Triple-quantum correlation NMR experiments in solids using J-couplings

We show that triple-quantum–single-quantum (TQ–SQ) correlation spectra of crystalline and disordered solids can be obtained under MAS using pulse sequences based on through-bond J-couplings. The feasibility of the experiments in coupled spin-1/2 systems is demonstrated for fully 13C-labelled L-alanine and Pb3P4O13 crystalline compounds, considered as model three-spin and four-spin systems, respectively. In the case of phosphate glasses, we show that the obtained TQ–SQ correlation spectra provide an improved description of the glass forming network connectivities and of the chain length distribution in the disordered network

Chimie : un vecteur vert

National audienceLes faits, longtemps sujets à discussion, sont désormais là. Le cinquième rapport du GIEC (2013) qualifie d'« extrêmement probable » un lien entre les dérèglements climatiques observés depuis 1950 et les variations de la composition de l'atmosphère terrestre provoqués par l'augmentation forte et récente des activités anthropiques. L'implication directe des gaz à effet de serre dans les phénomènes climatiques, et en particulier du dioxyde de carbone dont la concentration a augmenté de 40 % depuis l'époque préindustrielle, est toute aussi probable..

Structural characterization of water-bearing silicate and aluminosilicate glasses by high-resolution solid-state NMR

Various one- and two-dimensional high-resolution solid-state NMR techniques have been applied to hydrous silicate and aluminosilicate glasses: simple acquisition, cross-polarization (CP-MAS), heteronuclear correlation (HETCOR), dipolar dephasing, spin counting, double-quantum correlation, and rotational echo double resonance (REDOR). The comparison of the results obtained for sodium tetrasilicate and phonolite glasses suggests that the water incorporation mechanisms are qualitatively similar for these two compositions. From proton NMR experiments, we observe no evidence of proton clustering and a wide range of chemical shifts ranging from 0 to 16 ppm, even for the aluminosilicate phonolite glass, identifying at least three types of hydroxyl (OH) protons in addition to molecular H2O. This variety of OH groups can be discussed in terms of hydrogen bonding strength. For both compositions, the results indicate some depolymerization of the tetrahedral network, but the picture cannot be so simple as to completely exclude any of the different previously proposed models for water incorporation in silicate glasses

Atomic scale structure of amorphous aluminum oxyhydroxide, oxide and oxycarbide films probed by very high field 27Al nuclear magnetic resonance

The atomic scale structure of aluminum in amorphous alumina films processed by direct liquid injection chemical vapor deposition from aluminum tri-isopropoxide (ATI) and dimethyl isopropoxide (DMAI) is investigated by solid-state 27Al nuclear magnetic resonance (SSNMR) using a very high magnetic field of 20.0 T. This study is performed as a function of the deposition temperature in the range 300–560 °C, 150–450 °C, and 500–700 °C, for the films processed from ATI, DMAI (+H2O), and DMAI (+O2), respectively. While the majority of the films are composed of stoichiometric aluminum oxide, other samples are partially or fully hydroxylated at low temperature, or contain carbidic carbon when processed from DMAI above 500 °C. The quantitative analysis of the SSNMR experiments reveals that the local structure of these films is built from AlO4, AlO5, AlO6 and Al(O,C)4 units with minor proportions of the 6-fold aluminum coordination and significant amounts of oxycarbides in the films processed from DMAI (+O2). The aluminum coordination distribution as well as the chemical shift distribution indicate that the films processed from DMAI present a higher degree of structural disorder compared to the films processed from ATI. Hydroxylation leads to an increase of the 6-fold coordination resulting from the trend of OH groups to integrate into AlO6 units. The evidence of an additional environment in films processed from DMAI (+O2) by 27Al SSNMR and first-principle NMR calculations on Al4C3 and Al4O4C crystal structures supports that carbon is located in Al(O,C)4 units. The concentration of this coordination environment strongly increases with increasing process temperature from 600 to 700 °C favoring a highly disordered structure and preventing from crystallizing into γ-alumina. The obtained results are a valuable guide to the selection of process conditions for the CVD of amorphous alumina films with regard to targeted applications

Temperature-Dependent 4‑, 5- and 6‑Fold Coordination of Aluminum in MOCVD-Grown Amorphous Alumina Films: A Very High Field 27Al-NMR study

The only easy way to prepare amorphous alumina is via thin film deposition. For this reason, the disorder in amorphous alumina has not yet been fully investigated. We have used very high-field (20 T) solid state 27Al NMR spectroscopy to analyze the structural modifications of amorphous alumina thin films with deposition temperature (Td). The films were deposited by metalorganic chemical vapor deposition in the Td range of 360−720 °C. Depending on Td, film composition is either AlO1+x(OH)1−2x (0 ≤ x ≤ 0.5) or Al2O3. From 27Al 1D magic angle spinning(MAS) and 2D multiple-quantum magic angle spinning (MQMAS) NMR analyses, the films grown between 360 and 600 °C contain between 38 and 43 atom % of 5-fold coordinated aluminum sites ([5]Al). The percentages of [6]Al and [4]Al sites vary spectacularly, reaching their respective minimum (5 atom %) and maximum (54 atom%) around 515 °C. The analysis of a very thin film (85 nm) of Al2O3 reveals the presence of metallic aluminum at the interface with the substrate and suggests that the respective percentages of [n]Al sites slightly differ from those in thicker films. The observed Td dependence of amorphous alumina structure can be correlated with that of film properties previously reported,namely, Young’s modulus, hardness, and corrosion protection

Temperature Dependent 4-, 5- and 6-Fold Coordination of Aluminum in MOCVD-Grown Amorphous Alumina Films: From Local Coordination to Material Properties

Aluminum 5-fold coordination coexisting with 4-and 6-fold coordination structurally characterizes amorphous aluminum oxide. For nearly 30 years now, 27Al MAS NMR has enabled to detect and later on to quantify this feature thanks to advances in high-resolution instrumentation. The Introduction shortly reviews the results of investigations of 5-coordinate aluminum in amorphous alumina through NMR analysis. Aluminum oxide is not a glass-forming oxide. A convenient way to obtain the amorphous state is by thin film deposition. We present here 27Al NMR analysis of a series of thin films of aluminum oxide prepared by metalorganic chemical vapor deposition (MOCVD) in the temperature range 360 ≤ Td ≤ 720 °C. In this range, low Td yield OH-containing films, while high Td yield nanocrystallites-containing films. The variation of the [4]Al, [5]Al and [6]Al content with Td is presented and discussed. It is correlated with the Td dependence of mechanical and corrosion protection properties. These properties are optimal when the structural disorder is to the utmost. Al coordination dependence on film thickness and the formation of metallic aluminum during the deposition process are also presented

Rearrangement of the structure during nucleation of a cordierite glass doped with TiO2

Ordering of disordered materials occurs during the activated process of nucleation that requires the formation of critical clusters that have to surmount a thermodynamic barrier. The characterization of these clusters is experimentally challenging but mandatory to improve nucleation theory. In this paper, the nucleation of a magnesium aluminosilicate glass containing the nucleating oxide TiO2 is investigated using neutron scattering with Ti isotopic substitution and 27Al NMR. We identified the structural changes induced by the formation of crystals around Ti atoms and evidenced important structural reorganization of the glassy matrix

Laser-heated high-temperature NMR - a time-resolution study

International audienc

Percolation channels:A universal idea to describe the atomic structure and dynamics of glasses and melts

Understanding the links between chemical composition, nano-structure and the dynamic properties of silicate melts and glasses is fundamental to both Earth and Materials Sciences. Central to this is whether the distribution of mobile metallic ions is random or not. In silicate systems, such as window glass, it is well-established that the short-range structure is not random but metal ions cluster, forming percolation channels through a partly broken network of corner-sharing SiO4 tetrahedra. In alumino-silicate glasses and melts, extensively used in industry and representing most of the Earth magmas, metal ions compensate the electrical charge deficit of AlO4? tetrahedra, but until now clustering has not been confirmed. Here we report how major changes in melt viscosity, together with glass Raman and Nuclear Magnetic Resonance measurements and Molecular Dynamics simulations, demonstrate that metal ions nano-segregate into percolation channels, making this a universal phenomenon of oxide glasses and melts. Furthermore, we can explain how, in both single and mixed alkali compositions, metal ion clustering and percolation radically affect melt mobility, central to understanding industrial and geological processespublishersversionPeer reviewe

La Recherche en Chimie aux Frontières de la Connaissance

National audienceMixed research units are building blocks, flexible but permanent, in rapidly evolving fields of research. Several measures shape the activities of research teams and thus give rise to “poles of research”. They also help consolidate national networks, identify strong points, boost the sharing of top-level equipment and stimulate collaboration between academics and industrialists. Chemists’ diverse activities lie on a thematic continuum that reaches beyond disciplinary bounds and crisscrosses the industrial and academic spheres. The dichotomy between, on the one hand, the structure in terms of disciplines used by the authorities in charge and, on the other hand, the socioeconomic priorities set by funding agencies should enable scientists to pursue topnotch research. It should also lead to the emergence of new concepts corresponding to breakthroughs that will reshape chemistry in the future.L’Unité Mixte de Recherche est la brique élémentaire, souple et pérenne d’un paysage de la recherche en évolution rapide. De nombreux dispositifs viennent structurer l’activité de ces équipes pour faire émerger des pôles de recherche, consolider le maillage des réseaux nationaux, identifier les points forts, mutualiser des équipements de haut niveau et promouvoir les collaborations académiques et industrielles. La diversité de l’activité des chimistes se place dans un continuum thématique dépassant les frontières disciplinaires et traversant les mondes académiques et industriels. La dichotomie entre les structures disciplinaires de nos tutelles et l’affichage de défis socio-économiques par les agences de financement doivent permettre aux acteurs de mettre en œuvre des recherches de très haut niveau tout en favorisant l’émergence et la description de nouveaux concepts en rupture qui permettront de construire la chimie de demain