiques : céramique traditionnelle, porcelaine, céramiques réfractaires (mullite, chamotte), porcelaines électrotechniques, etc… Il est d’usage de contrôler la teneur et la nature des impuretés car leur présence peut limiter leurs applications.Sept kaolins ont été choisis pour les impuretés qu’ils contiennent à savoir ;• Feldspaths, quartz et oxydes de fer pour les kaolins de Tamazert (Algérie)• Matières organiques et oxyde de manganèse pour les kaolins de Djebel Debbagh (Algérie).• Matières organiques, oxydes de fer, gibbsite et anatase pour les kaolins des Charentes (France). La kaolinite ou l'halloysite, de même composition, est le minéral majeur dans chaque cas. L'ensemble des matériaux a été réduit par broyage à la taille de 63 μm. Le premier volet de l’étude consiste en une caractérisation physico-chimique des différents kaolins pour identifier et quantifier les principaux minéraux qui les composent. Le second volet concerne la compréhension des transformations thermiques qui se produisent lors du processus de deshydroxylation de la kaolinite (metakaolin) et lors de la formation de la mullite et de la cristobalite à de hautes températures (1600 °C). La microstructure, le retrait, la densification, la porosité sont les principaux paramètres étudiés dans ce volet.Le troisième volet porte sur les propriétés des kaolins lors du frittage à savoir : Les propriétés colorimétriques, mécaniques et diélectriques. L’effet des impuretés ainsi que la microstructure lors du frittage sur ces propriétés (colorimétrique, mécaniques et diélectriques) sont largement développés. Lors du frittage des différents kaolins la taille des cristallites de mullite augmente avec la température. Ces cristallites incorporent les impuretés colorantes tels que Fe2+/Fe3+, Ti4+/Ti2+ et Mn4+/Mn2+ (selon la température), ce qui résulte dans l’augmentation de la chromaticité et la diminution de la clarté à partir de 1100 °C. La transformation de la phase anatase à la phase rutile diminue le paramètre de clarté des kaolins des charentes. La présence de cristobalite dans le cas du kaolin de Djebel Debbagh riche en manganèse participe à l’augmentation de sa clarté au delà de 1400 °C. La présence de feldspath dans les kaolins de Tamazert améliore leurs propriétés diélectriques grâce à la formation de la phase vitreuse. Lors de l’augmentation de la température à1300 °C, ces propriétés augmentent, elles diminuent avec l’augmentation des fréquences (107-109Hz). Les pertes diélectriques sont plus importantes par rapport à celles rencontrées dans les matériaux céramiques (Porcelaines) utilisés dans les diélectriques qui sont en générale <10-3. Une dernière partie est consacrée à l’application d'un kaolin naturellement riche en anatase dans le domaine des porcelaines diélectriques. L’identification et la quantification des phases formées durant le frittage à 1300 °C , la porosité, la microstructure (observée par MEB) et les propriétés mécaniques et diélectriques sont déterminés. La permittivité relative théorique des porcelaines obtenues, calculée en utilisant la règle des mélanges des phases minéralogiques formées est en bon accord avec les valeurs expérimentales trouvées. / This work concerns the study of the effect of impurities on the physico-chemical phenomena occurring duringthe sintering of kaolin between 900 and 1600 °C and the resulting physical properties. Kaolin is used in the field ofceramics: traditional ceramics, porcelain, refractory ceramic (mullite, chamotte), electrotechnical porcelain, etc. ... It iscustomary to control the content and nature of impurities that may limit their applications.Seven kaolin were selected for the impurities they contain namely; Feldspar, quartz and iron oxides in kaolin of Tamazert (Algeria). Organic matters and manganese oxide for kaolin of Djebel debbagh (Algeria). Organic matter, iron oxides, gibbsite and anatase in kaolin of Charentes basin (France).Kaolinite and halloysite, with the same composition, is the major mineral in each case. All the materials werereduced by grinding to the size of 63 μm.The first part of the study consists of physico-chemical characterizations of different kaolin to identify andquantify the major minerals that compose them.The second part concerns the understanding of thermal transformations that occur during the process ofdehydroxylation of kaolinite (metakaolin) and during the formation of mullite and cristobalite at high temperatures(1600 ° C). The microstructure, shrinkage, densification, the porosity are the main parameters studied in this part.The third part deals with the properties of kaolin during sintering where colorimetric, mechanical and dielectricproperties were studied.The effect of impurities and the microstructure during sintering of these properties (color, mechanical anddielectric) are widely developed. During sintering, crystallite size of mullite of different kaolins increases withtemperature. These crystallites incorporate impurities coloring such as Fe2 +/ Fe3 +, Ti4 +/ Ti2 + and Mn4 +/ Mn 2 +(depending on temperature), resulting in the increase of the chromaticity and the decrease in brightness from 1100 ° C.The transformation of anatase to rutile phase decreases the parameter of clarity of the charente kaolin. Presence ofcristobalite in the case of kaolin of Djebel Debbagh (which is rich in manganese) participates to the increase in claritybeyond 1400 ° C. The presence of feldspar in kaolin of Tamazert improves their dielectric properties through theformation of the glassy phase. When increasing the temperature at 1300 ° C, these properties increase. Relativepermittivity of the calcined kaolin decrease with increasing frequency (107-109Hz). The dielectric losses are largercompared to those found in materials used in the dielectric which are in general <10-3.The last part is devoted to the application of kaolin naturally rich in anatase in the field of dielectric porcelain.The identification and quantification of phases formed during sintering at 1300 °C, porosity, microstructure (observedby SEM) and mechanical and dielectric properties are determined. The theoretical relative permittivity obtained bycalculation using a mixing rule of the mineralogical phases formed agrees with the experimental values.