Mechanochemical Induced Structure Transformations in Lithium Titanates: A Detailed PXRD and 6Li MAS NMR Study

Lithium titanates are used in various applications, such as anode materials for lithium intercalation (Li4Ti5O12) or breeding materials in fusion reactors (Li2TiO3). Here, we report the formation of nano-crystalline lithium titanates by a mechanochemical approach and present a deeper insight into their structural characteristics by X-ray diffraction (XRD) and solid-state NMR spectroscopy. The compounds were synthesized in a high-energy planetary ball mill with varying milling parameters and different grinding tools. NaCl type Li2TiO3 (α-Li2TiO3) was formed by dry milling of lithium hydroxide with titania (rutile or anatase) and by a milling induced structure transformation of monoclinic β-Li2TiO3 or spinel type Li4Ti5O12. Heating of mechanochemical prepared α-Li2TiO3 induces a phase transformation to the monoclinic phase similar to hydrothermal reaction products, but a higher thermal stability was observed for the mechanochemical formed product. Microstructure and crystallographic structure were characterized by XRD via Rietveld analysis. Detailed phase analysis shows the formation of the cubic phase from the various educts. A set of two lattice parameters for α-Li2TiO3 was refined, depending on the presence of OH− during the milling process. An average crystallite size of less than 15 nm was observed for the mechanochemical generated products. The local Li environment detected by 6Li NMR revealed Li defects in the form of tetrahedral instead of octahedral site occupation. Subsequent adjustment of the structural model for Rietveld refinement leads to better fits, supporting this interpretatio

Mechanochemical Induced Structure Transformations in Lithium Titanates: A Detailed PXRD and 6Li MAS NMR Study

Lithium titanates are used in various applications, such as anode materials for lithium intercalation (Li4Ti5O12) or breeding materials in fusion reactors (Li2TiO3). Here, we report the formation of nano-crystalline lithium titanates by a mechanochemical approach and present a deeper insight into their structural characteristics by X-ray diffraction (XRD) and solid-state NMR spectroscopy. The compounds were synthesized in a high-energy planetary ball mill with varying milling parameters and different grinding tools. NaCl type Li2TiO3 (α-Li2TiO3) was formed by dry milling of lithium hydroxide with titania (rutile or anatase) and by a milling induced structure transformation of monoclinic β-Li2TiO3 or spinel type Li4Ti5O12. Heating of mechanochemical prepared α-Li2TiO3 induces a phase transformation to the monoclinic phase similar to hydrothermal reaction products, but a higher thermal stability was observed for the mechanochemical formed product. Microstructure and crystallographic structure were characterized by XRD via Rietveld analysis. Detailed phase analysis shows the formation of the cubic phase from the various educts. A set of two lattice parameters for α-Li2TiO3 was refined, depending on the presence of OH− during the milling process. An average crystallite size of less than 15 nm was observed for the mechanochemical generated products. The local Li environment detected by 6Li NMR revealed Li defects in the form of tetrahedral instead of octahedral site occupation. Subsequent adjustment of the structural model for Rietveld refinement leads to better fits, supporting this interpretatio

Minimum fuel round trip from a L2L_2 Earth-Moon Halo orbit to Asteroid 2006 RH120_{120}

International audienceThe goal of this paper is to design a spacecraft round trip transfer from a parking orbit to Asteroid 2006\;RH$_{120}$, during its capture time by Earth's gravity, while maximizing the final mass or equivalently minimizing the delta-v. The parking orbit is chosen as a Halo orbit around the Earth-Moon $L_2$ libration point. The round-trip transfer is composed of three portions: a rendezvous transfer departing from the parking orbit to reach 2006\;RH$_{120}$, a lock-in portion with the spacecraft following the asteroid orbit, and finally a return transfer to $L_2$. An indirect method based on the maximum principle is used for our numerical calculations. To partially address the issue of local minima, we restrict the control strategy to reflect an actuation corresponding to up to three constant thrust arcs during each portion of the transfer. The model considered here is the circular restricted four-body problem (CR4BP) with the Sun considered as a perturbation of the Earth-Moon circular restricted three body problem. A shooting method is applied to solve numerically this problem, and the rendezvous point to and departure point from \RH\ are optimized using a time discretization of the trajectory of \RH

Reactive Milling Induced Structure Changes in Phenylphosphonic Acid Functionalized LiMn2O4 Nanocrystals - Synthesis, Rietveld Refinement, and Thermal Stability

Spinel LiMn2O4 formed in a solid‐state reaction was treated with a high energy planetary ball mill. A mechanochemical in situ surface functionalization of the nanocrystallites with a size smaller than 10 nm was achieved by addition of phenylphosphonic acid. The functionalization was proven by infrared spectroscopy and it can be shown that it prevents the formation of Mn2O3 during the milling process. Structural changes of the samples were investigated via XRD and Rietveld refinement. Mild milling conditions induce an anisotropic broadening of the reflections caused by a distribution of lattice parameters. In this first stage, we propose a structure model based on orthorhombic LiMn2O4. DSC and in situ XRD measurements also verify the presence of the orthorhombic low temperature phase. Medium milling conditions induce a change of intensities, correlated to a cation disorder. Harsher milling conditions induce the transformation to a tetragonal phase. The thermal stability of the formed phases was investigated via in situ high temperature XRD. The reformation of cubic spinel is observed in all samples; however, the transition point depends on the previous milling parameters

Snow as a driving factor of rock surface temperatures in steep rough rock walls

Observations show that considerable amounts of snow can accumulate in steep, rough rock walls. The heterogeneously distributed snow cover significantly affects the surface energy balance and hence the thermal regime of the rock walls.To assess the small-scale variability of snow depth and rock temperatures in steep north and south facing rock walls, a spatially distributed multi-method approach is applied at Gemsstock, Switzerland, combining 35 continuous near-surface rock temperature measurements, high resolution snow depth observations using terrestrial laser scanning, as well as in-situ snow pit investigations.The thermal regime of the rock surface is highly dependent on short- and longwave radiation, albedo, surface roughness, snow depth and on snow distribution in time and space. Around 2 m of snow can accumulate on slopes with angles up to 75°, due to micro-topographic structures like ledges. Hence, contrasts in mean annual rock surface temperature between the north and the south facing slopes are less than 4 °C. However, significant small-scale variability of up to 10 °C in mean daily rock surface temperature occurs within a few metres over the rock walls due to the variable snow distribution, revealing the heterogeneity and complexity of the thermal regime at a very local scale. In addition, multiple linear regression could explain up to 77% of near‐surface rock temperature variability, which underlines the importance of radiation and snow depth and thus also of the topography.In the rock faces the thermal insulation of the ground starts with snow depths exceeding 0.2 m. This is due to the high thermal resistance of a less densely packed snow cover, especially in the north facing slope. Additionally, aspect induced differences of snow cover characteristics and consequently thermal conductivities are observed in the rock walls

Thermal and mechanical responses resulting from spatial and temporal snow cover variability in permafrost rock slopes, steintaelli, swiss alps

The aim of this study is to investigate the influence of snow on permafrost and rock stability at the Steintaelli (Swiss Alps). Snow depth distribution was observed using terrestrial laser scanning and time-lapse photography. The influence of snow on the rock thermal regime was investigated using near-surface rock temperature measurements, seismic refraction tomography and one-dimensional thermal modelling. Rock kinematics were recorded with crackmeters. The distribution of snow depth was strongly determined by rock slope micro-topography. Snow accumulated to thicknesses of up to 3.8 m on less steep rock slopes (<50°) and ledges, gradually covering steeper (up to 75°) slopes above. A perennial snow cornice at the flat ridge, as well as the long-lasting snow cover in shaded, gently inclined areas, prevented deep active-layer thaw, while patchy snow cover resulted in a deeper active-layer beneath steep rock slopes. The rock mechanical regime was also snow-controlled. During snow-free periods, high-frequency thermal expansion and contraction occurred. Rock temperature locally dropped to -10 °C, resulting in thermal contraction of the rock slopes. Snow cover insulation maintained temperatures in the frost- cracking window and favoured ice segregation. Daily thermal-induced and seasonal ice-induced fracture kinematics were dominant, and their repetitive occurrence destabilises the rock slope and can potentially lead to failure

Inhibition of fatty acid synthase sensitizes prostate cancer cells to radiotherapy

Many common human cancers, including colon, prostate and breast cancer, express high levels of fatty acid synthase compared to normal human tissues. This elevated expression is associated with protection against apoptosis, increased metastasis and poor prognosis. Inhibitors of fatty acid synthase, such as the cerulenin synthetic analog C75, decrease prostate cancer cell proliferation, increase apoptosis and decrease tumor growth in experimental models. Although radiotherapy is widely used in the treatment of prostate cancer patients, the risk of damage to neighboring normal organs limits the radiation dose that can be delivered. In this study, we examined the potential of fatty acid synthase inhibition to sensitize prostate cancer cells to radiotherapy. The efficacy of C75 alone or in combination with X irradiation was examined in monolayers and in multicellular tumor spheroids. Treatment with C75 alone decreased clonogenic survival, an effect that was abrogated by the antioxidant. C75 treatment also delayed spheroid growth in a concentration-dependent manner. The radiosensitizing effect of C75 was indicated by combination index values between 0.65 and 0.71 and the reduced surviving fraction of clonogens, in response to 2 Gy X irradiation, from 0.51 to 0.30 and 0.11 in the presence of 25 and 35 μM C75, respectively. This increased sensitivity to radiation was reduced by the presence of the antioxidant. The C75 treatment also enhanced the spheroid growth delay induced by X irradiation in a supra-additive manner. The level of radiation-induced apoptosis in prostate cancer cells was increased further by C75, which induced cell cycle arrest in the G2/M phase, but only at a concentration greater than that required for radiosensitization. Radiation-induced G2/M blockade was not affected by C75 treatment. These results suggest the potential use of fatty acid synthase inhibition to enhance the efficacy of radiotherapy of prostate carcinoma and that C75-dependent cell cycle arrest is not responsible for its radiosensitizing effect

Seasonally intermittent water flow through deep fractures in an Alpine Rock Ridge: Gemsstock, Central Swiss Alps

Geological investigations and seismic refraction tomography reveal a series of 70° steep, parallel and continuous fractures at 2950 m asl within the Gemsstock rock ridge (Central Swiss Alps), at the lower fringe of alpine permafrost. Temperature measurements in a 40 m horizontal borehole through the base of the ridge show that whilst conductive heat transfer dominates within the rock mass, brief negative and positive temperature anomalies are registered in summer. These have very small amplitudes and coincide with summer rainfall events lasting longer than 12 h. In contrast, a complete lack of anomalous thermal signals during spring snowmelt suggests that runoff does not penetrate the open joints, despite high snow water equivalents of around 400 mm. This is attributed to the development of an approximately 20 cm thick, continuous and impermeable basal ice layer which forms at the interface between the snow cover and the cold rock on the shady North facing rock wall during snowmelt. Spring snowmelt water therefore does not affect rock temperatures in the centre of the rock mass, despite the presence of deep open joints. The mechanical impact of snowmelt infiltration on rock wall stability at depth is thus assumed to be negligible at this site

Distributed snow and rock temperature modelling in steep rock walls using Alpine3D

In this study we modelled the influence of the spatially and temporally heterogeneous snow cover on the surface energy balance and thus on rock temperatures in two rugged, steep rock walls on the Gemsstock ridge in the central Swiss Alps. The heterogeneous snow depth distribution in the rock walls was introduced to the distributed, process-based energy balance model Alpine3D with a precipitation scaling method based on snow depth data measured by terrestrial laser scanning. The influence of the snow cover on rock temperatures was investigated by comparing a snow-covered model scenario (precipitation input provided by precipitation scaling) with a snow-free (zero precipitation input) one. Model uncertainties are discussed and evaluated at both the point and spatial scales against 22 near-surface rock temperature measurements and high-resolution snow depth data from winter terrestrial laser scans.In the rough rock walls, the heterogeneously distributed snow cover was moderately well reproduced by Alpine3D with mean absolute errors ranging between 0.31 and 0.81 m. However, snow cover duration was reproduced well and, consequently, near-surface rock temperatures were modelled convincingly. Uncertainties in rock temperature modelling were found to be around 1.6 °C. Errors in snow cover modelling and hence in rock temperature simulations are explained by inadequate snow settlement due to linear precipitation scaling, missing lateral heat fluxes in the rock, and by errors caused by interpolation of shortwave radiation, wind and air temperature into the rock walls.Mean annual near-surface rock temperature increases were both measured and modelled in the steep rock walls as a consequence of a thick, long-lasting snow cover. Rock temperatures were 1.3–2.5 °C higher in the shaded and sunny rock walls, while comparing snow-covered to snow- free simulations. This helps to assess the potential error made in ground temperature modelling when neglecting snow in steep bedrock

Black Titania and Niobia within Ten Minutes - Mechanochemical Reduction of Metal Oxides with Alkali Metal Hydrides.

Partially or fully reduced transition metal oxides show extraordinary electronic and catalytic properties but are usually prepared by high temperature reduction reactions. This study reports the systematic investigation of the fast mechanochemical reduction of rutile-type TiO2 and H-Nb2 O5 to their partially reduced black counterparts applying NaH and LiH as reducing agents. Milling time and oxide to reducing agent ratio show a large influence on the final amount of reduced metal ions in the materials. For both oxides LiH shows a higher reducing potential than NaH. An intercalation of Li+ into the structure of the oxides was proven by PXRD and subsequent Rietveld refinements as well as 6 Li solid-state NMR spectroscopy. The products showed a decreased band gap and the presence of unpaired electrons as observed by EPR spectroscopy, proving the successful reduction of Ti4+ and Nb5+ . Furthermore, the developed material exhibits a significantly enhanced photocatalytic performance towards the degradation of methylene blue compared to the pristine oxides. The presented method is a general, time efficient and simple method to obtain reduced transition metal oxides