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The allotropes of carbon display a wide diversity of structures that include the three-dimensional (3D) diamond and graphite, two-dimensional (2D) graphene and curved nanotubes and fullerenes. Within this diversity are materials with extraordinary properties, paramount being cubic diamond, which has the highest known hardness and thermal conductivity.
Diamond is reported to have a number of polytypes, of which lonsdaleite (also called hexagonal diamond) has received particularly intense attention. Lonsdaleite was first described almost 50 years ago from the Canyon Diablo iron meteorite. Its formation was attributed to shock-induced transformation of graphite within the meteorite upon impact with Earth, and its occurrence was used as an indicator of shock. It has since been reported from several meteorites as well as from terrestrial sediments and has been attributed to asteroidal impacts, both extraterrestrial and on Earth.Lonsdaleite was proposed to have a wurtzite (ZnS)-type structure with space group P6 3/mmc ( a=0.251 and c=0.412 nm) and with all structural positions occupied by carbon. Observations and theoretical studies suggested a structural relationship among graphite, cubic diamond and lonsdaleite and an important role of the latter during the graphite-to-diamond transition,. Furthermore, an area centred around 18 GPa and 1,400 K in the pressure–temperature diagram for carbon was attributed to a phase called ‘retrievable hexagonal-type diamond’, which corresponds to the conditions where lonsdaleite has been reported.Lonsdaleite has also received much attention because of its potentially superior mechanical properties, such as compressive strength, hardness and rigidity, thought to rival or exceed those of cubic diamond.
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However, these exceptional properties have not been proven experimentally because of the inability to synthesize lonsdaleite as a pure phase. They show features reported for ‘lonsdaleite’,. ( a) XRD patterns from (i) Canyon Diablo and (ii) synthetic sample. Cubic diamond reflections are marked with solid black lines. The positions attributed to lonsdaleite are indicated by vertical dotted lines. ( b) SAED pattern from Canyon Diablo sample, indexed as diamond along.
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( c) SAED pattern from Canyon Diablo sample, indexed as diamond along. The white arrows in b point to positions having a d-value of 0.218 nm (attributed to the 100 reflection of ‘lonsdaleite’), and those in c mark hexagonally arranged reflections. SAED patterns with features matching those of b, c have been interpreted as evidence for ‘lonsdaleite’ projected along and, respectively. Here we provide a new explanation, based on faulted and twinned cubic diamond, for the diffraction features attributed to lonsdaleite. Because we question its existence, we will hereafter refer to it as ‘lonsdaleite’ to indicate scepticism that it exists as a discrete material.
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XRD and SAED patterns, EELS data and scanning transmission electron microscope (STEM) images of natural samples from the Canyon Diablo meteorite, the type specimen from which ‘lonsdaleite’ was first described, and of synthetic material prepared under conditions where ‘retrievable hexagonal-type diamond’ was reported, support our argument. The finding calls for re-evaluation of previous reports regarding ‘lonsdaleite.’.