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Contraintes topologiques et rigidité dans les verresBauchy, Mathieu, Micoulaut, Matthieu 16 October 2012 (has links) (PDF)
La théorie de la rigidité permet de prédire l'évolution en fonction de la composition de nombreuses propriétés des verres, en réduisant la structure moléculaire de ces derniers à de simples treillis mécaniques pouvant être flexibles, isostatiques ou rigides sur-contraints. Originellement développée pour les chalcogénures à température nulle et pression ambiante, cette théorie a été peu à peu étendue. Dans cette thèse, nous nous proposons d'établir une méthode générale d'analyse des contraintes topologiques par Dynamique Moléculaire, dans le but de pouvoir étudier la rigidité de systèmes plus complexes ou soumis à de nouvelles conditions thermodynamiques. Nous montrons ainsi que notre algorithme permet d'étudier aussi bien la rigidité des chalcogénures que des verres d'oxyde tout en off rant une image intuitive de la nature des contraintes à l'échelle atomique. Nous montrons également qu'il est possible de suivre le comportement de ces dernières en fonction de la composition, de la température et de la pression. Cette méthode permet de suivre en fonction de la composition les transitions de rigidité au sein des systèmes ainsi que de mettre en évidence l'existence de phases intermédiaires. Nous rapportons également l'existence d'une phase intermédiaire induite par la pression et montrons que cette dernière présente les mêmes signatures dynamiques et structurales que la phase intermédiaire traditionnelle en composition. En fin, nous mettons en évidence le caractère fortement hétérogène des contraintes topologiques au sein du réseau vitreux.
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Study of Lithium Solvation Environments in Water-saturated NitrobenzeneMoakes, Greg 14 November 2006 (has links)
It was found that there exist three major water environments when water is dissolved in nitrobenzene. 2H NMR has proved that these solvatomers exist irrespective of whether lithium salt is added to the system. 7Li NMR experiments suggested that the first solvatomer is majority nitrobenzene, the second a mixed solvation shell consisting of nitrobenzene and water and the third solvatomer is a large water aggregated at the glass surface. The mixed solvation state is short lived and is promoted by addition of water of by supersaturating the system upon cooling. This is a high energy state and decays either into the homogenous bulk NB state or to the surface of the glass wall, depending on if glass surface is present. In the 7Li NMR experiments, the hydrophobicity of the salt, determined by the anion, affects the relative intensity of the three 7Li resonances.
Addition of lithium serves to promote hydrogen bonding in the majority nitrobenzene solvatomer, as confirmed by FTIR and neutron diffraction studies. There is no evidence that it has an effect on the size of the mixed solvatomer or the water aggregate immobilized on the glass surface. A reasonable hypothesis is that lithium exchanges between the water species which are formed independent of lithium involvement. The system is summarized as follows:
Below critical water concentration (~200mM) nitrobenzene/water is a homogeneous distribution of water molecules in nitrobenzene. Addition of lithium salt to such a system has two main affects. First, the lithium promotes hydrogen bonding between the dissolved water molecules, as confirmed by FTIR and neutron scattering. Second, the hydrogen bonded water may precipitate causing microheterogeneity of the system, leading to a second resonance observed in both the 2H and 7Li NMR spectra (LiNB/W). In the presence of glass, a third solvation state can nucleate at the glass surface; this solvation state has character even closer to that of bulk water (LiW). These two supplementary solvation states can be artificially induced by either adding aliquots of water or cooling.
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The effect of pore dimension of zeolites on the separation of gas mixturesJee, Sang Eun 06 April 2010 (has links)
We examined the effect of the pore dimension of zeolites on the separation of gas mixtures using atomistic simulation methods. We studied two categories of the zeolites with small pores: pore modified silicalite for H₂/CH₄separation and small pore silica zeolites for CO₂/CH₄separation. The effect of pore modification of silicalite on the H₂/CH₄separation was examined. Under some degrees of surface modification, the CH₄flux was reduced much more than the H₂flux, resulting in high ideal selectivities. The use of small pore zeolites for CO₂/CH₄separations was studied. In DDR, we showed that CO₂diffusion rates are only weakly affected by the presence of CH₄, even though the latter molecules diffuse very slowly. Consequently, therefore, the permeance of CO₂in the equimolar mixtures is similar to the permeance for pure CO₂, while the CH₄permeance in the mixture is greatly reduced relatively to the pure component permeance. The calculated CO₂/CH₄separation selectivities are higher than 100 for a wide range of feed pressure, indicating excellent separation capabilities of DDR based membranes. Inspired by the observation in DDR we also examined the separation capabilities of 10 additional pure silica small pore zeolites for CO₂/CH₄separations. From these considerations, we predict that SAS, MTF and RWR will exhibit high separation selectivities because of their very high adsorption selectivities for CO₂over CH₄. CHA and IHW, which have similar pore structures to DDR, showed comparable separation selectivities to DDR because of large differences in the diffusion rates of CO₂and CH₄.
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Radioaktyviųjų nuklidų dinamika heterogeninėse dispersinėse sistemose / Dynamics of Radioactive Nuclides in Heterogenenous Dispersive SystemsŠapolaitė, Justina 28 December 2009 (has links)
Ši daktaro disertacija glaudžiai siejasi su Ignalinos AE uždarymo ir radioaktyviųjų atliekų utilizavimo problemomis bei paieškomis medžiagų, galinčių atlikti technogeninių ir gamtinių barjerų funkcijas. Tuo tikslu šiame darbe buvo įvertinti pusiausvyros ir kinetiniai sorbcijos parametrai heterogeninėse sistemose bei ištirti vyksmai, lemiantys radionuklidų pašalinimą iš skystųjų radioactyvųjų atliekų bei sulaikymą dirbtiniais ir gamtiniais barjerais.
Darbe buvo ištirti titano silikatai susintetinti Ukrainos Sorbcijos ir endoekologijos problemų institute bei geležies oksidai susintetinti ir apibūdinti Fizikos institute, naudojant Mesbauerio spektroskopiją. Taip pat laboratoriniams tyrimams buvo paimti molių, parinktų paviršinės saugyklos Lietuvoje dirbtiniams barjerams, ėminiai iš Galilaukės aikštelės (moreninis priemolis) ir pramoninio Šaltiškių karjero (triaso molis). Titano silikatų, geležies oksidų ir molio mėginių sorbcinė geba nustatyta Cs, Pu ir Am elementams, įvertinti jų pusiausvyros bei kinetiniai sorbcijos parametrai (pasiskirstymo koeficientas, Kd, sulaikymo faktorius, Rf).
Nustatyta, kad didžiausia Cs sorbcijos geba pasižymėjo titano silikatai, susintetinti naudojant TiOSO4, geresnė Pu sorbcijos kinetika nustatyta sintetiniams geležies oksidams. Didelę reikšmę Cs, Am ir Pu izotopų sulaikymui turi pH verčių kaita bei konkuruojančių jonų koncentracijų gradientas. Nustatyti du skirtingi Cs sorbcijos mechanizmai, esant mažoms ir didelėms Cs koncentracijoms... [toliau žr. visą tekstą] / This PhD thesis is closely linked to the Ignalina NPP decommissioning activities and radioactive waste management as well as related to the searching for effective and low-cost materials which could operate as technogenic and natural barriers. The aim of the work is to evaluate equilibrium and kinetic sorption parameters in heterogeneous systems as well as to investigate sorption mechanisms and processes responsible for radionuclide removal from liquid radioactive waste and retention by artificial and natural barriers.
Synthesized sorbents (titanium silicates and iron oxides) were used in sorption experiments. Samples of loam originated from the Galilaukė site and Triassic clay from industrial Šaltiškiai quarry selected as a candidate for the engineered barrier of the Lithuanian near-surface repository were taken for laboratory investigations. The sorption parameters (distribution coefficient (Kd), kinetic coefficients) of Cs, Pu and Am for newly synthesized inorganic sorbents, iron oxides and clay minerals have been evaluated.
It has been determined that titanium silicates synthesized using TiOSO4 are the most suitable for Cs isotope removal from contaminated solutions. The largest Pu Kd values and better sorption kinetics were determined for synthesized iron oxides. It has been found that gradients of competitive ion concentrations and variations in pH values can interfere Cs, Am and Pu retention by engineered barriers made from Šaltiškiai clay. It has been determined... [to full text]
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Dynamics of Radioactive Nuclides in Heterogeneous Dispersive Systems / Radioaktyviųjų nuklidų dinamika heterogeninėse dispersinėse sistemoseŠapolaitė, Justina 28 December 2009 (has links)
This PhD thesis is closely linked to the Ignalina NPP decommissioning activities and radioactive waste management as well as related to the searching for effective and low-cost materials which could operate as technogenic and natural barriers. The aim of the work is to evaluate equilibrium and kinetic sorption parameters in heterogeneous systems as well as to investigate sorption mechanisms and processes responsible for radionuclide removal from liquid radioactive waste and retention by artificial and natural barriers.
Synthesized sorbents (titanium silicates and iron oxides) were used in sorption experiments. Samples of loam originated from the Galilaukė site and Triassic clay from industrial Šaltiškiai quarry selected as a candidate for the engineered barrier of the Lithuanian near-surface repository were taken for laboratory investigations. The sorption parameters (distribution coefficient (Kd), kinetic coefficients) of Cs, Pu and Am for newly synthesized inorganic sorbents, iron oxides and clay minerals have been evaluated.
It has been determined that titanium silicates synthesized using TiOSO4 are the most suitable for Cs isotope removal from contaminated solutions. The largest Pu Kd values and better sorption kinetics were determined for synthesized iron oxides. It has been found that gradients of competitive ion concentrations and variations in pH values can interfere Cs, Am and Pu retention by engineered barriers made from Šaltiškiai clay. It has been determined... [to full text] / Ši daktaro disertacija glaudžiai siejasi su Ignalinos AE uždarymo ir radioaktyviųjų atliekų utilizavimo problemomis bei paieškomis medžiagų, galinčių atlikti technogeninių ir gamtinių barjerų funkcijas. Tuo tikslu šiame darbe buvo įvertinti pusiausvyros ir kinetiniai sorbcijos parametrai heterogeninėse sistemose bei ištirti vyksmai, lemiantys radionuklidų pašalinimą iš skystųjų radioactyvųjų atliekų bei sulaikymą dirbtiniais ir gamtiniais barjerais.
Darbe buvo ištirti titano silikatai susintetinti Ukrainos Sorbcijos ir endoekologijos problemų institute bei geležies oksidai susintetinti ir apibūdinti Fizikos institute, naudojant Mesbauerio spektroskopiją. Taip pat laboratoriniams tyrimams buvo paimti molių, parinktų paviršinės saugyklos Lietuvoje dirbtiniams barjerams, ėminiai iš Galilaukės aikštelės (moreninis priemolis) ir pramoninio Šaltiškių karjero (triaso molis). Titano silikatų, geležies oksidų ir molio mėginių sorbcinė geba nustatyta Cs, Pu ir Am elementams, įvertinti jų pusiausvyros bei kinetiniai sorbcijos parametrai (pasiskirstymo koeficientas, Kd, sulaikymo faktorius, Rf).
Nustatyta, kad didžiausia Cs sorbcijos geba pasižymėjo titano silikatai, susintetinti naudojant TiOSO4, geresnė Pu sorbcijos kinetika nustatyta sintetiniams geležies oksidams. Didelę reikšmę Cs, Am ir Pu izotopų sulaikymui turi pH verčių kaita bei konkuruojančių jonų koncentracijų gradientas. Nustatyti du skirtingi Cs sorbcijos mechanizmai, esant mažoms ir didelėms Cs koncentracijoms... [toliau žr. visą tekstą]
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Structure locale autour d'hétéroatomes dans des matériaux alumino- et borosilicates pour la catalyseNagendrachar Garaga, Mounesha 28 May 2013 (has links) (PDF)
En dépit de l'importance considérable des matériaux alumino- et borosilicates pour la catalyse, l'origine moléculaire de leur activité demeure mal comprise. Ceci tient à la difficulté de caractériser le désordre structural local généré au sein du réseau silicaté par l'incorporation d'hétéroatomes. Le caractère local de la résonance magnétique nucléaire (RMN) à l'état solide en fait une technique adaptée pour résoudre cette question majeure. Les silicates en feuillés auto-assemblés en présence de surfactants sont d'excellents systèmes modèles pour l'étude de la structure locale autour d'hétéroatomes de B ou d'Al car la synthèse, la structure moléculaire et la signature RMN 29Si simple de leurs formes siliceuses sont parfaitement maîtrisées. L'incorporation dans leurs réseaux silicatés de différentes quantités d'Al ou de B et leurs conséquences ont été étudiées par des méthodologies avancées de RMN permettant de sonder les interactions à travers l'espace ou les liaisons chimiques entre noyaux de 29Si, 27Al, 11B et/ou 1H, une approche qui peut être étendue à la substitution atomique dans une argile aluminosilicate et un nouveau borosilicate de calcium. Ces résultats ont été combinés à la modélisation moléculaire pour construire et valider des modèles structuraux capables de décrire les distorsions et les réarrangements parfois profonds du réseau résultant de la substitution. Cela a révélé des différences frappantes entre les conséquences de l'incorporation d'Al ou de B dans deux matériaux de morphologie semblables mais de structures moléculaires différentes, et offre une occasion unique de comprendre les propriétés régissant l'incorporation d'hétéroatomes dans les silicates.
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Dissolution of Valuable Metals from Nickel Smelter Slags by Means of High Pressure Oxidative Acid LeachingPerederiy, Ilya 11 January 2012 (has links)
In the production of base metals by smelting of sulphide ore concentrates, large amounts of iron are rejected with iron silicate slags. These slags contain Ni, Cu and Co in concentrations up to several percent units. Extraction of the entrapped base metals using high pressure oxidative acid leaching (HPOXAL) was investigated in this work.
Crystalline slags containing fayalite (Fe2SiO4), magnetite (Fe3O4), silica (SiO2) and matte (MeSn<1) were found to be highly amenable to leaching at 250°C, 90 psi (6.2 bar) O2 partial pressure and 70 g/L initial H2SO4. Extractions of Ni, Co and Cu exceeded 90% within 15-20 min and arrived at 95-97% after 45 min. The residues of leaching were identified as aggregates of crystalline hematite (Fe2O3) and amorphous silica.
Dissolution of fayalite and magnetite was shown to be acid driven. Since HPOXAL operates with substoichiometric additions of sulphuric acid (10-20% of the stoichiometric requirement), acid regeneration facilitated by iron oxidation and hydrolysis is crucial to high rates of leaching. Low acidities (<10 g/L) were shown to cause precipitation of ferrous sulphate, slowing acid regeneration and slag dissolution. Elevated acidities (>70 g/L) result in excessive concentrations of Fe(III) in the leach solution, complicating downstream processing.
The use of pyrrhotite tailings, an environmentally hazardous waste, as a substitute of sulphuric acid in slag leaching was investigated. Oxidative co-leaching of pyrrhotite tailings with naturally cooled converter slag at 250°C, 90 psi (6.2 bar) O2, 68 g/L equivalent H2SO4 was shown to have kinetics comparable to adding sulphuric acid with final extractions reaching 95-97% in 45 min.
Granulation of slag melt can produce an amorphous solid solution of SiO2 and metal oxides. Amorphous slag is not amenable to HPOXAL due to the formation of a passive layer of silica. Leaching of amorphous slag at low temperatures was shown to proceed nearly to completion. The difference in the leachability of amorphous slag at high and low temperatures is explained in terms of the rate of silicic acid re-polymerization leading to closure of pores in the leached layer.
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Dissolution of Valuable Metals from Nickel Smelter Slags by Means of High Pressure Oxidative Acid LeachingPerederiy, Ilya 11 January 2012 (has links)
In the production of base metals by smelting of sulphide ore concentrates, large amounts of iron are rejected with iron silicate slags. These slags contain Ni, Cu and Co in concentrations up to several percent units. Extraction of the entrapped base metals using high pressure oxidative acid leaching (HPOXAL) was investigated in this work.
Crystalline slags containing fayalite (Fe2SiO4), magnetite (Fe3O4), silica (SiO2) and matte (MeSn<1) were found to be highly amenable to leaching at 250°C, 90 psi (6.2 bar) O2 partial pressure and 70 g/L initial H2SO4. Extractions of Ni, Co and Cu exceeded 90% within 15-20 min and arrived at 95-97% after 45 min. The residues of leaching were identified as aggregates of crystalline hematite (Fe2O3) and amorphous silica.
Dissolution of fayalite and magnetite was shown to be acid driven. Since HPOXAL operates with substoichiometric additions of sulphuric acid (10-20% of the stoichiometric requirement), acid regeneration facilitated by iron oxidation and hydrolysis is crucial to high rates of leaching. Low acidities (<10 g/L) were shown to cause precipitation of ferrous sulphate, slowing acid regeneration and slag dissolution. Elevated acidities (>70 g/L) result in excessive concentrations of Fe(III) in the leach solution, complicating downstream processing.
The use of pyrrhotite tailings, an environmentally hazardous waste, as a substitute of sulphuric acid in slag leaching was investigated. Oxidative co-leaching of pyrrhotite tailings with naturally cooled converter slag at 250°C, 90 psi (6.2 bar) O2, 68 g/L equivalent H2SO4 was shown to have kinetics comparable to adding sulphuric acid with final extractions reaching 95-97% in 45 min.
Granulation of slag melt can produce an amorphous solid solution of SiO2 and metal oxides. Amorphous slag is not amenable to HPOXAL due to the formation of a passive layer of silica. Leaching of amorphous slag at low temperatures was shown to proceed nearly to completion. The difference in the leachability of amorphous slag at high and low temperatures is explained in terms of the rate of silicic acid re-polymerization leading to closure of pores in the leached layer.
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Apatite based materials for solid oxide fuel cell (SOFC) and catalytic applicationsGasparyan, Hripsime 01 October 2012 (has links)
Low cost silicates with apatite-structure (general formula of apatite A10-xM6O26±δ, where A = rare earth or alkaline earth and M= Si, Ge, P, V..) have been proposed recently as promising solid electrolyte materials (oxygen ion conductors) for use at intermediate temperature solid oxide fuel cells (SOFCs). These materials exhibit sufficiently high ionic conductivity (e.g. ~ 0.01 S cm-1 at 700 oC), which is dominated by the interstitial site mechanism and can exceed that of yttria-stabilized-zirconia (YSZ), the solid electrolyte used in state-of-the-art SOFCs. The apatite structure is tolerant to extensive aliovalent doping, which has been applied for improving ionic conductivity. In this work are presented results concerning synthesis, conductivity and catalytic characterization of Fe- and/or Al-doped apatite type lanthanum silicates (ATLS) of the general formula La10-zSi6-x-yAlxFeyO26±δ as well as electrochemical characterization of interfaces of ATLS pellets with perovskite and Ni-based electrodes. The aim was to investigate the properties of these ATLS material, in particular as it concerns their potential use as SOFC components or as catalysts in oxidation reactions.
The conductivity of pellets prepared from ATLS powders synthesized via four different methods and having different grain size was measured under air and at different temperatures in the range 600 -850 oC, aiming to identification of the effect of composition (doping), method of synthesis, grain size and pellet sintering conditions. For electrolytes of the same composition, those prepared via mechanochemical activation exhibited the highest conductivity, which was improved with increasing Al- and decreasing Fe-content.
In state-of-the-art SOFCs perovskite electrodes are used as cathodes and Ni-based electrodes as anodes, thus electrochemical characterization of perovskite and Ni-based/ATLS interfaces was carried out. As it concerns perovskite/ATLS interfaces, the characterization focused on the study of the open circuit AC impedance characteristics of a La0.8Sr0.2Ni0.4Fe0.6O3-δ/La9.83Si5Al0.75Fe0.25O26±δ interface, at temperatures 600 to 800 oC and oxygen partial pressures ranging from 0.1 to 20 kPa. Under the aforementioned conditions, it was observed that the impedance characteristics of the interface were determined by at least two different processes, corresponding to two partially overlapping depressed arcs in the Nyquist plots. The polarization conductance of the interface was found to increase with increasing temperature as well as with increasing oxygen partial pressure, following a power law dependence. The electrochemical characterization of Ni-based electrodes/ATLS interfaces involved study of the electrochemical characteristics of NiO-apatite cermet electrodes as well as a Ni sputtered electrode interfaced with Al- or Fe-doped apatite electrolytes, under hydrogen atmospheres. The impedance characteristics of these electrodes were found to be determined by up to three different processes, their relative contribution depending on the electrode microstructure, Ni content (as it concerns the cermet electrodes), temperature, hydrogen partial pressure and applied overpotential.
Aiming to investigation of potential catalytic properties of ATLS materials the catalytic activity for CO combustion of a series of ATLS powders was studied. For this purpose, two series of apatite-type lanthanum silicates La10-xSi6-y-zAlyFezO27-3x/2-(y+z)/2 (ATLS), undoped or doped with Al and/or Fe, were synthesized via sol-gel and modified dry sol-gel methods and tested as catalysts for CO combustion. The experiments revealed that the ATLS powders were catalytically active for CO combustion above approximately 300 oC, with light-off temperatures T50 (50% conversion of CO) ranging from 505 to 629 oC. The study focused on the effect on catalytic activity of the synthesis method and doping with Al and/or Fe. Non-doped ATLS with stoichiometric structure, namely La10Si6O27 prepared via the sol-gel method, exhibited the highest catalytic activity for CO oxidation among all tested compositions, the comparison being based on the measured catalytic rate (expressed per surface area of the catalyst) under practically differential conditions. Compared to La-Sr-Mn-O and La-Sr-Co-Fe-O perovskite powders, the tested ATLS powders exhibited lower catalytic activity for CO oxidation. / -
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Impact de la cristallisation sur la structure et la durabilité chimique de verres borosilicatés / Impact of crystallization on the structure and chemical durability of borosilicate glassNicoleau, Elodie 02 February 2016 (has links)
Ces travaux proposent une nouvelle approche pour appréhender la durabilité chimique de matrices de conditionnement de déchets radioactifs partiellement cristallisées. Dans le cadre des études menées sur le stockage en formation géologique profonde, les études de comportement à long terme se sont jusqu’alors focalisées sur des matrices vitreuses homogènes. Cependant, les phases cristallines peuvent être à l’origine de modifications de composition chimique des matrices vitreuses et de leurs propriétés : la description et la compréhension de leur influence sur la durabilité chimique sont alors de première importance. Un protocole d’étude de la durabilité de matrices hétérogènes modèles d’intérêt nucléaire contenant des phases cristallines de différentes natures a donc été développé. Il s’appuie sur une description détaillée de la morphologie, microstructure et structure des matrices vitreuses et des phases cristallines ainsi que sur l’étude de différents régimes d’altération. Trois phases cristallines susceptibles de se former lors d’une augmentation du taux d’incorporation en déchet au sein des verres de conditionnement de type Uranium Oxyde ont été étudiées : les molybdates d’alcalins et d’alcalino-terreux, les silicates de terres rares et l’oxyde de ruthénium.Les résultats acquis ont mis en évidence que la composition et la structure du verre englobant sont les paramètres qui pilotent les cinétiques d’altération des matrices vitreuses partiellement cristallisées. Ce comportement est identique quelle que soit la nature des phases cristallines tant qu’elles n’induisent pas de gradient de composition et qu’elles ne percolent pas au sein de la matrice vitreuse. Fort de ces enseignements, une méthodologie d’étude de matrices partiellement cristallisées sans gradient de composition est proposée. Son développement clé réside dans l’évaluation en première approche du comportement des matrices partiellement cristallisées au travers de l’étude expérimentale de la matrice vitreuse englobante dans les différents régimes d’altération. Cette méthodologie pourrait être adaptée aux cas de nouvelles formulations de verres de compositions plus complexes (p. ex. verre à haut taux d’incorporation) pouvant contenir des cristaux formés au cours du refroidissement. / This work describes a new approach to help understand the chemical durability of partially crystallized nuclear waste conditioning matrices. Among the studies carried out on nuclear waste deep geological disposal, long-term behavior studies have so far been conducted on homogeneous glassy matrices. However, as the crystalline phases may generate modifications in the chemical composition and properties of such matrices, the description and a better understanding of their effects on the chemical durability of waste packages are of primary importance.A protocol to study the durability of heterogeneous model matrices of nuclear interest containing different types of crystalline phases was developed. It is based on a detailed description of the morphology, microstructure and structure of the glassy matrix and crystalline phases, and on the study of various alteration regimes. Three crystal phases that may form when higher concentrations of waste are immobilized in Uranium Oxide type conditioning glasses were studied: alkali and alkaline earth molybdates, rare earth silicates and ruthenium oxide.The results highlight the roles of the composition and the structure of the surrounding glassy matrix as the parameters piloting the alteration kinetics of the partially crystallized glassy matrices. This behavior is identical whatever the nature of the crystalline phases, as long as these phases do not lead to a composition gradient and do not percolate within the glassy matrix. Given these results, a methodology to study partially crystallized matrices with no composition gradient is then suggested. Its key development lies firstly in the evaluation of the behavior of partially crystallized matrices through the experimental study of the residual glassy matrix in various alteration regimes. This methodology may be adapted to the case of new glass formulations with more complex compositions (e.g. highly waste-loaded glass), which may contain crystals formed during cooling.
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