Academic literature on the topic 'Eucryptite'

The structures of ordered and disordered β-eucryptite have been determined from Rietveld analysis of powder synchrotron x-ray and neutron diffraction data over a temperature range of 20 to 873 K. On heating, both materials show an expansion within the (001) plane and a contraction along the c axis. However, the anisotropic character of the thermal behavior of ordered β-eucryptite is much more pronounced than that of the disordered compound; the linear expansion coefficients of the ordered and disordered phases are αa = 7.26 × 10−6 K−1; αc = −16.35 × 10−6 K−1, and αa = 5.98 × 10−6 K−1; αc = −3.82 × 10−6 K−1, respectively. The thermal behavior of β-eucryptite can be attributed to three interdependent processes that all cause an increase in a but a decrease in c with increasing temperature: (i) Si/Al tetrahedral deformation, (ii) Li positional disordering, and (iii) tetrahedral tilting. Because disordered β-eucryptite does not exhibit tetrahedral tilting, the absolute values of its axial thermal coefficients are smaller than those for the ordered sample. At low temperatures, both ordered and disordered β-eucryptite exhibit a continuous expansion parallel to the c axis with decreasing temperature, whereas a remains approximately unchanged. Our difference Fourier synthesis reveals localization of Li ions below room temperature, and we suggest that repulsion between Li and Al/Si inhibits contraction along the a axes.

Glass-ceramic composite materials based on lead-borate glass and eucryptite – a compound with a negative coefficient of linear thermal expansion (CTE), along with the conditions for their production are studied in this paper. Effects of the amount and granulometric composition of the eucryptite as well as time/temperature processing conditions on the change of the linear thermal expansion coefficient of the sintered samples are also examined.

β-Spodumene (Li2O · Al2O · 4SiO2, LAS4) precursor powders were obtained through a sol-gel process using Si(OC2H5)4, Al(OC4H9)3, and LiNO3 as starting materials and LiF as a sintering aid. X-ray diffraction, scanning electron microscopy, scanning transmission electron microscopy with a wavelength dispersive spectrometer, and electron diffraction analysis were utilized to study the phase transition of the β-spodumene glass–ceramics prepared from the gel-derived precursor powders with LiF additive. For the LAS4 precursor powders containing no LiF, the only crystalline phase obtained was β-spodumene. For the pellets containing less than 4.0 wt% LiF and sintered at 1050 °C for 5 h, the crystalline phases were β-spodumene solid solution and β-eucryptite (Li2O · Al2O3 · 2SiO2, LAS2) solid solution. When the LiF content was 5.0 wt% and the sintering process was carried out at 1050 °C for 5 h, the crystalline phases were β-spodumene solid solution, β-eucryptite solid solution (triclinic), and eucryptite [rhombohedral (hex.)]. When the LiF addition attains 3.0 wt%, the fully densified grains are formed, accompanied with an increase in grain size for LiF addition. At the triple junction of grain boundaries a second phase segregates which is identified to be β-spodumene solid solution. In the sintering period of LAS4 precursor powders with LiF additive, the grains converted to β-eucryptite solid solution and β-spodumene solid solution remains at the grain boundaries.

In this paper, β-eucryptite glass ceramics were synthesized by using solid reaction method. Phase constitution, structure and properties of the material were studied by X-ray diffraction (XRD) and differential thermal analysis (DTA). Furthermore, the effects of heat treatment temperature and preservation time on the thermal expansion coefficient were also analyzed. The results showed that the crystallization temperature of β-eucryptite glass ceramics was in the range of 810-860 °C and the content was more than 90%. With the increase of heat treatment temperature, the material expansion coefficient decreased.

The corrosion resistance of chemically modified β-eucryptite (Li_0.41Mg_0.035AlP_0.52Si_0.480₄) having low expansion anisotropy and a near zero coefficient of thennal expansion was evaluated. Samples were exposed to aqueous hydrochloride acid at temperatures up to 100°C and environments containing sodium sulfate up to l000°C. The corrosion resistance was characterized by dilatometry, scanning electron microscopy, X-ray diffraction, energy dispersive x-ray analysis, weight variations, and mechanical properties variations. The results show that modified β-eucryptite is more severely corroded than commercial lithium-alumina-silicate glass-ceramics when exposed to these environments. Aqueous HCI removes AIP04 from modified β-eucryptite leaving a very porous structure. Molten salt corrodes modified β-eucryptite by penetration of sodium and sulfur which form an alkali melt under the surface. The modulus of rupture and the Young's modulus are reduced by both types of corrosion.
Master of Science

The production of ??-eucryptite [LiAlSiO4] and ??-spodumene [LiAlSi2O6] from topaz [Al2SiO4(F0.64OH0.36)2, containing ~3 wt% quartz impurity] from Torrington, NSW may be of commercial importance since both lithium aluminosilicates have negative or low coefficients of thermal expansion and are used commercially as raw materials in the glass, ceramics, and metallurgical industries. A review of the literature has revealed that the production of ??-eucryptite and ??-spodumene from topaz has not been reported before. The aim of the present work was to determine the kinetics and reaction mechanisms of formation of ??-eucryptite from topaz + lithium carbonate mixtures and ??-spodumene from topaz + lithium carbonate + silica mixtures. To this end, the related reactions and subsolidus phase equilibria of the Li2O-Al2O3-SiO2 ternary system were determined. The subsolidus phase equilibria for the Li2O-Al2O3-SiO2 ternary system were investigated by literature assessment, experimentation, and thermodynamic calculations. The experimentation confirmed the previously published tentative compatibility relations in the Al2O3 and the SiO2 corners. Thermodynamic calculations were used to define the phase relations in the Li2O corner. Thermodynamic calculations also were used to define the phase equilibria for two binary subsystems, Li2SiO3-LiAlO2 and Li4SiO4-LiAlO2. The decomposition of topaz and formation of ??-eucryptite from topaz + lithium carbonate mixtures and ??-spodumene from topaz + lithium carbonate + silica mixtures were investigated experimentally using differential thermal analysis (DTA), thermogravimetric analysis (TGA), X-ray diffraction (XRD), Raman microspectroscopy, scanning electron microscopy (SEM), transmission electron microscopy (TEM). Confirmatory thermodynamic calculations also were done. One significant finding of the present work was the formation of nanofibres from topaz + lithium carbonate mixtures at 1150???C. These fibres were formed by gas-phase reaction of SiF4 and AlOF produced from the reaction between topaz, lithium carbonate and by reaction of SiO2 and Li(OH), which was produced by Li2O volatilisation. These fibres, which were difficult to analyse, most likely consisted of metastable ???-spodumene solid solution or mullite in the incipient stage of formation. Formation of single-phase ???-spodumene from topaz + lithium carbonate + silica mixtures was observed after heating above 950???C for 24 h. Reaction paths for the formation of ??-spodumene over the temperature range 450???-1550???C were proposed. The formation of single-phase ??-spodumene was not simple and straightforward but a complex process involving several precursor phases. Specifically, there were two reaction mechanisms involving the formation of single-phase ???-spodumene by gas-solid reaction and gas-liquid-solid reaction. The reaction kinetics and thermodynamics of the formation of single-phase ??-spodumene at 750???-950???C were assessed. Essential work supplementary to that associated with the Li2O-Al2O3-SiO2 system consisted of determination of the decomposition mechanism of topaz, which was determined to take place in four stages. Reaction paths for the decomposition of topaz also were proposed. Another significant finding of the present work was the formation of transient single-crystal mullite from topaz + lithium carbonate + silica mixtures at ~600???C, which may be contrasted with the normal temperature range of 1000???-1400???C for formation from clay-based raw materials. This phenomenon occurred via a gas-solid growth mechanism. The present observation suggests a potential low-temperature route for the production of high-purity mullite fibres without glass contamination.

Course of synthesis of Li2O – Al2O3 – SiO2 (LAS) ceramic via sol – gel process made precursor was investigated. Powder precursor containing LAS components in molar ratio 1:1:4 were prepared by polycondensation technique in aqueous medium using lithium chloride (LiCl), hydrated aluminium nitrate (Al(NO3)39H2O) and silica sol (tosil), respectively. Heated sol was transformed into gel. The resulting gel was dried at temperature 105 °C and xerogel was next calcinated at 750°C. Further was evaluated influence of sintering additives (MgO, ZnO, Ca5(PO4)3OH) on the length of sintering interval. All of them have been stabilized spodumene in the solid solution. The properties of ceramic body prepared by sintering of precursor and grinded Li2CO2, Al2O3 a SiO2 powders were compared. Simultaneous thermogravimety and differential thermal analysis (TG-DTA), X-ray diffractions and heating microscopy were used to study sintering process of LAS ceramic.

This work is focused on Li ceramics and glass-ceramics with low thermal expansion. Composition of these material is based on mineralogical composition of ?-spodumene – Li2O•Al2O3•4SiO2. Sol-gel route of preparation was used for preparation of the material. Sol-gel route is profitable because of production of high purity and controlled grain size powder. Lower sintering temperature, higher degree of homogeneity and shorter time of heat treatment in comparison with traditional approach belong among other advantages of sol-gel route of preparation. Influence of Li+ substitution for K+, which has similar atomic radius, is assessed in this work. These ions are localized in the interstitial position of spodumene structure and are able to maintain the charge balance. Li+ ions were substituted with K+ in the amount of 0; 0,5; 1; 2; 5 and 10 wt. % in view of Li+ weight. In the next step influence of adding mineralizer was specified in the material modified this way. The effect of adding mineralizer on phase transformation and heat treatment tendency was considered. K+ were added to the mixture in the form of potash. Due to this addition forming of orthoclase phase next to spodumene, eucryptit and SiO2 (ss) was detected. Decrease in melting temperature and ability of melt to crystallize were consequence of orthoclase forming. No crystallization appears, when more than 1 wt.% of K+ was added.

Actuellement, la qualité de l’imagerie provenant de systèmes optiques spatiaux est limitée par la taille de leurs miroirs et la masse des structures supportant le miroir. Le développement de systèmes athermiques légers (un seul matériau) constitue le principal challenge dans l’amélioration de ces systèmes. De matériaux légers, résistants mécaniquement (E/ρ3 > 10, σf > 100 MPa) et stables thermiquement (< 2,0.e-6/K) doivent être développés. Dans ce cadre, notre travail porte sur l’élaboration de composites céramiques associant un matériau à coefficient de dilatation thermique (CTE) positif résistant mécaniquement (alumine ou zircone cériée) et un matériau à CTE très négatif (tungstate de zirconium ou β-eucryptite). L'étude du tungstate de zirconium a révélé plusieurs problèmes de décomposition et de réactions avec certaines matrices oxydes, menant à l’abandon de cet oxyde dans l’élaboration des composites. Dans le cas de la β-eucryptite, un phénomène de vermiculation a été mis en évidence, conduisant à la formation d’une porosité intragranulaire. L’optimisation des paramètres de frittage a permis de limiter cette porosité. L’étude du comportement thermique de la β-eucryptite confirme que son CTE très négatif provient principalement d’un phénomène de fissuration, généré par l’anisotropie de dilatation de sa maille cristalline. Cette fissuration est dépendante de la taille des grains mais également de la taille des agrégats de grains dans le cas des poudres. Ainsi, bien que le CTE intrinsèque de la β-eucryptite soit très faible (-0,4.e-6/K), son CTE extrinsèque peut atteindre des valeurs jusqu'à -10,9.e-6/K selon les conditions d’élaboration. Dans ce travail, deux stratégies d’élaboration de composites sont étudiées. Le premier cas consiste à diminuer le CTE des matrices oxydes à partir d’une poudre de β-eucryptite non microfissurée (-0,4.e-6/K) tandis que le second cas consiste à obtenir des matériaux à CTE très faible à partir d’une poudre de β-eucryptite microfissurée (-3,0.e-6/K). Lors de l’utilisation de la matrice en zircone cériée, le taux de dopage au cérium est optimisé afin de limiter la transformation de phase de la zircone. Cette transformation, induite par les contraintes de tension exercées par la β-eucryptite, affecte la linéarité du comportement thermique du composite. Dans les deux cas d’étude, les composites denses montrent une modification du CTE intrinsèque de la β-eucryptite passant de -0,4.e-6/K à plus de +3,2.e-6/K en raison des contraintes de compression appliquées par la matrice (alumine ou zircone cériée). La relaxation de ces contraintes nécessite une sous-densification des composites. A partir de ces observations, différents composites à CTE très faible sont élaborés. Toutefois, le sous-frittage des composites associé à la microfissuration de la β-eucryptite diminuent fortement les propriétés mécaniques des matériaux ainsi élaborés
High resolution satellite imagery from space optical systems is mainly limited by the mirror size and the mass of structures supporting the mirror. Nowadays, the development of light athermal systems is the major challenge to improve these optical systems. So, light materials having good mechanical properties (E/ρ3 > 10, σf > 100 MPa) and thermal stability (< 2.0e-6/K) are required. Within this context, our project consists in processing new ceramic composites by combining positive thermal expansion coefficient (TEC) materials having good mechanical properties (alumina or ceria doped zirconia) and negative TEC materials (zirconium tungstate or β-eucryptite) The processing of zirconium tungstate-based materials showed several decomposition and chemical reactions with some oxide matrix leading to its giving up. In the case of β-eucryptite, vermicular phenomenon occurs during sintering leading to the formation of intragranular porosity. Sintering parameters optimization can limit this porosity. The study of the thermal behavior of pure β-eucryptite materials shows that the very negative TEC results from microcracking, generated by the TEC anisotropy of its crystal lattice. This microcracking depends on the grain size and the aggregate size in the case of powder materials. Despite the fact that the TEC of its lattice (called intrinsic TE C equals to -0.4e-6/K) is very low, its bulk (or extrinsic) TEC can reach values until -10.9e-6/K according to the processing conditions. In this work, two strategies for developing composites were studied. The first one consists in decreasing the matrix TEC using an uncracked β-eucryptite powder (-0.4e-6/K) while the second one consists in elaborating near zero TEC materials from a microcracked β-eucryptite powder (-3.0e-6/K). When ceria-doped zirconia is used, ceria content must be adjusted in order to limit zirconia phase transformation. This transformation is driven by tensile stresses induced by the β-eucryptite and modifies the composite thermal behavior linearity. In both studied cases, dense composites show a modification of the β-eucryptite intrinsic TEC from -0.4e-6/K to more than +3.2e-6/K as a consequence of compressive stresses applied by the oxide matrix. An uncompleted densification of composites is required to relax these stresses. Taking into account these observations, several very low TEC composites were elaborated. However, the uncompleted densification of composites and the β-eucryptite microcracking greatly decrease the mechanical properties of these materials