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  • About
  • The Global ETD Search service is a free service for researchers to find electronic theses and dissertations. This service is provided by the Networked Digital Library of Theses and Dissertations.
    Our metadata is collected from universities around the world. If you manage a university/consortium/country archive and want to be added, details can be found on the NDLTD website.
11

A fundamental investigation of non-Fickian and Case II penetrant transport in glassy ploymers

Ekenseair, Adam Keith 01 December 2010 (has links)
The relative rates of the diffusional and relaxational processes during the absorption of penetrant molecules in glassy polymers determine the nature of the transport process and lead to Fickian, Case II, and anomalous absorption behavior. While previous models account for anomalous behavior, there is still a disconnect between theory and experiment, as data must be fit to the model with previously determined independent parameters. With trends leading to smaller device scales and increasingly complex polymer structures, there is a need for a quantitative understanding of the manner in which a polymer’s network structure alters both the rate and the mode of penetrant transport. To this end, samples of glassy poly(methyl methacrylate), poly(2-hydroxyethyl methacrylate), and poly(vinyl alcohol) were synthesized primarily by an iniferter-mediated, thermally-initiated free radical polymerization procedure. The thermal and mechanical properties of these polymers, as well as the polymer network structure, were varied through crosslinking and confirmed by detailed characterization. The dynamics of small molecule penetrant transport were examined in each polymer, with an emphasis on the occurrence of non-Fickian and Case II transport. The degree of crosslinking and choice of crosslinking molecule were shown to be powerful tools in tuning the observed penetrant transport process. For instance, the transport dynamics were altered from Fickian to Case II by increasing the degree of crosslinking and from Case II to Fickian by increasing the crosslinking interchain bridge length. Within the purely Case II regime, the rate of penetrant transport, or the Case II front velocity, was shown to scale with the square root of the degree of crosslinking in all systems investigated. A novel procedure for the in situ examination of penetrant transport in glassy polymers was developed utilizing high-resolution X-ray computed tomography. This completely nondestructive technique was used to visualize features in the interior of opaque solid objects and obtain digital information on their 3-D structure and properties. In this manner, the time-dependent penetrant concentration profiles throughout a swelling polymer were determined and analyzed. / text
12

Roxithromycin : a solubility and stability study / Elzet van Niekerk

Van Niekerk, Elzet January 2011 (has links)
Roxithromycin is a semi-synthetic, macrolide antibiotic, derived from erythromycin A. It acts as a bacteriostatic drug at low concentrations and a bactericidal drug at high concentrations. It binds to the 50S subunit of the 70S ribosome, which causes the reversible inhibition of RNA-dependent bacterial protein synthesis. It is well known that active pharmaceutical ingredients (APIs) may exist in numerous solid states. Differences in the solid state significantly influence the physical and chemical properties of an API. The in vivo performance of a dosage form will also be influenced by the solid state properties of a given pharmaceutical active. The amorphous characteristics of APIs have a significant impact on their performance and thus offer the potential for exciting new pharmaceuticals. Whilst amorphous forms of poorly soluble APIs are more soluble than their crystalline counterparts, they tend to be physically unstable, which makes their formulation into solid dosage forms quite challenging. Roxithromycin has only 50% oral bioavailability due to its poor aqueous solubility and for this reason, its potential for optimal therapeutic effect are limited. Poor solubility is thus an important obstacle in formulation development. During this study, amorphous forms of roxithromycin were prepared via quench cooling, and desolvation of chloroform- and ethyl acetate solvates. These amorphous forms were characterised by means of several techniques, whilst their solubilities and stabilities were also investigated. The outcomes of the solubility studies illustrated the complexity of this API and its amorphous forms with regards to their interactions with water. Solubility studies confirmed the superior solubility of the roxithromycin glass (prepared through quench cooling) and amorphous forms (desolvation of solvates) over the roxithromycin monohydrate in water. The solubility in water improved in the order of roxithromycin monohydrate < roxithromycin glass < roxithromycin glass powder < amorphous chloroform desolvate. The roxithromycin monohydrate, as well as the amorphous forms of roxithromycin demonstrated stability over a one-month period of exposure 40°C and relative humidity (RH) of 75%. The roxithromycin glass powder tended to revert to the more stable crystalline monohydrate after week 3 of stability testing. The roxithromycin glass at lower temperatures of 25°C and 30°C (both at 75% RH) tended to transform into the more crystalline form at week 4 of the study. These transformations were, however, not as significant as during the 40°C / 75% RH study. The conclusion could therefore be made that this transformation into the crystalline form was more temperature – than moisture dependant. At a higher temperature (at identical humidity conditions), the transformation into the crystalline form was much faster. Stability studies on the two roxithromycin desolvates were also performed in order to determine whether these amorphous forms, would differ, with regards to their stability, from the glass prepared through heating and cooling. It was determined that the desolvates were more stable than the roxithromycin glass. / Thesis (MSc (Pharmaceutics))--North-West University, Potchefstroom Campus, 2012
13

Roxithromycin : a solubility and stability study / Elzet van Niekerk

Van Niekerk, Elzet January 2011 (has links)
Roxithromycin is a semi-synthetic, macrolide antibiotic, derived from erythromycin A. It acts as a bacteriostatic drug at low concentrations and a bactericidal drug at high concentrations. It binds to the 50S subunit of the 70S ribosome, which causes the reversible inhibition of RNA-dependent bacterial protein synthesis. It is well known that active pharmaceutical ingredients (APIs) may exist in numerous solid states. Differences in the solid state significantly influence the physical and chemical properties of an API. The in vivo performance of a dosage form will also be influenced by the solid state properties of a given pharmaceutical active. The amorphous characteristics of APIs have a significant impact on their performance and thus offer the potential for exciting new pharmaceuticals. Whilst amorphous forms of poorly soluble APIs are more soluble than their crystalline counterparts, they tend to be physically unstable, which makes their formulation into solid dosage forms quite challenging. Roxithromycin has only 50% oral bioavailability due to its poor aqueous solubility and for this reason, its potential for optimal therapeutic effect are limited. Poor solubility is thus an important obstacle in formulation development. During this study, amorphous forms of roxithromycin were prepared via quench cooling, and desolvation of chloroform- and ethyl acetate solvates. These amorphous forms were characterised by means of several techniques, whilst their solubilities and stabilities were also investigated. The outcomes of the solubility studies illustrated the complexity of this API and its amorphous forms with regards to their interactions with water. Solubility studies confirmed the superior solubility of the roxithromycin glass (prepared through quench cooling) and amorphous forms (desolvation of solvates) over the roxithromycin monohydrate in water. The solubility in water improved in the order of roxithromycin monohydrate < roxithromycin glass < roxithromycin glass powder < amorphous chloroform desolvate. The roxithromycin monohydrate, as well as the amorphous forms of roxithromycin demonstrated stability over a one-month period of exposure 40°C and relative humidity (RH) of 75%. The roxithromycin glass powder tended to revert to the more stable crystalline monohydrate after week 3 of stability testing. The roxithromycin glass at lower temperatures of 25°C and 30°C (both at 75% RH) tended to transform into the more crystalline form at week 4 of the study. These transformations were, however, not as significant as during the 40°C / 75% RH study. The conclusion could therefore be made that this transformation into the crystalline form was more temperature – than moisture dependant. At a higher temperature (at identical humidity conditions), the transformation into the crystalline form was much faster. Stability studies on the two roxithromycin desolvates were also performed in order to determine whether these amorphous forms, would differ, with regards to their stability, from the glass prepared through heating and cooling. It was determined that the desolvates were more stable than the roxithromycin glass. / Thesis (MSc (Pharmaceutics))--North-West University, Potchefstroom Campus, 2012
14

Modification of glassy carbon under strontium ion implantation

Odutemowo, Opeyemi Shakirah January 2013 (has links)
Glassy carbon is a disordered form of carbon with very high temperature resistance, high hardness and strength and chemical stability even in extreme environments. Glassy carbon is also unaffected by nearly all acids and cannot be graphitized even at very high temperature. Because of these characteristics, there is a possibility that glassy carbon can replace copper, iron, titanium alloys and other materials employed in making canisters used in nuclear waste storage. The modification of glassy carbon due to strontium ions implantation and heat treatment is reported. Glassy carbon (GC) samples were implanted with 200 keV strontium ions to a fluence of 2×1016 ions/cm2 at room temperature. Sequential isochronal annealing was carried out on the implanted samples at temperatures ranging from 200 oC - 900 oC for one hour. The influence of ion implantation and annealing on surface topography was examined by the scanning electron microscopy (SEM), while Raman spectroscopy was used to monitor the corresponding structural changes induced in the glassy carbon. The depth profiles of the implanted strontium before and after annealing were determined using Rutherford Backscattering Spectroscopy (RBS). Compared to SRIM predictions the implanted strontium profiles was broader. After annealing at 300 oC, bulk and surface diffusion of the strontium atoms took place. Annealing at 400 oC- 700 oC not only resulted in further diffusion of strontium towards the surface, the diffusion was accompanied with segregation of strontium on the surface of the glassy carbon substrate. Evaporation of the strontium atoms was noticed when the sample was annealed at 800 oC and 900 oC respectively. These annealing temperatures are higher than the melting point of strontium (~769 oC). The Raman spectrum of the virgin glassy carbon shows the disorder (D) and graphitic (G) peaks which characterize disordered carbon materials. Merging of these two peaks was observed when the virgin sample was implanted with strontium ions. Merging of these peaks is due to damage caused by the implantation of strontium. The Raman spectrum recorded after heat treatment showed that only some of the damage due to implantation was annealed out. Annealing at 20000C for 5 hours resulted in a Raman spectrum very similar to that of virgin glassy carbon indicating that the damage due to the ion implantation was annealed out. SEM showed large differences in the surface topography of the polished glassy carbon surfaces and those of as-implanted samples. Annealing did not significantly change the surface microstructure of the implanted samples. / Dissertation (MSc)--University of Pretoria, 2013. / gm2014 / Physics / unrestricted
15

DYNAMICS OF PROTEINS IN GLASSY SOLVENTS

Dirama, Taner E. January 2005 (has links)
No description available.
16

Slow Dynamics In Complex Fluids : Confined Polymers And Soft Colloids

Kandar, Ajoy Kumar 07 1900 (has links) (PDF)
The thesis describes the study of slow dynamics of confined polymers and soft colloids. We study the finite size effect on the dynamics of glassy polymers using newly developed interfacial microrheology technique. Systematic measurement have been performed to address the issue of reduction of glass transition under confinements. Slow and heterogeneous dynamics are the underlined observed behavior for dynamics in confined glassy polymers. The slow relaxation dynamics and dynamical heterogeneity in polymer grafted nanoparticles (PGNPs) systems were studied using advanced X - ray photon correlation spectroscopy (XPCS) techniques. Our studies presented in this thesis on dynamics of polymer grafted nanoparticle systems in melts and solution are the first attempt to study them experimentally. Thus our work shed the light about new technique to study confined system more accurately and explore new soft colloidal system to study fascinating dynamics and interesting phase behavior. In Chapter 1, we provide the theoretical background along with brief review of the literature for understanding the results presented in this thesis. The details of the experimental set up and their operating principle along with the details of the experimental conditions are provided in Chapter 2. In Chapter 3 we present our newly developed technique (interfacial microrhelogy) and its consequences to study the complex fluids at interface. Chapter 4 discusses the concentration and temperature dependent glassy dynamics in confined glassy polymers. In Chapter 5 we provide the structural and dynamical study of polymer grafted nanoparticles in melts and solutions. We provide the summary of our result and the future prospective of the work in Chapter 6. Chapter-1 provides the ground work and theoretical aspects for understanding the results presented in this thesis. It starts with the discussion about the slow dynamics of complex fluids and transit to dynamic behavior of polymer in confinement, glassy dynamics in confinements . This also discusses the basic aspects of studying viscoelastic properties using rheology, interface rheology, microrheology, interface microrheology techinques. In continuation it discusses structure and dynamics of different soft colloids investigated for last decade and then theoretical aspects of XPCS is discussed. Towards the end of this Chapter, we discuss the procedure to explain and understand systems dynamical heterogeneity near glass like phase transition. Chapter-2 contains the details of the experimental techniques which has been used for the study of confined polymers and soft colloids. Brief introduction to basic principles of the measurements followed by details of the material and methods have been provided. Chapter-3 we discuss the interafacial microrheology of different complex fluids and advantages of the techniques is discussed in Chapter 3. This includes discussion about the technique sensitivity at the surface using quantum dots (QDs) as a probe and about the configuration of the QDs at/on monolayer. Later on establishment of the technique has been demonstrated through easurements on arachidic acid, poly(methylmethacrylate) (PMMA), poly(vinylacetate) (PVAc), poly(methylacrylate) (PMA) monolayers. The extracted subdiffusive nature of QDs in on monolayers through mean square displacement has been explained using fractional Brownian motion model. Towards the end of the chapter we discuss about the extraction of real and imaginary elastic modulus from mean square displacement data using generalized Stokes-Einstein relation for the quasi two dimensional systems and explains about the possible viscoelastic transition in the different monolayers. The concentration and temperature dependent glassy dynamics of confined polymers (PMMA) are discussed in Chapter-4. We demonstrate the microscopic nature of spatio-temporal variation of dynamics of glassy polymers confined to a monolayer of 2 3 nm thickness as a function of surface density and temperature. It illustrates the systems dynamical heterogeneity and explain the observed large reduction of glass transition temperature in confined system through finite size effect. In Chapter 5 we discuss the result based on systematic studies of dynamics of PGNPs in melts and solutions. In addition it also illustrates the structural anisotropy and anomalous dynamical transitions in binary mixture of PGNPs and homopolymers in good solvent condition. It provides temperature and wave vector dependent XPCS measurements on polymer grafted nanoparticles with the variation of functionality. The functionality ( f ) dependent nonmonotonic relaxation in melts of PGNPs and solvent quality dependent non monotonic relaxation of PGNPs system have been elaborated in the continuation. We present possible phase behavior of PGNPs system in good solvent with addition of homopolymer of two different molecular weight. Chapter 6 contains the summary and the future perspective of the work presented.
17

Thermal And Electrical Properties Of Silver And Iodine Doped Chalcogenide Glasses

Pattanayak, Pulok 02 1900 (has links)
Silver containing chalcogenide glasses have been extensively studied during the last few decades; the main interest in these materials being their electrical conductivity which changes by several orders of magnitude upon silver doping. Glassy chalcogenides doped with silver have applications in optical elements, gratings, micro-lenses, waveguides, bio & chemical sensors, solid electrolytes, batteries, etc. Chalcohalide glasses have become important in the recent times, from both scientific & technological points of view, due to the interesting properties exhibited by these glasses such as the transparency in the infrared region, the stability against devitrification, solubility of rare earth elements, etc. In this thesis work, the thermal properties and electrical switching behavior of certain silver and iodine doped chalcogenide glasses have been investigated The thesis contains five chapters: Chapter 1: This chapter is an introduction to the fundamental aspects of amorphous semiconductors with a particular reference to chalcogenide glasses. The advantages and applications of chalcogenide glasses are also described. Chapter 2: The methods of preparation and characterization of the glasses investigated are described in this chapter. Also, the details of the experiments undertaken, namely temperature modulated Alternating Differential Scanning Calorimetry (ADSC), electrical switching analysis, Photo-thermal Deflection Spectroscopy (PDS), etc, are outlined. Chapter 3: In this chapter, the thermal behavior and electrical switching of silver doped Ge-Se and As-Se chalcogenide glasses are described. Bulk, melt-quenched Se-rich Ge0.15Se0.85-xAgx glasses have been found to be microscopically phase separated and composed of Ag2Se clusters and GeSe2-Se network. When the silver concentration exceeds 10 atom %, the Ag2Se clusters embedded in the GeSe2-Se network percolate. The signature of this percolation threshold is clearly observed as the sudden appearance of two exothermic crystallization peaks in ADSC runs. Density, molar volume and micro hardness studies also strongly support the view of a percolation transition. The super-ionic conduction observed earlier in these glasses at higher silver proportions, is likely to be connected with the silver phase percolation. It has been found that Ge0.15Se0.85-xAgx glasses of lower silver concentration (x = 0.07 and 0.08) do not exhibit electrical switching at voltages up to 1100 V. A negative resistance behavior and threshold type electrical switching is seen in Ge0.15Se0.85-xAgx samples with x 0.09. Also, fluctuations are observed in the I-V characteristics of these samples, which have been attributed to the difference in thermal conductivities between the Ag2Se inclusions and the Ge-Se base glass. A sharp drop has been observed in the switching voltage with Ag concentration which is due to the more metallic nature of silver and the presence of Ag+ ions. Further, the saturation in the decrease of VT around x = 0.10, is related to silver phase percolation in these glasses. Bulk As20Se80-xAgx glasses (0 x 15) have been found to exhibit two endothermic glass transitions and two exothermic crystallization reactions on heating. Based on which it is suggested that As20Se80-xAgx glasses are also microscopically phase separated, containing Ag2Se phases embedded in an As-Se backbone. The occurrence of microscopic phase separation in As20Se80-xAgx glasses is also confirmed by SEM studies. With increasing silver concentration, the Ag2Se phase percolates in the As-Se matrix, with a well-defined percolation threshold at x = 8. This silver phase percolation is exemplified by sudden jumps in the composition dependence of the second crystallization peak and non-reversible heat-flow, Hnr obtained at the second glass transition reaction of As20Se80-xAgx glasses. The super-ionic conduction observed earlier in these glasses at higher silver proportions, is likely to be associated with the observed silver phase percolation. Like Ge0.15Se0.85-xAgx glasses, As20Se80-xAgx glasses also exhibit threshold type electrical switching with fluctuations in the I-V characteristics; these fluctuations have been attributed to the difference in thermal conductivities between the Ag2Se inclusions and the As-Se base glass. A sharp drop has been observed in the switching voltage with Ag concentration which is due to the more metallic nature of silver and the presence of Ag+ ions. Further, the saturation in the decrease of VT around x = 8, is found to be related to silver phase percolation in these glasses, which has been proposed on the basis of ADSC experiments. Chapter 4: The chapter 4 deals with thermal studies, electrical switching investigations and Photo-thermal Deflection Spectroscopic (PDS) measurements on certain Ge-Te-I and As-Te-I chalcohalide glasses. It has been found that the compositional variation of the glass transition temperature of Ge22Te78-xIx glasses, obtained by Alternating Differential Scanning Calorimetry (ADSC), exhibits a broad hump around 5 atom % of iodine. Further, a sharp minimum is seen in the composition dependence of non-reversing enthalpy (Hnr) of Ge22Te78-xIx glasses at x = 5, which is suggestive of a thermally reversing window at this composition. Electrical switching studies on Ge22Te78-xIx glasses indicate that these glasses exhibit memory type electrical switching. At lower iodine concentrations, a decrease is seen in switching voltages with an increase in iodine content (in comparison with the base Ge22Te78 glass), which is due to the decrease in network connectivity. The increase seen in switching voltages of Ge22Te78-xIx glasses at higher iodine contents, suggests that the influence of the metallicity is stronger at higher iodine proportions. It is also interesting to note that the composition dependence of the threshold voltages shows a slope change at x = 5, the inverse rigidity percolation threshold of the Ge22Te78-xIx system. . Further, it is found that the thermal diffusivities ( D) of Ge22Te78-xIx glasses decrease with the increase in iodine content, which has been understood on the basis of fragmentation of the Ge-Te network with the addition of iodine. Also, a cusp is seen in the composition dependence of thermal diffusivity at the composition x = 5 (average coordination number, r = 2.39), which has been identified to be the inverse rigidity percolation threshold of the system at which the network connectivity is lost. ADSC studies on As45Te55-xIx chalcohalide glasses (3 x 10) reveal that there is not much variation in the glass transition temperature of As45Te55-xIx glasses, even though there is a wide variation in r . Based on this observation we suggest that the variation in glass transition temperature of network glasses is dictated by the variation in average bond energy rather than the average coordination number. Further, the non-reversing enthalpy Hnr of As45Te55-xIx glasses is found to exhibit a sharp minimum at the composition x = 6. A broad hump is also seen in glass transition and crystallization temperatures in the composition range 5 x 7. These results indicate a narrow thermally reversing window in As45Te55-xIx glasses around the composition x = 6. As45Te55-xIx glasses have been found to exhibit a memory to threshold type change in switching behavior with iodine content (x 6), which has been understood on the basis of the sharp increase in thermal diffusivity above x = 6. It is also observed that the switching voltages do not change appreciably with composition/average coordination number. Though no pronounced signature of a stiffness transition is seen in the variation with composition of VT, fluctuations are seen in the switching voltages around x = 6, the composition corresponding to the sharp thermally revering window. PDS studies indicate that the thermal diffusivities () of As45Te55-xIx chalcohalide exhibit a sharp minimum at the composition x = 6. This result reasserts the presence of a sharp thermally reversing window in As45Te55-xIx glasses around the composition x = 6. Chapter 5: The significant results obtained in the present thesis work have been summarized in this chapter. Further, the scope for future work is also presented.
18

Non-local rheology of soft glassy materials / Rhéologie non locale des matériaux vitreux mous

Mansard, Vincent 10 September 2012 (has links)
Les matériaux vitreux mous (émulsion concentrée, mousse, suspension concentrée...) présentent un comportement rhéologique entre solide et liquide. Aux petites contraintes le système reste élastique, mais au-dessus d’une contrainte seuil, le système s’écoule comme un liquide visqueux. Ce comportement se trouve dans de nombreux fluides industriels comme dans les cosmétiques, l’agro-alimentaire ou encore le béton. Une contrainte seuil n’apparait que au dessus d’une certaine fractions volumique. Au dessus de cette fraction les particules se bloquent entre elle, la relaxation n’est plus possible et l’écoulement devient fortement coopératif.Cette coopérativité influe sur la rhéologie à petite échelle, Quand le confinement devient de l’ordre de quelques particules, la viscosité ne dépend plus uniquement, comme habituellement, de la contrainte locale mais aussi de la contrainte au voisinage. C’est ce qu’on appelle rhéologie non-localeJ’ai étudié expérimentalement ce comportement en utilisant les outils de micro fluidiques. J’ai étudié une micro-émulsion concentrée s’écoulant dans un microcanal en observant directement l’écoulement des gouttes avec un microscope confocal. Les résultats sont comparés au model “Kinetic-Elasto-Plastic” de Bocquet et al. 2009 et à des simulations de dynamique moléculaire. / Soft glassy materials (concentrated emulsion, foams, concentrated suspension…) present rheological properties between solids and liquid. Under small stress they stay elastic but at stress higher than a yield stress they begin to flow as a liquid. Those fluids are used in cosmetics, food industry or building materials as concrete. The yield stress behavior only appears when the volume fraction is high enough, where the particles are blocked by their neighbors. So the systems cannot relax and the flow become highly cooperative.This cooperativity impacts the rheology at small scale. When the confinement is of the order of few particles, the viscosity does not only depend on the local stress as usually but also on the stress in the neighborhood. This is called non-local rheology.I studied experimentally this behavior by flowing concentrated emulsion in a microchannel and observing directly the flow of the droplet with a confocal microscopy. The results from these microfluidics experiments are compared to predictions of the Kinetic Elasto Plastic model of Bocquet et al. 2009 and molecular dynamic simulation of jammed soft particles.
19

Modification of glassy carbon electrode (GCE) with prussian blue as a mediator on carbon nanotube materials through sequential deposition

Abdullahi Mohamed, Farah 08 1900 (has links)
Prussian blue (PB) nanoparticles were synthesized from FeCl3.6H2O, K4[Fe(CN)6].3H2O, and from Fe(NO3)3.9H2O and K4[Fe(CN)6].3H2O, and then characterized by Fourier transform infrared (FT-IR), Ultraviolet-visible spectroscopy, X-ray diffraction (XRD), Energy dispersive spectroscopy (EDS), Scanning electron microscopy (SEM), Raman spectroscopy and thermogravimetric analysis. Graphene oxide and carbon nanotubes were also synthesized and characterized. PB nanoparticles, carbon nanotubes (CNT), graphene oxide (GO) and cetyltrimethylammonium bromide (CTAB) were sequentially deposited onto glassy carbon electrode surface to form chemically modified electrode for the detection of hydrogen peroxide (H2O2) and dopamine. The following electrodes were fabricated, GC-PB, GC-MWCNT, GCGO, GC-CTAB, GC-MWCNT-PB, GC-GO-PB and GC-CTAB-PB. Cyclic and Square wave voltammetric techniques were used to measure the hydrogen peroxide detectability of the electrodes at pH ranges of (3 - 7.4) in 0.1M phosphate buffer solution, in the absence or presence of 25 μL of H2O2. The GC-CNT-PB, GC-GO-PB,GC-CTAB-PB electrodes showed a good response for the detection of hydrogen peroxide in both acidic and neutral media while the GCPB electrode only showed good response in acidic media.
20

Síntese e caracterização de materiais vítreos de composição 50B203-(50-x)PbO-xLiF / Synthesis and characterization of 50B203-(50-x)PbO-xLiF vitreous materials composition

Garcia, Agnaldo 18 December 2006 (has links)
Esse trabalho descreve a caracterização térmica, estrutural e elétrica do sistema vítreo 50B203-(50-x)PbO-xLiF com x variando de 0,0 a 50,0. A técnica de calorimetria diferencial exploratória (DSC) foi utilizada na determinação das temperaturas características. A difratometria de raios x foi utilizada na detecção e identificação de fases cristalinas originadas durante a síntese ou durante o processo de aquecimento das amostras. As técnicas de espectroscopia Raman e Ressonância Magnética Nuclear (RMN) foram utilizadas na obtenção de informações estruturais da ordem a curto alcance em função da composição das amostras. A técnica de espectroscopia de impedância complexa foi utilizada na determinação das condutividades elétrica em função da quantidade de LiF e da temperatura. Amostras vítreas sem a presença de fases cristalinas foram obtidas para composições contendo no máximo 40moI % de LiF. Através da análise da medida de densidade, foi possível constatar que o aumento da quantidade de LiF leva a formação de uma estrutura mais aberta. A análise do espectro Raman das amostras vítreas mostrou que com o aumento da concentração de LiF, ocorre uma mudança significativa nas unidades estruturais borato presentes nas amostras. Na amostra vítrea contendo 40 mol% de LiF observou-se a existência de uma superunidade estrutural formada por diferentes unidades borato. Apesar dessa variação das unidades borato, as medidas de RMN do 11B mostraram que a razão entre as unidades trigonal B03 e tetraédrica B04 permanece praticamente constante em todo intervalo de composição analisada. A condutividade elétrica aumenta à medida que a concentração de LiF aumenta devido ao aumento do numero de portadores de carga. A 330&#176;C uma condutividade de 3,55 x 10-5 S/cm foi medida para a amostra contendo 40 moI % de LiF. Utilizando as amostras contendo 40 e 45 mol% de LiF preparadas e caracterizadas durante a realização desse trabalho, foi possível construir um dispositivo para ser utilizado na demonstração do processo de condução elétrica em materiais vítreos condutores para alunos do ensino médio / This work describes the thermal, structural and electric characterization of 50B203-(50-x)PbO-xLiF glass system with x varying from 0,0 to 50,0. The differential scanning calorimetry (DSC) technique was used to determine the glass transition and the crystallization temperatures. The X-ray diffraction technique was used to detect and in the identification of the crystallized phases present on the glassy samples after the melt and during the heating. The Raman spectroscopy and the Nuclear Magnetic Resonance techniques were used in order to verify the structural changes induced by the substitution of PbO by LiF on the anionic borate units and on the B03/B04 species ratio. The impedance complex spectroscopy technique was used to evaluate the variation of the electrical conductivity and activation energy as a function of the LiF content. Homogenous glassy sample containing less than 45 mol % of LiF without any trace of crystallization were obtained. The analysis of the Raman spectra shows that as the amount of LiF increases the concentration of anionic borate species changes and that these changes are an indicative of the formation of B-F bonds. However, according to the 11B NMR data, these structural rearrangement should be of such nature that the ratio sup>[3]B/[4]B is near1y invariant. As expected, the electrical conduction increases as the amount of LiF increases because the number of carriers increases. At 330&#176;C; , the conductivity varies from 3.93 x 10-10 (S/cm) for the sample without LiF to 3.55 x 10-5(S/cm) for the sample containing 40 mol % of LiF. The activation energy (Ea) varied respectively from 1.55 eV to 0.97 eV. Using the glassy samples with 40 and 45 mol% of LiF, we could built a set up that can be used to demonstrate the electrical conduction process on glass materials to high school students

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