EXAFS and XRD Study of the Structural Evolution during Isothermal Sintering of SnO2 Xerogels

The formation of an ordered (crystalline) phase during isothermal sintering of SnO2 monolithic xerogels, at 200, 250, 300, 400, 500, 600 and 700°C, has been analyzed by the combined use of EXAFS and XRD techniques. For the desiccated gel (110°C), EXAFS results show the formation of small microcrystallites with the incipient cassiterite structure. Between 110 and 250°C, the dehydratation reaction leads to an amorphization evidenced by a decrease of the long and short range crystallographic order. It is due to fissure formation in the xerogel network. For higher temperatures, a continuous coagulation of the crystallites occurs, leading to grain growth. Grain and pore growth obeys the same kinetic relation, so that the microstructure grows by simple enlargement while its morphology is static.

Small-angle x-ray scattering study of the structural evolution of the drying of sonogels with the liquid phase exchanged by acetone

The structural evolution on the drying of wet sonogels of silica with the liquid phase exchanged by acetone, obtained from tetraethoxisilane sonohydrolysis, was studied in situ by small-angle x-ray scattering (SAXS). The periods associated to the structural evolution as determined by SAXS are in agreement with those classical ones established on basis of the features of the evaporation rate of the liquid phase in the obtaining of xerogels. The wet gel can be described as formed by primary particles (microclusters), with characteristic length a ∼ 0.67 nm and surface which is fractal, linking together to form mass fractal structures with mass fractal dimension D=2.24 in a length scale ξ∼6.7 nm. As the network collapses while the liquid/vapor meniscus is kept out of the gel volume, the mass fractal structure becomes more compacted by increasing D and decreasing ξ, with smoothing of the fractal surface of the microclusters. The time evolution of the density of the wet gels was evaluated exclusively from the SAXS parameters ξ, D, and a. The final dried acetone-exchanged gel presents Porod's inhomogeneity length of about 2.8 nm and apparently exhibits an interesting singularity D →3, as determined by the mass fractal modeling used to fit the SAXS intensity data for the obtaining of the parameters ξ and D.

Structural evolution of Eu-doped hydroxyapatite nanorods monitored by photoluminescence emission

This paper reports the synthesis of Eu-doped hydroxyapatite (HA:Eu) resulting in particles with nanorod diameters from 9 to 26 nm using the microwave hydrothermal method (HTMW). Eu3+ ions were used as a marker in the HA network by basic hydrolysis followed by the HTMW treatment. The crystalline HA:Eu nanorod nature in a short-range order was detected by photoluminescence (PL) measurements from Eu3+ emission into the HA matrix. Thus, was possible to verify that HA crystallization is favored in a short structural order when the HTMW treatment time was increased from 0 to 40 min and that the Eu3+ substitution in the HA lattice is site-selective. (C) 2012 Elsevier B.V. All rights reserved.

Geological and Structural evolution of the Eurasia Africa plate boundary in the Gulf of Cadiz Central Eastern Atlantic Sea.

Iberia Africa plate boundary, cross, roughly W-E, connecting the eastern Atlantic Ocean from Azores triple junction to the Continental margin of Morocco. Relative movement between the two plate change along the boundary, from transtensive near the Azores archipelago, through trascurrent movement in the middle at the Gloria Fracture Zone, to transpressive in the Gulf of Cadiz area. This study presents the results of geophysical and geological analysis on the plate boundary area offshore Gibraltar. The main topic is to clarify the geodynamic evolution of this area from Oligocene to Quaternary. Recent studies have shown that the new plate boundary is represented by a 600 km long set of aligned, dextral trascurrent faults (the SWIM lineaments) connecting the Gloria fault to the Riff orogene. The western termination of these lineaments crosscuts the Gibraltar accretionary prism and seems to reach the Moroccan continental shelf. In the past two years newly acquired bathymetric data collected in the Moroccan offshore permit to enlighten the present position of the eastern portion of the plate boundary, previously thought to be a diffuse plate boundary. The plate boundary evolution, from the onset of compression in the Oligocene to the Late Pliocene activation of trascurrent structures, is not yet well constrained. The review of available seismics lines, gravity and bathymetric data, together with the analysis of new acquired bathymetric and high resolution seismic data offshore Morocco, allows to understand how the deformation acted at lithospheric scale under the compressive regime. Lithospheric folding in the area is suggested, and a new conceptual model is proposed for the propagation of the deformation acting in the brittle crust during this process. Our results show that lithospheric folding, both in oceanic and thinned continental crust, produced large wavelength synclines bounded by short wavelength, top thrust, anticlines. Two of these anticlines are located in the Gulf of Cadiz, and are represented by the Gorringe Ridge and Coral Patch seamounts. Lithospheric folding probably interacted with the Monchique – Madeira hotspot during the 72 Ma to Recent, NNE – SSW transit. Plume related volcanism is for the first time described on top of the Coral Patch seamount, where nine volcanoes are found by means of bathymetric data. 40Ar-39Ar age of 31.4±1.98 Ma are measured from one rock sample of one of these volcanoes. Analysis on biogenic samples show how the Coral Patch act as a starved offshore seamount since the Chattian. We proposed that compression stress formed lithospheric scale structures playing as a reserved lane for the upwelling of mantle material during the hotspot transit. The interaction between lithospheric folding and the hotspot emplacement can be also responsible for the irregularly spacing, and anomalous alignments, of individual islands and seamounts belonging to the Monchique - Madeira hotspot.

Geochronological and structural evolution of the western and central Kaoko Belt in NW Namibia

This thesis focusses on the tectonic evolution and geochronology of part of the Kaoko orogen, which is part of a network of Pan-African orogenic belts in NW Namibia. By combining geochemical, isotopic and structural analysis, the aim was to gain more information about how and when the Kaoko Belt formed. The first chapter gives a general overview of the studied area and the second one describes the basis of the Electron Probe Microanalysis dating method. The reworking of Palaeo- to Mesoproterozoic basement during the Pan-African orogeny as part of the assembly of West Gondwana is discussed in Chapter 3. In the study area, high-grade rocks occupy a large area, and the belt is marked by several large-scale structural discontinuities. The two major discontinuities, the Sesfontein Thrust (ST) and the Puros Shear Zone (PSZ), subdivide the orogen into three tectonic units: the Eastern Kaoko Zone (EKZ), the Central Kaoko Zone (CKZ) and the Western Kaoko Zone (WKZ). An important lineament, the Village Mylonite Zone (VMZ), has been identified in the WKZ. Since plutonic rocks play an important role in understanding the evolution of a mountain belt, zircons from granitoid gneisses were dated by conventional U-Pb, SHRIMP and Pb-Pb techniques to identify different age provinces. Four different age provinces were recognized within the Central and Western part of the belt, which occur in different structural positions. The VMZ seems to mark the limit between Pan-African granitic rocks east of the lineament and Palaeo- to Mesoproterozoic basement to the west. In Chapter 4 the tectonic processes are discussed that led to the Neoproterozoic architecture of the orogen. The data suggest that the Kaoko Belt experienced three main phases of deformation, D1-D3, during the Pan-African orogeny. Early structures in the central part of the study area indicate that the initial stage of collision was governed by underthrusting of the medium-grade Central Kaoko zone below the high-grade Western Kaoko zone, resulting in the development of an inverted metamorphic gradient. The early structures were overprinted by a second phase D2, which was associated with the development of the PSZ and extensive partial melting and intrusion of ~550 Ma granitic bodies in the high-grade WKZ. Transcurrent deformation continued during cooling of the entire belt, giving rise to the localized low-temperature VMZ that separates a segment of elevated Mesoproterozoic basement from the rest of the Western zone in which only Pan-African ages have so far been observed. The data suggest that the boundary between the Western and Central Kaoko zones represents a modified thrust zone, controlling the tectonic evolution of the Kaoko belt. The geodynamic evolution and the processes that generated this belt system are discussed in Chapter 5. Nd mean crustal residence ages of granitoid rocks permit subdivision of the belt into four provinces. Province I is characterised by mean crustal residence ages <1.7 Ga and is restricted to the Neoproterozoic granitoids. A wide range of initial Sr isotopic values (87Sr/86Sri = 0.7075 to 0.7225) suggests heterogeneous sources for these granitoids. The second province consists of Mesoproterozoic (1516-1448 Ma) and late Palaeo-proterozoic (1776-1701 Ma) rocks and is probably related to the Eburnian cycle with Nd model ages of 1.8-2.2 Ga. The eNd i values of these granitoids are around zero and suggest a predominantly juvenile source. Late Archaean and middle Palaeoproterozoic rocks with model ages of 2.5 to 2.8 Ga make up Province III in the central part of the belt and are distinct from two early Proterozoic samples taken near the PSZ which show even older TDM ages of ~3.3 Ga (Province IV). There is no clear geological evidence for the involvement of oceanic lithosphere in the formation of the Kaoko-Dom Feliciano orogen. Chapter 6 presents the results of isotopic analyses of garnet porphyroblasts from high-grade meta-igneous and metasedimentary rocks of the sillimanite-K-feldspar zone. Minimum P-T conditions for peak metamorphism were calculated at 731±10 °C at 6.7±1.2 kbar, substantially lower than those previously reported. A Sm-Nd garnet-whole rock errorchron obtained on a single meta-igneous rock yielded an unexpectedly old age of 692±13 Ma, which is interpreted as an inherited metamorphic age reflecting an early Pan-African granulite-facies event. The dated garnets survived a younger high-grade metamorphism that occurred between ca. 570 and 520 Ma and apparently maintained their old Sm-Nd isotopic systematics, implying that the closure temperature for garnet in this sample was higher than 730 °C. The metamorphic peak of the younger event was dated by electronmicroprobe on monazite at 567±5 Ma. From a regional viewpoint, it is possible that these granulites of igneous origin may be unrelated to the early Pan-African metamorphic evolution of the Kaoko Belt and may represent a previously unrecognised exotic terrane.

Structural evolution of the Lesser Himalayan fold-thrust belt of west central Nepal

The Lesser Himalayan fold-thrust belt on the south flank of the Jajarkot klippe in west central Nepal was mapped in detail between the Main Central thrust in the north and the Main Boundary thrust in the south. South of the Jajarkot klippe, the fold-thrust belt involves sandstone, shale and carbonate rocks that are unmetamorphosed in the foreland and increase in metamorphic grade with higher structural position to sub-greenschist facies towards the hinterland. The exposed stratigraphy is correlative with the Proterozoic Ranimata, Sangram, Galyang, Syangia Formations and Lakharpata Group of Western Nepal and overlain by the Paleozoic Tansen and Kali Gandaki Groups. Based on field mapping and cross-section construction, three distinct thrust sheets were identified separated by top-to-the-south thrust faults. From the foreland (south) to the hinterland (north), the first thrust sheet in the immediate hanging wall of the Main Boundary thrust defines an open syncline. The second thrust sheet contains a very broad synformal duplex, which is structurally stacked against the third thrust sheet containing a homoclinal panel of the oldest exposed Proterozoic stratigraphy. Outcrop scale folds throughout the study area are predominantly south vergent, open, and asymmetric reflecting the larger regional scale folding style, which corroborate the top-to-the-south deformation style seen in the faults of the region. Field techniques were complemented with microstructural and quartz crystallographic c-axis preferred orientation analyses using a petrographic microscope and a fabric analyzer, respectively. Microstructural analysis identified abundant strain-induced recrystallization textures and occasional occurrences of top-to-the-south shear-sense indicators primarily in the hinterland rocks in the immediate footwall of the Main Central Thrust. Top-to-the-south shearing is also supported by quartz crystallographic c-axis preferred orientations. Quartz recrystallization textures indicate an increase in deformation temperature towards the Main Central thrust. A line balance estimate indicates that approximately 15 km of crustal shortening was accommodated by folding and faulting in the fold-thrust belt south of the Jajarkot klippe. Additionally, estimations of shortening velocity suggest that the shortening velocity operating in this section of the fold-thrust belt between 23 to 14 Ma was slower than what is currently observed as a result of the ongoing deformation of the Sub-Himalayan fold-thrust belt.

Structural evolution in a hydrothermal reaction between Nb2O5 and NaOH solution: From Nb2O5 grains to microporous Na2Nb2O6 center dot(2)/3H2O fibers and NaNbO3 cubes

Niobium pentoxide reacts actively with concentrate NaOH solution under hydrothermal conditions at as low as 120 degrees C. The reaction ruptures the corner-sharing of NbO7 decahedra and NbO6 octahedra in the reactant Nb2O5, yielding various niobates, and the structure and composition of the niobates depend on the reaction temperature and time. The morphological evolution of the solid products in the reaction at 180 degrees C is monitored via SEM: the fine Nb2O5 powder aggregates first to irregular bars, and then niobate fibers with an aspect ratio of hundreds form. The fibers are microporous molecular sieve with a monoclinic lattice, Na2Nb2O6 center dot(2)/3H2O. The fibers are a metastable intermediate of this reaction, and they completely convert to the final product NaNbO3 Cubes in the prolonged reaction of 1 h. This study demonstrates that by carefully optimizing the reaction condition, we can selectively fabricate niobate structures of high purity, including the delicate microporous fibers, through a direct reaction between concentrated NaOH solution and Nb2O5. This synthesis route is simple and suitable for the large-scale production of the fibers. The reaction first yields poorly crystallized niobates consisting of edge-sharing NbO6 octahedra, and then the microporous fibers crystallize and grow by assembling NbO6 octahedra or clusters of NbO6 octahedra and NaO6 units. Thus, the selection of the fibril or cubic product is achieved by control of reaction kinetics. Finally, niobates with different structures exhibit remarkable differences in light absorption and photoluminescence properties. Therefore, this study is of importance for developing new functional materials by the wet-chemistry process.

Structural evolution of the Lesser Himalayan fold-thrust belt of west central Nepal

The Lesser Himalayan fold-thrust belt on the south flank of the Jajarkot klippe in west central Nepal was mapped in detail between the Main Central thrust in the north and the Main Boundary thrust in the south. South of the Jajarkot klippe, the fold-thrust belt involves sandstone, shale and carbonate rocks that are unmetamorphosed in the foreland and increase in metamorphic grade with higher structural position to sub-greenschist facies towards the hinterland. The exposed stratigraphy is correlative with the Proterozoic Ranimata, Sangram, Galyang, Syangia Formations and Lakharpata Group of Western Nepal and overlain by the Paleozoic Tansen and Kali Gandaki Groups. Based on field mapping and cross-section construction, three distinct thrust sheets were identified separated by top-to-the-south thrust faults. From the foreland (south) to the hinterland (north), the first thrust sheet in the immediate hanging wall of the Main Boundary thrust defines an open syncline. The second thrust sheet contains a very broad synformal duplex, which is structurally stacked against the third thrust sheet containing a homoclinal panel of the oldest exposed Proterozoic stratigraphy. Outcrop scale folds throughout the study area are predominantly south vergent, open, and asymmetric reflecting the larger regional scale folding style, which corroborate the top-to-the-south deformation style seen in the faults of the region. Field techniques were complemented with microstructural and quartz crystallographic c-axis preferred orientation analyses using a petrographic microscope and a fabric analyzer, respectively. Microstructural analysis identified abundant strain-induced recrystallization textures and occasional occurrences of top-to-the-south shear-sense indicators primarily in the hinterland rocks in the immediate footwall of the Main Central Thrust. Top-to-the-south shearing is also supported by quartz crystallographic c-axis preferred orientations. Quartz recrystallization textures indicate an increase in deformation temperature towards the Main Central thrust. A line balance estimate indicates that approximately 15 km of crustal shortening was accommodated by folding and faulting in the fold-thrust belt south of the Jajarkot klippe. Additionally, estimations of shortening velocity suggest that the shortening velocity operating in this section of the fold-thrust belt between 23 to 14 Ma was slower than what is currently observed as a result of the ongoing deformation of the Sub-Himalayan fold-thrust belt.

Structural evolution of spark plasma sintered AlFeCuCrMgx (x = 0, 0.5, 1, 1.7) high entropy alloys

The present paper reports synthesis of novel AlFeCuCrMgx (x = 0, 0.5, 1, 1.7 mol) high entropy alloys (HEAs) by mechanical alloying (MA) followed by spark plasma sintering (SPS). Phase evolution, microstructure and phase transformation study of the sintered alloy were investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and differential scanning calorimetry (DSC). XRD of the sintered alloys revealed the formation of two BCC phases in the AlFeCuCr alloy and more complex structures in AlFeCuCrMgx (x = 0.5, 1, 1.7) alloys containing AlFe type, BCC, and Cu2Mg type phases. TEM bright field image and selected area diffraction pattern (SAED) revealed the formation of tetragonal closed packed Cr precipitates within the Cu2Mg phase of AlFeCuCrMgx alloys (x = 0.5, 1, 1.7). DSC study of the alloys revealed no substantial phase change up to 1000 °C for AlFeCuCr alloy. Although, for x = 0.5, 1 & 1.7 phase transformation occurs at 818 °C, 885 °C & 483 °C respectively. Mg content had a significant effect on hardness, increasing to a peak hardness of 853 HVN for AlFeCuCrMg0.5 alloy before decreasing to 533 HVN for the AlFeCuCrMg1.7 alloy. The phase evolution in these alloys has been considered using thermodynamic parameters, and the structure-property relationship has also been proposed by conventional strengthening mechanisms.

Evolution of structural phase coexistence in a half doped manganite Pr0.5Sr0.5MnO3: An evidence for magneto-structural coupling

Temperature dependent x-ray diffraction measurements have been performed to understand the implications of magnetic phase coexistence on crystallographic structure in a half-doped manganite Pr0.5Sr0.5MnO3. The compound shows a structural phase transition from high-temperature tetragonal-I4/mcm to low-temperature orthorhombic-Fmmm symmetry around the ferromagnetic to antiferro-magnetic transition. Rietveld analysis shows the coexistence of these two structures emerges at high temperature within the ferromagnetic state, and persists down to lowest temperature. Below around 40 K, however, this structural evolution stops, and a significant fraction (similar to 22%) of untransformed high-temperature phase remains. This agrees with earlier magnetization study, thus establishing its magneto-structural coupling. (C) 2012 Elsevier B.V. All rights reserved.

Evidence of nanoscale structural phase separation in large bandwidth La0.2Sr0.8MnO3

We have investigated the structural evolution of La0.2Sr0.8MnO3 using temperature dependent high resolution synchrotron x-ray diffraction technique. In a wide temperature range, La0.2Sr0.8MnO3 reveals nanoscale structural inhomogeneity consisting of cubic and tetragonal phases. The present results suggest that domains of nanometer size of the tetragonal (low temperature) phase start nucleating in the cubic (high temperature) phase even above the Neel temperature (T-N). The tetragonal phase fraction increases substantially below T-N. Detailed analysis suggests that the twinned phase is tetragonal, orbital ordered, and insulating. At temperatures below 170 K, a small amount of the cubic phase is retained. The present results reveal the significance of the connectivity between the nanoscale structural phase separation with the physical properties.

Complex structural phase transitions in slightly Ca modified Na0.5Bi0.5TiO3

A temperature dependent neutron powder diffraction study, in conjunction with dielectric and ferroelectric characterization, of slightly Ca modified Na0.5Bi0.5TiO3 (NBT) revealed an instability with regard to a non-polar orthorhombic (Pbnm) distortion above room temperature. This intermediate orthorhombic phase has earlier been reported for unmodified NBT by electron diffraction studies, but has never been captured by global (x-ray/neutron) diffraction techniques. Calcium substitution seems to amplify the magnitude of this intermediate orthorhombic distortion thereby making the corresponding superlattice reflections become visible in the neutron diffraction pattern. The study revealed the following sequence of very complex structural evolution with temperature: Cc -> Cc + Pbnm -> Pbnm + P4/mbm -> P4/mbm -> Pm (3) over barm.

Microscopic description of the evolution of the local structure and an evaluation of the chemical pressure concept in a solid solution

Extended x-ray absorption fine-structure studies have been performed at the Zn K and Cd K edges for a series of solid solutions of wurtzite Zn1-xCdxS samples with x = 0.0, 0.1, 0.25, 0.5, 0.75, and 1.0, where the lattice parameter as a function of x evolves according to the well-known Vegard's law. In conjunction with extensive, large-scale first-principles electronic structure calculations with full geometry optimizations, these results establish that the percentage variation in the nearest-neighbor bond distances are lower by nearly an order of magnitude compared to what would be expected on the basis of lattice parameter variation, seriously undermining the chemical pressure concept. With experimental results that allow us to probe up to the third coordination shell distances, we provide a direct description of how the local structure, apparently inconsistent with the global structure, evolves very rapidly with interatomic distances to become consistent with it. We show that the basic features of this structural evolution with the composition can be visualized with nearly invariant Zn-S-4 and Cd-S-4 tetrahedral units retaining their structural integrity, while the tilts between these tetrahedral building blocks change with composition to conform to the changing lattice parameters according to the Vegard's law within a relatively short length scale. These results underline the limits of applicability of the chemical pressure concept that has been a favored tool of experimentalists to control physical properties of a large variety of condensed matter systems.