Impact-formed complex diamond-graphite nanostructures

Shock waves resulting from asteroidal and laboratory impacts convert sp 2 -bonded graphitic material to sp 3 -bonded diamond. Depending on the shock pressure and temperature conditions, complex nano- structures can form that are neither graphite nor diamond but belong to the diaphite material group, which are characterized by structurally intergrown layered sp 2 - and sp 3 -bonded carbon domains. Our ultrahigh-resolution transmission electron microscopy images combined with density functional theory calculations demonstrate that diaphites have two related but distinct structural families. Here, we describe diaphite nanostructures from natural and laboratory shocked samples, provide a framework for classifying the members of these materials, and draw attention to their excellent mechanical and electronic material properties

Quantifying hexagonal stacking in diamond

Diamond is a material of immense technological importance and an ancient signifier for wealth and societal status. In geology, diamond forms as part of the deep carbon cycle and typically displays a highly ordered cubic crystal structure. Impact diamonds, however, often exhibit structural disorder in the form of complex combinations of cubic and hexagonal stacking motifs. The structural characterization of such diamonds remains a challenge. Here, impact diamonds from the Popigai crater were characterized with a range of techniques. Using the MCDIFFaX approach for analysing X-ray diffraction data, hexagonality indices up to 40% were found. The effects of increasing amounts of hexagonal stacking on the Raman spectra of diamond were investigated computationally and found to be in excellent agreement with trends in the experimental spectra. Electron microscopy revealed nanoscale twinning within the cubic diamond structure. Our analyses lead us to propose a systematic protocol for assigning specific hexagonality attributes to the mineral designated as lonsdaleite among natural and synthetic samples

Metastable structural transformations and pressure-induced amorphization in natural (Mg,Fe)2SiO4 olivine under static compression: A Raman spectroscopic study

[EN] Raman spectroscopic data were obtained for (Mg,Fe)(2)SiO4 samples during compression to 57 GPa. Single crystals of San Carlos olivine compressed hydrostatically above 41 GPa showed appearance of a new "defect" peak in the 820-840 cm(-1) region associated with SiOSi linkages appearing between adjacent SiO44- tetrahedra to result in five- or sixfold-coordinated silicate species. Appearance of this feature is accompanied by a broad amorphous background. The changes occur at lower pressure than metastable crystalline transitions of end-member Mg2SiO4 forsterite (Fo-I) into Fo-II and Fo-III phases described recently. We complemented our experimental study using density functional theory (DFT) calculations and anisotropic ion molecular dynamics (AIMD) simulations to study the Raman spectra and vibrational density of states (VDOS) of metastably compressed Mg2SiO4 olivine, Fo-II and Fo-III, and quenched melts at high and low pressures. By 54 GPa all sharp crystalline peaks disappeared from observed Raman spectra indicating complete pressure-induced amorphization (PIA). The amorphous (Mg,Fe)(2)SiO4 spectrum contains Si-O stretching bands at lower wavenumber than expected for SiO44- indicating high coordination of the silicate units. The amorphous spectrum persisted on decompression to ambient conditions but with evidence for reappearance of tetrahedrally coordinated units. Non hydrostatic compression of polycrystalline olivine samples showed similar appearance of the defect feature and broad amorphous features between 43-44 GPa. Both increased in intensity as the sample was left at pressure overnight but they disappeared during decompression below 17 GPa with recovery of the starting olivine Raman signature. A hydrated San Carlos olivine sample containing 75-150 ppm OH was also studied. Significant broadening of the SiO44- stretching peaks was observed above 43 GPa but without immediate appearance of the defect or broad amorphous features. However, both of these characteristics emerged after leaving the sample at 47 GPa overnight followed by complete amorphization that occurred upon subsequent pressurization to 54 GPa. During decompression the high-density amorphous spectrum was retained to 3 GPa but on final pressure release a spectrum similar to thermally quenched low-pressure olivine glass containing isolated SiO44- groups was obtained. Leaving this sample overnight resulted in recrystallization of olivine. Our experimental data provide new insights into the metastable structural transformations and relaxation behavior of olivine samples including material recovered from meteorites and laboratory shock experiments.Our work was supported by the U.K. NERC via Grant NE/K002902/1 and Spanish MINECO under projects MAT2014-46649-C4-1/2-P.Santamaría Pérez, D.; Thomson, A.; Segura, A.; Pellicer Torres, J.; Manjón, F.; Cora, F.; Mccoll, K.... (2016). Metastable structural transformations and pressure-induced amorphization in natural (Mg,Fe)2SiO4 olivine under static compression: A Raman spectroscopic study. American Mineralogist. 101(7):1642-1650. https://doi.org/10.2138/am-2016-5389CCBYS16421650101

Shock-formed carbon materials with intergrown sp3- and sp2-bonded nanostructured units

Diamond is the hardest material found in nature. Its applications range from abrasives and electronics to nanomedicine and laser technology. The common form of diamond is cubic. Yet, dense carbon materials formed by shock compression have been described as hexagonal diamond or lonsdaleite. This study provides a structural understanding of lonsdaleite and demonstrates the existence of bulk materials containing extensive regions of nanostructured diamond and graphene-like intergrowths called diaphites. The structural complexities found in Canyon Diablo iron meteorite diamonds occur in a wide range of carbonaceous materials, and their identification can place constraints on the pressure?temperature conditions experienced during an impact. The predicted advanced properties of such materials highlight their potential use in future engineering applications. Studies of dense carbon materials formed by bolide impacts or produced by laboratory compression provide key information on the high-pressure behavior of carbon and for identifying and designing unique structures for technological applications. However, a major obstacle to studying and designing these materials is an incomplete understanding of their fundamental structures. Here, we report the remarkable structural diversity of cubic/hexagonally (c/h) stacked diamond and their association with diamond-graphite nanocomposites containing sp3-/sp2-bonding patterns, i.e., diaphites, from hard carbon materials formed by shock impact of graphite in the Canyon Diablo iron meteorite. We show evidence for a range of intergrowth types and nanostructures containing unusually short (0.31 nm) graphene spacings and demonstrate that previously neglected or misinterpreted Raman bands can be associated with diaphite structures. Our study provides a structural understanding of the material known as lonsdaleite, previously described as hexagonal diamond, and extends this understanding to other natural and synthetic ultrahard carbon phases. The unique three-dimensional carbon architectures encountered in shock-formed samples can place constraints on the pressure?temperature conditions experienced during an impact and provide exceptional opportunities to engineer the properties of carbon nanocomposite materials and phase assemblages

Delocalized electron holes on oxygen in a battery cathode

Oxide ions in transition metal oxide cathodes can store charge at high voltage offering a route towards higher energy density batteries. However, upon charging these cathodes, the oxidized oxide ions condense to form molecular O2 trapped in the material. Consequently, the discharge voltage is much lower than charge, leading to undesirable voltage hysteresis. Here we capture the nature of the electron holes on O2− before O2 formation by exploiting the suppressed transition metal rearrangement in ribbon-ordered Na0.6[Li0.2Mn0.8]O2. We show that the electron holes formed are delocalized across the oxide ions coordinated to two Mn (O–Mn2) arranged in ribbons in the transition metal layers. Furthermore, we track these delocalized hole states as they gradually localize in the structure in the form of trapped molecular O2 over a period of days. Establishing the nature of hole states on oxide ions is important if truly reversible high-voltage O-redox cathodes are to be realized.</p