Rare-earth metal catalysts for high-pressure synthesis of rare diamonds

The combination of the unique properties of diamond and the prospects for its high-technology applications urges the search for new solvents–catalysts for the synthesis of diamonds with rare and unusual properties. Here we report the synthesis of diamond from melts of 15 rare-earth metals (REM) at 7.8 GPa and 1800–2100 °C. The boundary conditions for diamond crystallization and the optimal parameters for single crystal diamond synthesis are determined. Depending on the REM catalyst, diamond crystallizes in the form of cube–octahedrons, octahedrons and specific crystals bound by tetragon–trioctahedron and trigon–trioctahedron faces. The synthesized diamonds are nitrogen-free and belong to the rare type II, indicating that the rare-earth metals act as both solvent–catalysts and nitrogen getters. It is found that the REM catalysts enable synthesis of diamond doped with group IV elements with formation of impurity–vacancy color centers, promising for the emerging quantum technologies. Our study demonstrates a new field of application of rare-earth metals.

Diamond formation in an electric field under deep Earth conditions

Most natural diamonds are formed in Earth’s lithospheric mantle; however, the exact mechanisms behind their genesis remain debated. Given the occurrence of electrochemical processes in Earth’s mantle and the high electrical conductivity of mantle melts and fluids, we have developed a model whereby localized electric fields play a central role in diamond formation. Here, we experimentally demonstrate a diamond crystallization mechanism that operates under lithospheric mantle pressure-temperature conditions (6.3 and 7.5 gigapascals; 1300° to 1600°C) through the action of an electric potential applied across carbonate or carbonate-silicate melts. In this process, the carbonate-rich melt acts as both the carbon source and the crystallization medium for diamond, which forms in assemblage with mantle minerals near the cathode. Our results clearly demonstrate that electric fields should be considered a key additional factor influencing diamond crystallization, mantle mineral–forming processes, carbon isotope fractionation, and the global carbon cycle.

Crystallization of Diamond from Melts of Europium Salts

Diamond crystallization in melts of europium salts (Eu2(C2O4)3·10H2O, Eu2(CO3)3·3H2O, EuCl3, EuF3, EuF2) at 7.8 GPa and in a temperature range of 1800–2000 °C was studied for the first time. Diamond growth on seed crystals was realized at a temperature of 2000 °C. Spontaneous diamond nucleation at these parameters was observed only in an Eu oxalate melt. The maximum growth rate in the europium oxalate melt was 22.5 μm/h on the {100} faces and 12.5 μm/h on the {111} faces. The diamond formation intensity in the tested systems was found to decrease in the following sequence: Eu2(C2O4)3·10H2O > Eu2(CO3)3·3H2O > EuF3 > EuF2 = EuCl3. Diamond crystallization occurred in the region of stable octahedral growth in melts of Eu3+ salts and in the region of cubo-octahedral growth in an EuF2 melt. The microrelief of faces was characterized by specific features, depending on the system composition and diamond growth rate. In parallel with diamond growth, the formation of metastable graphite in the form of independent crystals and inclusions in diamond was observed. From the spectroscopic characterization, it was found that diamonds synthesized from Eu oxalate contain relatively high concentrations of nitrogen (about 1000−1200 ppm) and show weak PL features due to inclusions of Eu-containing species.

How do diamonds grow in metal melt together with silicate minerals? An experimental study of diamond morphology

The origin and evolution of metal melts in the Earth's mantle and their role in the formation of diamond are the subject of active discussion. It is widely accepted that portions of metal melts in the form of pockets can be a suitable medium for diamond growth. This raises questions about the role of silicate minerals that form the walls of these pockets and are present in the volume of the metal melt during the growth of diamonds. The aim of the present work was to study the crystallization of diamond in a complex heterogeneous system: metal-melt–basalt–carbon. The experiments were performed using a multianvil high-pressure apparatus of split-sphere type (BARS) at a pressure of 5.5 GPa and a temperature of 1500 ∘C. The results demonstrated crystallization of diamond in metal melt together with garnet and clinopyroxene, whose chemical compositions are similar to those of eclogitic inclusions in natural diamond. We show that the presence of silicates in the crystallization medium does not reduce the chemical ability of metal melts to catalyze the conversion of graphite into diamond, and, morphologically, diamond crystallizes mainly in the form of a cuboctahedron. When the content of the silicate material in the system exceeds 5 wt %, diamond forms parallel-growth aggregates, but 15 wt % of silicate phases block the crystallization chamber, preventing the penetration of metallic melt into them, thus interrupting the growth of diamond. We infer that the studied mechanism of diamond crystallization can occur at lower-mantle conditions but could also have taken place in the ancient continental mantle of the Earth, under reducing conditions that allowed the stability of Fe–Ni melts.

Effect of sulfur on diamond growth and morphology in metal–carbon systems

Sulfur additives inhibit diamond crystallization in the Fe–Ni–C system at 6 GPa and 1400 °C and affect the diamond crystal morphology and nitrogen impurity content.

Experimental Modeling of Diamond Formation Processes in Fe-C-S System at High P-T Parameters

The problem of diamond formation, despite the huge amount of accumulated information, has not been finally resolved. Currently, the most well-established hypothesis is that the diamond will be formed as a result of metasomatosis. According to this theory, the source of carbon were fluids of C-H-O-N-S composition. There are still questions concerning the environment for diamond crystallization. One of the most common inclusions in diamonds from kimberlite tubes are sulfides. They are also represented in diamondiferous xenoliths of peridotite and eclogite from diamondiferous tubes, but their quantity in diamonds is still higher in comparison with xenoliths. Modern scientific researches allow to assert that large diamonds, such as Kullinan (3106 carats), Koh-i-Noor, etc., were formed at great depths of about 360 – 750 km. Inclusions in these diamonds are, along with silicate minerals, iron-nickel alloy, iron-nickel carbide and sulfide (pyrrhotite). The present study is devoted to studying the model growth environment of a diamond in the Fe-C-S system with a sulfur content of 3 wt. % in relation to iron. The experiments of 0.5 hours duration were carried out at 6 GPa and 1450 С on a high-pressure apparatus of "cutting sphere" type. As a result, diamond synthesis was obtained. The following phases were recorded during the analysis of growth medium composition (metal-sulfide sintering): solid solution of carbon in iron, iron sulfide, iron carbide. Iron sulfide is represented by pyrrhotite. Thus, the phases established in solid products of the experiments fully correspond to the phases isolated from inclusions of natural diamonds.

Coesite inclusion in diamondferous kyanite-bearing eclogite from kimberlite pipe Udachnaya (Siberian Craton)

A find of coesite in a kyanite graphite-diamond-bearing eclogite xenolith from the Udachnaya-Vostochnaya kimberlite pipe is described in this paper. The coesite relics were found in intensely fractured garnet indicating some influence of the kimberlite melt, which is supported by the typical secondary mineral assemblage around this inclusion. These data indicate that shallower diamond-free coesite rocks (2,7 GPa) underwent metamorphism distinct from diamond-bearing coesite eclogites (~4 GPa). The metasomatic alteration of rock interacting with C-O-H fluid during diamond crystallization may be another possible reason for the missing coesite in diamond-bearing xenoliths.