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At least 19 records

Melting diamond in the diamond cell by laser-flash heating

The phase behavior of carbon at high pressure and the search for carbon structures denser than diamond has been explored for decades showing large discrepancies, with many fundamental questions remaining unresolved. Here we show evidence of melting above the graphite-diamond-liquid (GDL) triple point (~13 GPa, 4000 K) up to 50 GPa on samples recovered from single flash-heating events using spectroscopic and electron microscopic methods. The results show that for all pressures, diamond melts below the triple point temperature contradicting previous studies, most of which predict a positive slope of the melting curve.

36 MATERIALS SCIENCE↗

Material transport in laser-heated diamond anvil cell melting experiments

A previously undocumented effect in the laser-heated diamond anvil cell, namely, the transport of molten species through the sample chamber, over distances large compared to the laser beam diameter, is presented. This effect is exploited to determine the melting behavior of high-pressure silicate assemblages of olivine composition. At pressures where beta-spinel is the phase melted, relative strengths of partitioning can be estimated for the incompatible elements studied. Iron was found to partition into the melt from beta-spinel less strongly than calcium, and slightly more strongly than manganese. At higher pressures, where a silicate perovskite/magnesiowuestite assemblage is melted, it is determined that silicate perovskite is the liquidus phase, with iron-rich magnesiowuestite accumulating at the end of the laser-melted stripe.

Campbell, Andrew J.↗

Flash melting of tantalum in a diamond cell to 85 GPa

Here, we demonstrate a new level of precision in measuring melting temperatures at high pressure using laser flash-heating followed by Scanning Electron Microscopy and Focused Ion Beam Milling. Furthermore, the new measurements on tantalum put unprecedented constraints on its highly debated melting slope, calling for a reevaluation of theoretical, shock compression and diamond cell approaches to determine melting at high pressure. X-ray analysis of the recovered samples confirmed the absence of chemical reactions, which likely played a significant role in previous experiments.

36 MATERIALS SCIENCE↗

The primary carbon and the formation of carbon species in terrestrial magmas

There is general agreement that primary carbon and redox state of mantle play an important role in the formation of carbon species in the terrestrial basalts as well as in the composition of gases, evacuated by these liquids to the upper layers of the Earth. It is expected, that interaction between native carbon and production of partial melting of the upper mantle : C(graphite,diamond) + O2(-) (melt) + O2 = CO3(2-) (melt) (1) leads to the formation of CO3(2-) (carbonate ion) in melt. Next mechanism, that may control the presence of free carbon and the formation of C-bearing components in magmas, is the carbon solubility in minerals under mantle conditions by participating in point defect equilibria.

Kadik, A.↗

Melting of troilite at high pressure in a diamond cell by laser heating

A system for measuring melting temperatures at high pressures is described. The sample is heated with radiation from a YAG laser. The beam is reflected downward through a microscope objective, through the upper diamond anvil, and focused onto the sample. Hense, intense heating is produced only at the sample and not within the diamond anvils. A vidicon system is used to observe the sample during heating. Incandescent light from the heated sample passes back through the objective lens into a grating spectrometer. The spectrum of the incandescent light is received by the photodiode array and stored in the multichannel analyzer. These data can then be transferred to floppy disk for analysis. A curve fitting program is used to compare the spectra with standard blackbody curves and to determine the temperature. Pressure is measured by the ruby fluorescence method. The system was used to study the melting behavior of natural troilite (FeS).

Bassett, William A.↗

Sub-melt nanosecond pulsed-laser induced densification and strain-field relaxation in single-crystal diamond

Dislocations and polishing-induced defect networks in synthetic diamond introduce local strain fields and broaden Raman features, limiting performance in optical, thermal, and electronic applications. Laser annealing is emerging as a promising approach to repair surface and near-surface defects in diamond without entering the melt regime, yet surface densification, defect-state modification, and associated structural changes have not been well quantified. In this work, we show that sub-melt nanosecond pulsed-laser annealing (PLA) induces near-surface densification and defect-mediated strain relaxation in single-crystal Chemical Vapor Deposition (CVD) diamond. Single- and two-pulse PLA were applied, and structural evolution was quantified using co-registered ISO 25,178 white-light interferometry, depth-resolved Raman spectroscopy, and cross-sectional STEM with geometric phase analysis (GPA). Across a 5 × 6 grid (n = 30), responsive regions exhibit large reductions in local slope (Sdq 45–65%), developed area (Sdr 60–90%), height spread (Sp, Sz 30–65%), void volume (Vv 57–60%), and roughness amplitude (Sa, Sq 48–57%), consistent with densification of ∼4–6.5 nm. Raman profiling shows narrowing of the diamond line and improved spectral uniformity to depths of ∼2–3 μm. Given that the Raman probing depth significantly exceeds the densified layer thickness, this response is interpreted as consistent with long-range strain-field redistribution originating from the near-surface region. STEM-GPA strain maps further support this interpretation, showing smoother strain fields, suppressed hotspots, and redistribution of localized strain concentrations following PLA. These results are consistent with defect-mediated strain relaxation and densification-driven modification of the near-surface energy state. The approach provides a scalable pathway for improving near-surface structural quality in diamond relevant to electronic, photonic, and quantum applications.

Areal surface metrology (ISO 25,178)↗

Stability and breakdown of Ca{sup 13}CO{sub 3} melt associated with formation of {sup 13}C-diamond in static high pressure experiments up to 43 GPa and 3900 K

Melting of calcium carbonate Ca{sup 13}CO{sub 3}, stability of the melt and its decomposition were studied in static high pressure experiments at pressures of 11-43 GPa and temperatures of 1600-3900 K using diamond anvil cell technique with laser heating. We observed formation of {sup 13}C-graphite (below 16 GPa) and {sup 13}C-diamond (between 16 and 43 GPa) on decomposition of the Ca{sup 13}CO{sub 3} melt at temperatures above 3400 K. At temperatures below 3400 K congruent melting of calcium carbonate was confirmed. The experimental results were applied to construction of the phase diagram of CaCO{sub 3} up to 43 GPa and 3900 K focusing at the melting curve of calcium carbonate and the decomposition phase boundary of CaCO{sub 3} melt. - Graphical abstract: Highlights: Black-Right-Pointing-Pointer Phase states of CaCO{sub 3} were studied at P=11-43 GPa and T=1600-3900 K. Black-Right-Pointing-Pointer {sup 13}C-diamond easily crystallizes in carbonate-carbon (Ca{sup 13}CO{sub 3-}{sup 13}C-graphite) melt-solutions. Black-Right-Pointing-Pointer Ca-carbonate melts congruently that was observed in experiments in DAC with laser heating. Black-Right-Pointing-Pointer Decomposition of CaCO{sub 3} melt, indicated by formation of graphite and/or diamond. Black-Right-Pointing-Pointer Decomposition of CaCO{sub 3} was observed at temperatures above 3400 K in the pressure interval studied.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Thermodynamics of diamond formation from hydrocarbon mixtures in planets

Hydrocarbon mixtures are extremely abundant in the Universe, and diamond formation from them can play a crucial role in shaping the interior structure and evolution of planets. With first-principles accuracy, we first estimate the melting line of diamond, and then reveal the nature of chemical bonding in hydrocarbons at extreme conditions. We finally establish the pressure-temperature phase boundary where it is thermodynamically possible for diamond to form from hydrocarbon mixtures with different atomic fractions of carbon. Notably, here we show a depletion zone at pressures above 200 GPa and temperatures below 3000 K-3500 K where diamond formation is thermodynamically favorable regardless of the carbon atomic fraction, due to a phase separation mechanism. The cooler condition of the interior of Neptune compared to Uranus means that the former is much more likely to contain the depletion zone. Our findings can help explain the dichotomy of the two ice giants manifested by the low luminosity of Uranus, and lead to a better understanding of (exo-)planetary formation and evolution.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Equilibrium and non-equilibrium effects in high pressure phase transformations of carbon

The behavior of carbon in the range 1–100 GPa and 1–10 kK is central to problems in planetary interiors, inertial confinement fusion targets, and high-pressure synthesis of carbon-based materials, but experiments in this regime are difficult and often provide only indirect constraints on phase behavior. As a result, phase boundary loci, structure, and limits of metastability at high pressure remain uncertain. In this work, machine-learning enhanced atomistic simulations are used to address this knowledge gap. We determine the melt line up to 100 GPa, the graphite-diamond phase boundary up to the melt line, and analyze structure of the coexisting phases. We show that the coexisting liquid evolves smoothly with pressure without evidence for a first-order liquid–liquid transition. Orientation-resolved graphite melting simulations indicate that basal-plane interfaces develop a dewetting layer and undergo layer-by-layer melting, producing kinetic hysteresis and an apparent orientation dependence of the melt line. Non-equilibrium quenches from the melt are used to construct a kinetically limiting graphite–diamond phase boundary for rapid quenches from above the melt line, and show that graphite is metastable at pressures of up to ≈ 25 GPa. These results provide bounds on equilibrium and metastable behavior in carbon relevant for interpreting high-pressure experiments and for designing synthesis pathways to specific carbon microstructures.

Lyu, Yanjun [Department of Materials Science and E↗

Equation of state and strength of diamond in high-pressure ramp loading

Diamond is used extensively as a component in high-energy-density experiments, but existing equation of state (EOS) models do not capture its observed response to dynamic loading. In particular, in contrast with first-principles theoretical models of equilibrium multiphase EOS, no solid-solid phase changes have been detected, and no general-purpose EOS models match the measured ambient isotherm. We have performed density functional theory (DFT) calculations of the diamond phase to ~10 TPa, well beyond its predicted range of thermodynamic stability, and used these results as the basis of a Mie-Grüneisen EOS. We also performed DFT calculations of the elastic moduli, and calibrated an algebraic elasticity model for use in simulations. We then estimated the flow stress of diamond by comparison with the stress-density relation measured experimentally in ramp-loading experiments. Furthermore, the resulting constitutive model allows us to place a constraint on the Taylor-Quinney factor (the fraction of plastic work converted to heat) from the observation that diamond does not melt on ramp compression.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Carbon isotopic signatures of super-deep diamonds mediated by iron redox chemistry

Among redox sensitive elements, carbon is specifically important because it may have been a driver rather than a passive recorder of Earth’s redox evolution. The extent to which the isotopic composition of carbon records the redox processes that shaped the Earth is still debated. In particular, the highly reduced deep mantle may be metal-saturated, yet, it is still unclear how the presence of metallic phases influences the carbon isotopic compositions of super-deep diamonds. Here we report ab initio results for the vibrational properties of carbon in carbonates, diamond, and Fe 3 C under pressure and temperature conditions relevant to super-deep diamond formation. Previous work on this question neglected the effect of pressure on the equilibrium carbon isotopic fractionation between diamond and Fe 3 C but our calculations show that this assumption overestimates the fractionation by a factor of ~1.3. Our calculated probability density functions for the carbon isotopic compositions of super-deep diamonds derived from metallic melt can readily explain the very light carbon isotopic compositions observed in some super-deep diamonds. Our results therefore support the view that metallic phases are present during the formation of super-deep diamonds in the mantle below ~250 km.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Redox Interactions between Iron and Carbon in Planetary Mantles: Implications for Degassing and Melting Processes

Carbon stability in planetary mantles has been studied by numerous authors because it is thought to be the source of C-bearing atmospheres and of C-rich lavas observed at the planetary surface. In the Earth, carbonaceous peridotites and eclogites compositions have been experimentally studied at mantle conditions [1] [2] [3]. [4] showed that the fO2 variations observed in martian meteorites can be explained by polybaric graphite-CO-CO2 equilibria in the Martian mantle. Based on thermodynamic calculations [4] and [5] inferred that the stable form of carbon in the source regions of the Martian basalts should be graphite (and/or diamond), and equilibrium with melts would be a source of CO2 for the martian atmosphere. Considering the high content of iron in the Martian mantle (approx.18.0 wt% FeO; [6]), compared to Earth s mantle (8.0 wt% FeO; [7]) Fe/C redox interactions should be studied in more detail.

Martin, A.↗

Samarium: from a distorted-fcc phase to melting under dynamic compression using in-situ x-ray diffraction

Abstract Lattice and electronic structure interactions for f -electrons are fundamental challenges for lanthanide equation of state development. Difficulties in first-principles calculations, such as density functional theory (DFT), emphasize the need for well-characterized experimental data. Here, we measure in-situ x-ray diffraction of shocked samarium (Sm) and temperature along the Hugoniot for the first time, providing direct evidence for phase transitions. We report direct evidence of a distorted fcc (dfcc) phase at 23 GPa. Shocked samarium melts from the dfcc phase starting at 33 GPa (1333 K), with complete melt at 40 GPa (1468 K). Previous work indicated shock melt at 27 GPa (1200 K), underscoring the significance of x-ray measurements for detecting phase transitions. Interestingly, our observed melting is in sharp contrast with the melting reported by a diamond anvil cell study. These experimental data can tightly constrain first principles calculations and serve as key touchstones for equation of state modeling.

36 MATERIALS SCIENCE↗

Application of Chlorine-Assisted Chemical Vapor Deposition of Diamond at Low Temperatures

Low temperature deposition of diamond has been achieved by a chlorine-assisted diamond chemical vapor deposition (CA-CVD) process. This method begins with the thermal dissociation of molecular chlorine into atomic chlorine in a resistively heated graphite furnace at temperatures between 1300 and 1500 deg. C. The atomic chlorine, upon mixing, subsequently reacts with molecular hydrogen and hydrocarbons. The rapid exchange reactions between the atomic chlorine, molecular hydrogen, and hydrocarbons give rise to the atomic hydrogen and carbon precursors required for diamond deposition. Homoepitaxial diamond growth on diamond substrates has been studied over the substrate temperature range of 100-950 C. It was found that the diamond growth rates are approximately 0.2 microns/hr in the temperature range between 102 and 300 C and that the growth rates do not decrease significantly with a decrease in substrate temperature. This is unique because the traditional diamond deposition using H2/CH4 systems usually disappears at substrate temperatures below approx. 500 deg. C. This opens up a possible route to the deposition of diamond on low-melting point materials such as aluminum and its alloys.

Pan, Chenyu↗