Nanocrystalline hexagonal diamond formed from glassy carbon

Carbon exhibits a large number of allotropes and its phase behaviour is still subject to significant uncertainty and intensive research. The hexagonal form of diamond, also known as lonsdaleite, was discovered in the Canyon Diablo meteorite where its formation was attributed to the extreme conditions experienced during the impact. However, it has recently been claimed that lonsdaleite does not exist as a well-defined material but is instead defective cubic diamond formed under high pressure and high temperature conditions. Here we report the synthesis of almost pure lonsdaleite in a diamond anvil cell at 100 GPa and 400 °C. The nanocrystalline material was recovered at ambient and analysed using diffraction and high resolution electron microscopy. We propose that the transformation is the result of intense radial plastic flow under compression in the diamond anvil cell, which lowers the energy barrier by “locking in” favourable stackings of graphene sheets. This strain induced transformation of the graphitic planes of the precursor to hexagonal diamond is supported by first principles calculations of transformation pathways and explains why the new phase is found in an annular region. Our findings establish that high purity lonsdaleite is readily formed under strain and hence does not require meteoritic impacts

The composition, structure and properties of four different glassy carbons

Glassy carbon (GC) is a class of disordered carbon materials that is known to be superelastic and non-graphitizing up to 3000 °C. The maximum heat treatment temperature is often used as a proxy to denote structure and physical properties. GC synthesised at low temperatures (~1000 °C) is often classified as Type I GC which has advantages of higher elastic modulus, resistance to oxidation, and lower permeability to gases. Type II GC is synthesised at higher temperatures (>2000 °C), has fewer impurities, is more electrically conductive, and is rated to a higher service temperature. Here Type I and II GC samples sourced from two suppliers are investigated using Rutherford backscattering spectrometry and elastic recoil detection analysis for composition, Raman spectroscopy, transmission electron microscope imaging, X-ray and neutron diffraction for structure determination, nanoindentation for mechanical properties, and Van der Pauw measurements for resistivity. The results show that the broad classifications of Type I or Type II do not correlate with the physical properties of the samples. We conclude that the quoted maximum heat treatment temperature alone is not sufficient to specify the properties of GC and that a careful microstructural examination of the material should be used to inform materials selection.JEB and DGM acknowledge funding under the ARC Discovery Project scheme (DP140102331). DRM and DGM acknowledge funding under the ARC Discovery Project scheme (DP170102087). BH acknowledges funding through the ORNL Neutron Scattering Facilities, DOE Office of Science User Facilities operated by the Oak Ridge National Laboratory

Investigation of Room Temperature Formation of the Ultra-Hard Nanocarbons Diamond and Lonsdaleite

Diamond is an attractive material due to its extreme hardness, high thermal conductivity, quantum optical, and biomedical applications. There is still much that is not understood about how diamonds form, particularly at room temperature and without catalysts. In this work, a new route for the formation of nanocrystalline diamond and the diamond-like phase lonsdaleite is presented. Both diamond phases are found to form together within bands with a core-shell structure following the high pressure treatment of a glassy carbon precursor at room temperature. The crystallographic arrangements of the diamond phases revealed that shear is the driving force for their formation and growth. This study gives new understanding of how shear can lead to crystallization in materials and helps elucidate how diamonds can form on Earth, in meteorite impacts and on other planets. Finally, the new shear induced formation mechanism works at room temperature, a key finding that may enable diamond and other technically important nanomaterials to be synthesized more readily.Portions of this work were performed at HPCAT (Sector 16) and GeoSoilEnviroCARS (The University of Chicago, Sector 13), Advanced Photon Source (APS), Argonne National Laboratory. HPCAT operations were supported by DOE-NNSA under Award No. DE-NA0001974, with partial instrumentation funding by NSF. GeoSoilEnviroCARS is supported by the National Science Foundation – Earth Sciences (EAR – 1634415) and Department of Energy- GeoSciences (DE-FG02-94ER14466). The Advanced Photon Source is a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under Contract No. DE-AC02-06CH11357. D.G.M., B.H., R.B. and D.R.M. would like to acknowledge the support from the Australian Research Council (ARC) Discovery Project scheme (DP170102087). J.E.B. would like to acknowledge the Australian Research Council (ARC) for ARC Discovery Project scheme (DP190101438). B.H. and R.B. were supported by resources at the Spallation Neutron Source (SNS) and the High Flux Isotope Reactor (HFIR), DOE Office of Science User Facilities operated by the Oak Ridge National Laboratory (ORNL). ORNL is funded under DOE-BES contract number, DE-AC05-00OR2272

External magnetic field guiding in HiPIMS to control sp3 fraction of tetrahedral amorphous carbon films

Amorphous carbon films have many applications that require control over their sp3 fraction to customise the electrical, optical and mechanical properties. Examples of these applications include coatings for machine parts, biomedical and microelectromechanical devices. In this work, we demonstrate the use of a magnetic field with a high-power impulse magnetron sputtering (HiPIMS) source as a simple, new approach to give control over the sp3 fraction. We provide evidence that this strategy enhances the deposition rate by focusing the flux, giving films with high tetrahedral bonding at the centre of the deposition field and lower sp3 fractions further from the centre. Resistive switching appears in films with intermediate sp3 fractions. The production of thin amorphous carbon films with selected properties without the need for electrical bias opens up applications where insulating substrates are required. For example, deposition of sp3 rich films on polymers for wear resistant coatings as well as fabrication of resistive switching devices for neuromorphic technologies that require tuning of the sp3 fraction on insulating substrates are now possible