Natural Diamond Crystals Research Articles

Morphological features of natural diamond crystals treated in a rotary vortex apparatus and subjected to oxidative etching

Morphological features of natural diamond crystals treated in a rotary vortex apparatus and subjected to oxidative etching

Determination of the internal structural heterogeneity of natural diamond: Methodological aspects of using confocal Raman spectroscopy with polarization analysis

Aim. To describe a technique for studying the internal structural heterogeneity of natural diamond crystals, based on confocal Raman spectroscopy with polarization analysis, including angular resolution, at high spectral (0.5–0.6 cm–1) and spatial (1 μm) resolution. Results. The parameters of the F2g vibrational mode in diamond (position, width, intensity, shape, including the Gaussian and Lorentzian contributions to the broadening) are determined by the superposition influence of a number of factors, including the type and content of structural stresses, deformations, various types of defects, as well as orientation of crystallographic axes of the crystal relative to the directions of incident and scattered rays and the directions of their electric polarization vectors. The proposed analytical technique includes: (1) analysis of the crystallographic orientation of the sample in the spectrometer coordinate system and possible misorientations of its fragments with an error of ≈8–15°; (2) visualization of the distribution of structural stresses, deformations, twins, impurity defects and their associates based on sample surface mapping by spectral parameters of the F2g vibration mode; (3) obtaining statistical characteristics of the internal structural heterogeneity of the samples based on diagrams of spectral parameter frequency with a statistically significant number (≈103): unimodality (uni-, bimodal distributions) and distribution dispersion (from ≈0.1 to ≈0.6 cm–1 for width and from ≈0.04 to ≈0.6 cm–1 for line position). The procedure was tested using two synthetic CVD diamond single crystals doped with nitrogen and boron. The possibility of typification of natural samples by statistical characteristics of internal heterogeneity is considered using the example of samples from kimberlite pipes of Yakutia and placers of the Western Cis-Urals. Conclusions. A method for determining the internal structural heterogeneity of natural diamond crystals based on confocal Raman spectroscopy with polarization analysis is proposed. The possibility of using statistical characteristics of heterogeneity as a typomorphic feature of the original diamond source is demonstrated. The proposed diagrams are promising for sample comparison and typification.

Porous Natural Diamond with Embedded Metal (Pt0.50–Co0.50)

Natural diamond crystals with a highly porous surface were used as substrates for synthesizing single-phase bimetallic Pt–Co nanoparticles at temperatures of 500 °C and 800 °C. The metal nanoparticles inside the pores were determined to take the form of single-phase Pt0.50Co0.50 solid solutions with different degrees of superstructure ordering. A detailed characterization of both nanoalloys revealed a tetragonal symmetry with a space group, P4/mmm. For the sample obtained at 500 °C, the lattice parameters were a = 2.673(2), c = 3.735(3) Å, and c/a = 1.397(1); for the samples obtained at 800 °C, the parameters were—a = 2.688(2), c = 3.697(3) Å, and c/a = 1.375(1). Within the experimental parameters, no significant chemical interaction of the diamond with the Pt–Co particles was identified. The results demonstrate a strong anchoring effect of the metallic material within the etching pores. The successful synthesis of bimetallic Pt–Co particles embedded inside the caverns can facilitate a study of their magnetic properties. The presence of Pt–Co in specific diamond compositions can also be used for marking diamond crystals as a means for their subtle identification, as well as confirming the possibility of capturing significant amounts of metal along with diamonds during their dissolution in the deep Earth.

Photoluminescent Microbit Inscripion Inside Dielectric Crystals by Ultrashort Laser Pulses for Archival Applications.

Inscription of embedded photoluminescent microbits inside micromechanically positioned bulk natural diamond, LiF and CaF2 crystals was performed in sub-filamentation (geometrical focusing) regime by 525 nm 0.2 ps laser pulses focused by 0.65 NA micro-objective as a function of pulse energy, exposure and inter-layer separation. The resulting microbits were visualized by 3D-scanning confocal Raman/photoluminescence microscopy as conglomerates of photo-induced quasi-molecular color centers and tested regarding their spatial resolution and thermal stability via high-temperature annealing. Minimal lateral and longitudinal microbit separations, enabling their robust optical read-out through micromechanical positioning, were measured in the most promising crystalline material, LiF, as 1.5 and 13 microns, respectively, to be improved regarding information storage capacity by more elaborate focusing systems. These findings pave a way to novel optomechanical memory storage platforms, utilizing ultrashort-pulse laser inscription of photoluminescent microbits as carriers of archival memory.

The Size and Shape of Diamond Crystals of Different Origin

The size and shape of diamond crystals of different origin are analyzed. Diamonds with a size of less than about 0.5 mm are classified as microcrystals. Diamonds found in meteorites typically show non-faceted anhedral crystals of various sizes. Only the Canyon Diablo iron meteorite has cubic microcrystals of unclear crystallogenesis. Nano, micro- and macro-sized crystals of diamond in meteorites are usually aggregate in nature. The release of diamond polyhedra in meteorites is limited by the too small size of its crystals in chondrites and by its solid-phase transformation from very fine-grained diamond and graphite in ureilites and octahedrites. The size and shape of diamond crystals found in meteorite impact craters are determined by the nature of the source carbon material. The process of solid-phase transformation of graphite or other carbon-bearing materials (e.g., coal, plant remains) to diamond in meteorite craters does not allow euhedral crystal to be formed. At the same time, in the case of diamonds formed from impacts, on the (0001) faces of impact apographitic diamonds, polyhedra of nano-microdiamonds crystallize from the gas phase. These crystals are often form autoepitaxially, because they crystallize in an oriented manner on the lonsdaleite -diamond matrix. Diamonds found in metamorphic rocks, ophiolites and modern volcanites show faceted microcrystals. A wide range of sizes, from 0.1 mm to 10 cm, is characteristic of faceted diamond crystals from kimberlites, lamproites and lamprophyres. Diamond crystals from different mantle rocks acquire a multifaceted shape after reaching certain embryo sizes — the most likely appearance of diamond polyhedra larger than 40-50 nm. Octahedra forms are dominant for natural diamond crystals of different sizes and origin.

Surface Porosity of Natural Diamond Crystals after the Catalytic Hydrogenation

The study of diamond surfaces is traditionally undertaken in geology and materials science. As a sample material, two natural diamond crystals of type Ia were selected, and their luminescence and nitrogen state was characterized. In order to etch the surface catalytic hydrogenation was performed using Fe particles as an etchant. Micromorphology of the surface was investigated by scanning electron and laser confocal microscopy. It was demonstrated that etching occurred perpendicular to the crystal surface, with no signs of tangential etching. The average depth of caverns did not exceed 20–25 μm with a maximal depth of 40 μm. It is concluded that catalytic hydrogenation of natural type Ia diamonds is effective to produce a porous surface that can be used in composites or as a substrate material. Additionally, the comparison of results with porous microsculptures observed on natural impact diamond crystals from the Popigai astrobleme revealed a strong resemblance.

The effect of oxygen fugacity on diamond resorption in ascending kimberlite melt

When transported by magmas to the Earth's surface, diamond crystals underwent resorption, the intensity of which significantly differed in various kimberlite pipes. We experimentally simulated diamond resorption at different oxygen fugacities (fO2) in ascending kimberlite magma enriched in CO2 and H2O. The experiments were carried out using specially prepared unaltered Group I kimberlite from the Udachnaya East pipe (Yakutia) and model carbonatite at 3.0 GPa, 1200–1400 °C, and fO2 in a range of NNO–2 to NNO + 3.2 log units (where NNO is Ni-NiO buffer). Over the investigated range of conditions, resorption of octahedral diamond crystals is found to occur according to a single scenario. Negative trigons and shield-shaped laminae develop on the {111} faces and crystal edges are truncated by the surfaces of tetrahexahedroids. The rate of diamond resorption increases in all studied systems as fO2 and temperature are raised. In this case, water-enriched melts are the most aggressive media in the investigated T–fO2 interval. Among the most oxidized high-temperature melts, it is carbonatite melts depleted in SiO2 that provide the maximum rate of diamond resorption. Furthermore, the rates of diamond resorption we obtained are an order of magnitude higher than those previously measured in silicate melts containing CO2 and H2O, at fO2 values from the NNO buffer to NNO-2. Therefore, high oxygen fugacity, a temperature of ~1400 °C, and essentially carbonate composition of water-containing magma could provide a high intensity of diamond resorption at the mantle stage of magma ascent to the surface. Apparently, this process primarily influenced the formation of the appearance and preservation of natural diamond crystals in kimberlite pipes.

Composition and structure of the diamond/low carbon steel transition zone obtained by contact heating in vacuum at Fe–C eutectic temperature

The study covers the structure, elemental and phase composition of products formed in the contact interaction between diamond and low-carbon steel in vacuum at the Fe–C eutectic melting temperature. Cylindrical tablets made of low carbon steel with a maximum carbon content of 0.1 wt.% and natural diamond crystals in the form of a pyramid (or truncated pyramid) were used as contact pairs. The flat bases of diamond crystals were mounted on the horizontal surface of steel tablets with the load applied to the top of diamond crystals. Contact samples were sintered in a vacuum furnace at a maximum heating temperature of ~1165 °C. After holding at this temperature for 5 minutes, the furnace was turned off and the temperature in its chamber decreased in free cooling mode. Sintered diamond/steel tablet samples were studied by optical and scanning electron microscopy, X-ray diffraction analysis and Raman spectroscopy. It was found that the Fe–C eutectic melt forms in the diamond/steel tablet contact zone, a thin layer of which, when solidified, welds a diamond crystal to the steel tablet under the temperature-time heating mode specified in the experiment. Their bonding strength is such that welded samples without separation can withstand intense cyclic loads during grinding and polishing when making longitudinal sections of samples necessary for metallographic studies. It was shown that the Fe–C eutectic alloy is a gray cast iron with a ferrite-perlite metal base and lamellar graphite inclusions. The microhardness of the solidified Fe–C eutectic was ~1714 MPa. The initial steel tablet with a ferrite-perlite structure was subjected to cementation during sintering in contact with diamond. The most intensive cementation occurred in the ~110 μm thick unmelted upper layer of the steel tablet, which adjoined the Fe–C eutectic during sintering. The microhardness of this layer was ~4945 MPa. As it deepens into the steel tablet there is a gradual transition of the perlite-cementite structure to a perlite one and further to the initial ferrite-perlite microstructure inwards the steel tablet. At the same time, the microhardness changes from ~ 4945 to 1570 MPa.

Diamond and Low Carbon Steel Interaction at Melting Temperature of Fe-C Eutectic

The structure, elemental and phase composition of the products formed during the contact interaction of diamond with low-carbon steel in vacuum at the Fe-C eutectic melting temperature were studied. Cylindrical tablets made of low carbon steel (less than 0.1 % wt. C), and pyramid shaped natural diamond crystals were used as a contact pairs. Diamond crystals were mounted by their flat base on the horizontal surface of steel tablet and a load was applied to the diamond crystals top. Contact samples were sintered in a vacuum furnace at a maximum heating temperature of ~1165 °C. Sintered diamond-steel tablet samples were studied by optical and scanning electron microscopy, X-ray diffraction analysis. It was shown that the initial steel tablet with a ferrite-perlite structure passed cementation during sintering in contact with diamond. The most intensive cementation is undergone by the non-melted upper layer of the steel tablet ~110 μm thick, which adjoined the Fe-C eutectic melt during sintering. The microhardness of this layer was ~4945 MPa. As it deepens into steel tablet a gradual transition of structure from perlite-cementite to perlite and further to the initial ferrite-perlite microstructure is observed. Herewith, the microhardness changes from ~ 4945 to 1570 MPa.

Minimal Dissymmetry Effect in the Thermodynamic System

The minimal dissymmetry effect, which manifests itself within Curie’s principle, is a consequence of the limiting principles of thermodynamics: the second law for a closed system and the entropy-production minimum for an open system. Also being a limiting principle, the minimal dissymmetry effect makes it possible to introduce a quantitative characteristic of dissymmetry into classical Curie’s principle. It is shown that the dissymmetry of a dynamic form of growth and dissolution of natural diamond crystals is due to the complex effect of several factors of different scales and strengths.

Microrelief of Rounded Diamond Crystals as an Indicator of the Redox Conditions of Their Resorption in a Kimberlite Melt

We conducted a detailed study of the morphology of diamond crystals partially dissolved in a water-bearing kimberlite melt at pressure of 6.3 GPa, temperature of 1400 °C, and two oxygen fugacities (fO2) corresponding to the Re-ReO2 buffer and near the magnetite–hematite (MH) buffer. The triangular etch pits on the {111} faces, which formed during experimental diamond dissolution, were found to completely correspond to negative trigons on natural diamond crystals in the shape and sidewalls inclination angle. Furthermore, two experimental fO2 values were associated with two relief types of the rounded tetrahexahedroid surfaces typical of natural rounded diamonds. Therefore, the surface microrelief on rounded natural diamond crystals was concluded to be an indicator of the redox conditions of natural diamond resorption.

On the real combinations of cubes and octahedra.

All the real combinations of cubes and octahedra (77657 in total) are enumerated and characterized by facet symbols and symmetry point groups. The most symmetrical polyhedra (with automorphism group orders not less than 6, 163 in total) are shown. It is assumed that they represent the most probable forms of natural diamond crystals. The results are discussed with respect to the Curie dissymmetry principle.

Incipient stages of transformation of round natural diamonds under dissolution in Fe-S melt at high pressure

Research subject. The article presents the results of a microscopic and photogoniometric study of natural rounded diamonds of tetraghexahedral habit from the kimberlite pipe “Internationalnaya” (Yakutia). The diamonds was partially dissolved in a sulphur-containing iron melt (sulphur content of 15–30 wt %) at 4.5 GPa and 1450ºС.Methods. The experiments were carried out on a multi-puncheon apparatus of a “split-sphere” type in high-pressure solid-phase cells made of refractory oxides ZrO2, CaO, MgO using a cylindrical shape graphite heater. The crystals were studied using an MBS-10 optical microscope with a photo camera, and a Jeol JSM-6510LV scanning electron microscope. A goniometric study of diamond crystals was carried out by a photo method in a cylindrical chamber. It was found that when a sulphur content was 15 wt %, diamond crystals of tetrahexahedral habit were transformed into a curved shaped octahedroids with morphological features similar to natural diamonds found in kimberlites. When the sulphur content was 23–30 wt %, the rate of dissolution of diamonds in the Fe-S melt sharply reduced, while the diamond surface at the micro level became covered with numerous etching hillocks, whose sidewalls have surfaces similar to flat-faced {111} form. Dissolution of the rounded diamonds in the Fe-S melt at high pressure occurred by a “normal” mechanism, that is perpendicular to the surface of the dissolving crystal through trigonal dissolution layers, while a tangential-layered mechanism played a minor role.Conclusion. The natural diamond crystals could underwent dissolution in the mantle before they were captured by kimberlite magma. Two fundamentally different types of homomorphic and typomorphic features of the dissolution forms observed on natural diamonds can be determined, namely: on one side, those associated with storage in mantle before the crystals were captured by the kimberlite magma, and on the other side, with the kimberlite process itself. The presence of octahedral diamonds with parallel (trigonal) striation in kimberlite deposits may indicate on a high degree of diamond preservation due to relatively insignificant effect of the kimberlite magma. This, undoubtedly, should help to decipher the diamond genesis and, possibly, improve the mineralogical criteria used in diamond exploration.

Preservation conditions of CLIPPIR diamonds in the earth’s mantle in a heterogeneous metal–sulphide–silicate medium (experimental modeling)

The genesis of CLIPPIR diamonds (Cullinan–like, large, inclusion–poor, pure, irregular, and resorbed) have attracted much interest due to their possible crystallization from metal melt in deep horizons of the earth’s mantle. These diamonds usually show a pronounced resorption and irregular morphology. The present paper reports new experimental data on the dissolution of diamond crystals at high P–T parameters in Fe–S melt containing large amounts of silicate components (5–20 wt%). The experiments were performed using a split–sphere multi–anvil apparatus (BARS) at a pressure of 4 GPa and a temperature of 1450 °C. The samples consisted of natural diamond crystals placed in mixtures of Fe, S, and kimberlite. Wide variations in dissolution rates of diamond crystals were obtained. The absence of diamond dissolution in a heterogeneous medium indicates that the amount of solid silicate phases present in metal melt plays a role in the preservation of diamonds. This study demonstrated how diamonds can be stored in natural environments due to the heterogeneity of the medium composition which could insulate diamonds from the metal–sulphide melt. The obtained results improve our understanding of processes that lead to preservation of CLIPPIR diamonds in the deep mantle.

Analysis of Natural Diamonds by Rutherford Backscattering

The method of Rutherford backscattering (RBS) of 4He ions is used to detect impurities in the surface region of natural diamond crystals. In order to decrease the influence of luminescence from the surface of diamond, the recording of scattered ions is performed by an annular detector, which decreases the statistical error and improves the measurement accuracy. The limit of impurity detection is 1014 at/cm2 for light impurities and 1012 at/cm2 for heavy impurities.

Luminescence of Plastically Deformed Diamond in the Range 800–1050 nm

Two photoluminescence line systems were observed for natural diamond crystals upon excitation by laser radiation with λ = 785 nm and were attributed to plastic deformation lamellae. The first system consisted of a set of doublets separated from each other by 0.0435 eV with 0.0162 eV between maxima and the head line positioned at 1.392 eV. The second system included lines at 1.309, 1.288, 1.256, and 1.214 eV. In some instances, the intensities of the systems reached 50% of the Raman line intensity.

Morphological Features of Diamond Crystals Dissolved in Fe0.7S0.3 Melt at 4 GPa and 1400°C

An experimental study of the dissolution of natural and synthetic diamonds in a sulfur-bearing iron melt (Fe0.7S0.3) with high P–T parameters (4 GPa, 1400°С) was performed. The results demonstrated that under these conditions, octahedral crystals with flat faces and rounded tetrahexahedral diamond crystals are transformed into rounded octahedroids, which have morphological characteristics similar to those of natural diamonds from kimberlite. It was suggested that, taking into account the complex history of individual natural diamond crystals, including the dissolution stages, sulfur-bearing metal melts up to sulfide melts were not only diamond-forming media during the early evolution of the Earth, but also natural solvents of diamond in the mantle environment before the formation of kimberlitic melts.

The displacement disorder of atoms in diamond crystals revealed by X-ray imaging plate detector

Cylindrical Imaging Plate Area Detector of Rigaku (IPD) was used to register the X-ray diffraction patterns from diamond crystals grown by Chemical Vapor Deposition (CVD) process. The analysis revealed a deviation from cubic diamond lattice symmetry. X-ray diffraction patterns have been taken by oscillation and stationary crystal methods. Due to high resolution, sensitivity and speed, the IPD detector, allows registration of scattering in the vicinity of Bragg reflections such as broadening, splitting, and satellite reflections. These details were recognized via comparison with the diffraction pattern from a nearly perfect natural diamond crystal and a single crystal of silicon, which were used as diffraction standards. We report data on highly oriented diamond film (HOD) on (001) Si. Powder diffraction patterns show a split of the 111 diffraction line. The line at 2.056Å corresponds to cubic diamond, and the other line at 2.036Å is assigned to a disordered polytype. Two superstructure spots were located at 4.076Å and 4.092Å. Creation of this polytype during growth annihilates desired heteroepitaxy. The issues of lattice disorder, specifically for diamond crystals, are discussed in the framework of kinematical theory of X-ray diffraction.

Natural and synthetic diamond crystals of fibrous and rough-lamellar structure and structural mechanism of their normal growth

Various forms of normal growth of natural and synthetic diamond crystals with fibrous and roughlamellar structure obtained under nonequilibrium conditions are considered. The structural mechanisms of the experimentally observed fibrous (in 〈111〉 and 〈100〉 directions) and rough-laminar (by {110} and {100} layers (or lamellae)) normal growth of diamond crystals are proposed on the basis of nonequilibrium noncrystalline structures consisting of tetrahedrally coordinated atoms.

Sites of the N1 nitrogen paramagnetic centers in natural diamond crystals: Dissymmetrization of the structure as a result of plastic deformation

Using the method of EPR spectroscopy, it is shown that the N1 nitrogen centers (N–C–N+) are unevenly distributed over possible sites in natural brown crystals of plastically deformed diamonds. The influence of deformational dissymmetrization of the structure on the anisotropy of some physical properties of natural diamonds is discussed.