Éditeur(s) : HAL CCSD Elsevier
Résumé : International audience
The nucleation and growth processes of spherulitic alkali feldspar have been investigated in this study through X-ray microtomography and electron backscatter diffraction (EBSD) data. Here we present the first data on Shape Preferred Orientation (SPO) and Crystal Preferred Orientation (CPO) of alkali feldspar within spherulites. The analysis of synchrotron X-ray microtomography and EBSD datasets allowed us to study the morphometric characteristics of spherulites in trachytic melts in quantitative fashion, highlighting the three-dimensional shape, preferred orientation, branching of lamellae and crystal twinning, providing insights about the nucleation mechanism involved in the crystallization of the spherulites. The nucleation starts with a heterogeneous nucleus (pre-existing crystal or bubble) and subsequently it evolves forming “bow tie” morphologies, reaching radially spherulitic shapes in few hours. Since each lamella within spherulite is also twinned, these synthetic spherulites cannot be considered as single nuclei but crystal aggregates originated by heterogeneous nucleation. A twin boundary may have a lower energy than general crystal–crystal boundaries and many of the twinned grains show evidence of strong local bending which, combined with twin plane, creates local sites for heterogeneous nucleation.This study shows that the growth rates of the lamellae (10− 6–10− 7 cm/s) in spherulites are either similar or slightly higher than that for single crystals by up to one order of magnitude. Furthermore, the highest volumetric growth rates (10− 11–10− 12 cm3/s) show that the alkali feldspar within spherulites can grow fast reaching a volumetric size of ~ 10 μm3 in 1 s.
ISSN: 0024-4937

hal-01172356
https://hal.archives-ouvertes.fr/hal-01172356
DOI : 10.1016/j.lithos.2014.12.003

Éditeur(s) : HAL CCSD Elsevier
Résumé : International audience
Experimentally Assisted Molecular Modelling (EAMM) is an original approach for predicting the structure of organic micro-crystals and deducing their habit in the presence of various solvents and additives. It is applied here in the case of n-octylamino-nitrobenzoxadiazole (nOA-NBD), a fluorescent compound. This general approach is first of all described and validated by its blind application to three known and closely-related crystals. Then, the whole process is applied to predict the molecular crystal generated by n-octylamino-NBD, including the molecule conformation, its structure (cell parameters, molecular packing, X-ray powder diagrams) and its theoretical plus actual habits in the presence of a solvent (p-xylene) and two additives (acetic acid and n-dodecane). The conformation of the predicted molecule is validated by comparison with two similar molecules embedded in observable crystals. Then, the choice between two proposed structures (with the same energy and two equiprobable packings) is based on the comparison between experimental and re-computed X-ray powder diffraction diagrams, and also on the interpretation of an actual TEM image in the light of the proposed cell parameters. This choice is confirmed by the comparison between the vapour-grown face development (proposed by the BFDH or the attachment energy models) and the actual face development in a pure solvent. Finally, the actual habit deduced from comparing the crystal attachment energy with the adsorption energy of solvent or additive molecules is validated by SEM images of NBD micro-crystals in presence of the solvent alone or in presence of both additives. In conclusion, the EAMM approach appears to be a decisive tool for quickly simulating structural and habit properties of the molecular crystals, accessible or not by experimentation. Thus, a numerical selection of molecules becomes possible in view of deriving organic materials with predetermined properties, such as the fluorescence properties of the compound considered in the present study.
ISSN: 0022-0248

hal-00857894
https://hal.archives-ouvertes.fr/hal-00857894
DOI : 10.1016/j.jcrysgro.2011.07.035

Éditeur(s) : HAL CCSD Oxford University Press (OUP)
Résumé : International audience
Two types of olivine occur in kimberlites from Greenland, Canada and southern Africa. The first, xenocrystic olivine, displays several different forms. Most distinctive are 'nodules', a term we use to describe the large (1-5 mm), rounded, single crystals or polycrystalline aggregates that are a common constituent of many kimberlites. Olivine compositions are uniform within single nodules but vary widely from nodule to nodule, from Fo81 to 93. Within many nodules, sub- to euhedral asymmetric tablets have grown within larger anhedral olivine grains. Dislocation structures, particularly in the anhedral grains, demonstrate that this olivine was deformed before being incorporated into the kimberlite magma. Olivine grains in the kimberlite matrix between the nodules have morphologies similar to those of the tablets, suggesting that most matrix olivine grains are parts of disaggregated nodules. We propose that a sub- to euhedral form is not sufficient to identify phenocrysts in kimberlites and provide some criteria, based on morphology, internal deformation and composition, that distinguish phenocrysts from xenocrysts. The second type of olivine is restricted to rims surrounding xenocrystic grains. Only this olivine crystallized from the kimberlite magma. Major and trace element data for the rim olivine are used to calculate the composition of the parental kimberlite liquid, which is found to contain between about 20 and 30% MgO. The bulk compositions of many kimberlites contain higher MgO contents as a result of the presence of xenocrystic olivine. The monomineralic, dunitic, character of the nodules, and the wide range from Fo-rich to Fo-poor olivine compositions, provide major constraints on the origin of the nodules. Dunite is a relatively rare rock in the mantle and where present its olivine is persistently Fo-rich. The dunitic source of the nodules in kimberlites lacked minerals such as pyroxene and an aluminous phase, which make up about half of most mantle-derived rocks. It appears that these minerals were removed from the mantle peridotite that was to become the source of the nodules, and the Fo content of the retained olivine was modified during interaction with CO2-rich fluids whose arrival at the base of the lithosphere immediately preceded the passage of the kimberlite magmas. Fragments of the resultant dunite were entrained into the kimberlite, where they were retained both as intact nodules and as disaggregated grains in the matrix.
ISSN: 0022-3530

insu-00543321
https://hal-insu.archives-ouvertes.fr/insu-00543321
BIBCODE : 10.1093/petrology/egp080
DOI : 10.1093/petrology/egp080

Éditeur(s) : HAL CCSD MDPI
Résumé : International audience
This work investigates the structural formation and analyses of titania membranes (TM) prepared using different vacuum exposure times for molecular weight (MW) cut-off performance and oil/water separation. Titania membranes were synthesized via a sol-gel method and coated on macroporous alumina tubes followed by exposure to a vacuum between 30 and 1200 s and then calcined at 400 °C. X-ray diffraction and nitrogen adsorption analyses showed that the crystallite size and particle size of titania increased as a function of vacuum time. All the TM membranes were mesoporous with an average pore diameter of ~3.6 nm with an anatase crystal morphology. Water, glucose, sucrose, and polyvinylpyrrolidone with 40 and 360 kDa (PVP-40 kDa and PVP-360 kDa) were used as feed solutions for MW cut-off and hexadecane solution for oil filtration investigation. The TM membranes were not able to separate glucose and sucrose, thus indicating the membrane pore sizes are larger than the kinetic diameter of sucrose of 0.9 nm, irrespective of vacuum exposure time. They also showed only moderate rejection (20%) of the smaller PVP-40 kDa, however, all the membranes were able to obtain an excellent rejection of near 100% for the larger PVP-360 kDa molecule. Furthermore, the TM membranes were tested for the separation of oil emulsions with a high concentration of oil (3000 ppm), reaching high oil rejections of more than 90% of oil. In general, the water fluxes increased with the vacuum exposure time indicating a pore structural tailoring effect. It is therefore proposed that a mechanism of pore size tailoring was formed by an interconnected network of Ti-O-Ti nanoparticles with inter-particle voids, which increased as TiO2 nanoparticle size increased as a function of vacuum exposure time, and thus reduced the water transport resistance through the TM membranes. © 2016 by the authors.
ISSN: 1996-1944

hal-01683214
https://hal.univ-antilles.fr/hal-01683214
DOI : 10.3390/ma9110938

Éditeur(s) : HAL CCSD Elsevier
Résumé : International audience
The Longmen Shan (Sichuan, China) is characterised by an unusual morphology which results from a Triassic prism tectonics and a more recent Neogene thick-skin thrusting. Among its specific features is the high elevation of the internal zones in continuity with the Songpan Garze fold-and-thrust belt (SG), which is associated with an abrupt 20 km Moho offset between the Sichuan Basin and the Tibetan plateau as revealed by the analysis of teleseismic data acquired by a dense seismic network. The jump in crustal thickness is located at the apex of the Wenchuan shear zone (WSZ) and marks the western boundary of the metamorphosed units of SG characterized by temperatures varying from 590 degrees C down to 300 degrees C as commonly observed in mature accretionary wedges. Both the structural style marked by intense shortening in tight kink folds and geophysical data suggest the presence of an horizontal discontinuity at similar to 15 km depth over a thick crust (similar to 63 km).;The Longmen Shan east of the WSZ is characterized by thick-skin detachment which thrusts the internal sedimentary units and the Proterozoic basement over the series of the Sichuan Basin deposited on a thinner crust of similar to 44 km thick. The major front is the Beichuan Fault Zone (BFZ) which brought the internal zones onto Triassic and Jurassic series with lower temperatures (less than 400 degrees C). Locally, temperatures of similar to 425 degrees C are found just below the klippes.;These results are in agreement with an original contact of the SG zone represented by an accretionary wedge of sediments thrusted over the margin of the continental crust of the Yangtze craton in the early stage (Indosinian) of the evolution. The present-day slow E-W component of the convergence, added to the difference in crustal thickness caused the Yangtze crust to indent the Songpan Tibetan crust which was softened by a high thermal regime. As a response the edge of the Tibet crust was inflated to the bottom (up to 70 km), whereas to the top, the crystalline massif were exhumed and pushed the deformation eastward as emerging and blind thrusts. This configuration reflects a moderate shortening of the crust which behaves as a soft thick material abutting the resistant and cold Yangtze crust.
ISSN: 0040-1951

hal-00534849
https://hal.archives-ouvertes.fr/hal-00534849
DOI : 10.1016/j.tecto.2010.03.018

Éditeur(s) : HAL CCSD Elsevier
Résumé : International audience
The detailed morphology and internal structure of the Calabrian accretionary wedge and adjacent Eastern Sicily margin are imaged in unprecedented detail by a combined dataset of multi-beam bathymetry and high-resolution seismic profiles. The bathymetric data represent the results of 6 recent marine geophysical surveys since 2010 as well as a compilation of earlier surveys presented as a 2 arc-sec (60 m) grid. Several distinct morpho-tectonic provinces are identified including: the deeply incised Malta–Hyblean Escarpment, numerous submarine canyons, broad regions of relatively flat seafloor dominated by fields of sediment waves, the gently undulating anticlinal fold-and-thrust belts of the external Calabrian accretionary wedge and the adjacent portion of the Western Mediterranean Ridge. The Calabrian arc can be divided into 4 domains (from SE to NW): 1) the undeformed Ionian abyssal plain, 2) the external evaporitic wedge, 3) the internal clastic wedge, 4) the Calabrian backstop (Variscan crystalline basement). The Calabrian accretionary wedge can also be divided laterally into two major lobes, the NE- and the SW lobes, and two minor lobes. The kinematics of the limit between the two major lobes is investigated and shown to be sinistral in the external (evaporitic) wedge. A network of radial slip lines within the southernmost external wedge unequivocally demonstrate ongoing dextral displacement of a rigid indenter (representing the corner of the clastic wedge) into the evaporitic wedge thereby confirming the geodynamic model of an active lateral slab tear fault here off eastern Sicily. The slab tear produces a series of major sub-parallel dextral strike-slip faults offshore Mt. Etna and south of the Straits of Messina consistent with the relative motions between Calabria and the Peloritan domain (NE Sicily). Abundant strike-slip faulting, and wide-spread folding and thrusting observed throughout the entire accretionary wedge, indicate regional shortening between the Ionian abyssal plain (foreland) and the Calabrian–Peloritan backstop caused by active subduction.
ISSN: 0012-821X

hal-01523990
https://hal.archives-ouvertes.fr/hal-01523990
DOI : 10.1016/j.epsl.2016.12.020

Éditeur(s) : HAL CCSD Public Library of Science
Résumé : International audience
Among persisting questions on bone calcification, a major one is the link between protein expression and mineral deposition. A cell culture system is here proposed opening new integrative studies on biomineralization, improving our knowledge on the role played by non-collagenous proteins in bone. This experimental in vitro model consisted in human primary osteoblasts cultured for 60 days at the surface of a 3D collagen scaffold mimicking an osteoid matrix. Various techniques were used to analyze the results at the cellular and molecular level (adhesion and viability tests, histology and electron microscopy, RT-and qPCR) and to characterize the mineral phase (histological staining, EDX, ATG, SAED and RMN). On long term cultures human bone cells seeded on the osteoid-like matrix displayed a clear osteoblast phenotype as revealed by the osteoblast-like morphology, expression of specific protein such as alkaline phosphatase and expression of eight genes classically considered as osteoblast markers, including BGLAP, COL1A1, and BMP2. Von Kossa and alizarine red allowed us to identify divalent calcium ions at the surface of the matrix, EDX revealed the correct Ca/P ratio, and SAED showed the apatite crystal diffraction pattern. In addition RMN led to the conclusion that contaminant phases were absent and that the hydration state of the mineral was similar to fresh bone. A temporal correlation was established between quantified gene expression of DMP1 and IBSP, and the presence of hydroxyapatite, confirming the contribution of these proteins to the mineralization process. In parallel a difference was observed in the expression pattern of SPP1 and BGLAP, which questioned their attributed role in the literature. The present model opens new experimental possibilities to study spatio-temporal relations between bone cells, dense collagen scaffolds, NCPs and hydroxyapatite mineral deposition. It also emphasizes the importance of high collagen density environment in bone cell physiology.
ISSN: 1932-6203

hal-01142641
http://hal.upmc.fr/hal-01142641
http://hal.upmc.fr/hal-01142641/document
http://hal.upmc.fr/hal-01142641/file/Silvent_2013_Collagen.pdf
DOI : 10.1371/journal.pone.0057344

Éditeur(s) : HAL CCSD National Research Council Canada
Résumé : International audience
The spadix of Arum italicum Miller consists of two main parts: a clavate sterile portion (appendix) and a cylindroid fertile portion. In the fertile portion with both male and female zones, there are two zones of sterile flowers (bristles). The basal portion of bristles is surrounded by a verrucose structure consisting of a mass of tissular excrescences. During early stages of development, there is no free space between the different zones of the inflorescence. The elongation of the inflorescence axis is what eventually separates the different zones from each other. There are no atypical flowers that are morphologically intermediate between male and female flowers as is the case in other genera of Aroideae (e.g., Cercestis, Philodendron, Schismatoglottis). The structure of the bristles in the inflorescences of Arum does not correspond to any type of atypical flower (unisexual or bisexual) that has been analysed previously in the Araceae. From a developmental point of view, it is not possible to determine if the bristles correspond to aborted or modified female or male flowers. In the early stages of development, the stamens, staminodes, and appendix are covered by globular masses of extracellular calcium oxalate crystals.
Le spadice de l’Arum italicum comporte deux parties principales : une portion claviforme stérile (appendice) et une portion cylindroïde fertile. Dans la portion fertile avec zones mâles et femelles, il y a deux zones de fleurs stériles (soies). La portion basales des soies est entourée par une structure verruqueuse, constituée d’une masse d’excroissances tissulaires. Aux premiers stades du développement, il n’y a pas d’espace libre entre les différentes zones de l’inflorescence. L’élongation de l’axe de l’inflorescence est ce qui sépare éventuellement les différentes zones l’une de l’autre. Il n’y pas de fleurs atypiques intermédiaires entre des fleurs mâles et des fleurs femelles, comme c’est le cas dans d’autres genres d’Aroideae (p. ex. Cercestis, Philodendron, Schismataglottis). La structure des soies chez les inflorescences de l’Arum ne correspond à aucune des fleurs atypiques (unisexuées ou bisexuées) qui ont précédemment été analysées chez les Araceae. Considérant le développement, il n’est pas possible de déterminer si les soies correspondent à des modifications de fleurs femelles ou mâles avortées. Aux premiers stades du développement, les étamines, les staminodes et les appendices sont couverts de masses globuleuses constituées de cristaux extracellulaires d’oxalate de calcium.
ISSN: 0008-4026

hal-01206194
https://hal.archives-ouvertes.fr/hal-01206194