Indentation onto Stishovite (SiO₂), MgO, and a Covered Superalloy: “Pop-In” Repair, Phase-Transition Onsets, Polymorph Energies, and Transition-Energies

The Berkovich indentation loading curves of the initially only extraterrestrial available polymorphs of SiO2 are physically analyzed by applying the now well established FN-h3/2 plots for conical/pyramidal indentations, in view of determining the phase-transition onset forces, indentation energies, and transition energies. Two phase-transitions of synthesized Stishovite yielding 2 polymorphs (one of them is Seifertite) with these properties are characterized. A third post-Stishovite polymorph is safely projected for higher load indentation. Both of them are now available at room temperature on earth for further investigation and the projected third of them is waiting. The published “pop-ins” had to be removed by self-evident repair of the force-depth curve. The meaning of published “pop-ins” is elucidated, apparently for the first time. The reasons for them and their avoidance are manifold. They are not materials’ properties but mechanical artefacts. Published pop-ins are not at all connected to phase-transitions, despite theoretical considerations claiming elastic-plastic conversion at the start of “pop-ins”. Spherical indentation analyses before them are obsolete. Final support is inter alia that one of the two new MgO twinning transitions is within a published “pop-in excursion”. The putting of a pop-in arrow at smooth loading curve without discontinuities is criticized, as the transfer between chemically different phases is neither phase transition nor “pop-in”. The polymorph’s onset forces, their energies and their endo- or exo-thermic phase-transition energies are reported. The development of the Stishovite, post-Stishovite and MgO polymorphs is mechanochemical analyzed. High pressure polymorph energetic properties are important for the earth’s sub mantel investigations and for public safety of technical materials such as MgO for constructions, or covered superalloys for e.g. airplanes, turbines, etc. Breakage and catastrophic cracks are more easily initiated at polymorph interfaces, the onset and transition energies must be above the highest possible mechanical and thermal stress for their being safe.

Ophiolite-Hosted Diamond: A New Window for Probing Carbon Cycling in the Deep Mantle

As reported in our prior work, we have recovered microdiamonds and other unusual minerals, including pseudomorph stishovite, moissanite, qingsongite, native elements, metallic alloys, and some crustal minerals (i.e., zircon, quartz, amphibole, and rutile) from ophiolitic peridotites and chromitites. These ophiolite-hosted microdiamonds display different features than kimberlitic, metamorphic, and meteoritic diamonds in terms of isotopic values and mineral inclusions. The characteristic of their light carbon isotopic composition implies that the material source of ophiolite-hosted diamonds is surface-derived organic matter. Coesite inclusions coexisting with kyanite rimming an FeTi alloy from the Luobusa ophiolite show a polycrystalline nature and a prismatic habit, indicating their origin as a replacement of stishovite. The occurrence in kyanite and coesite with inclusions of qingsongite, a cubic boron nitride mineral, and a high-pressure polymorph of rutile (TiO2 II) point to formation pressures of 10–15 GPa at temperatures^1300℃, consistent with depths greater than 380 km, near the mantle transition zone (MTZ). Minerals such as moissanite, native elements, and metallic alloys in chromite grains indicate a highly reduced environment for ophiolitic peridotites and chromitites. Widespread occurrence of diamonds in ophiolitic peridotites and chromitites suggests that the oceanic mantle may be a more significant carbon reservoir than previously thought. These ophiolite-hosted diamonds have proved that surface carbon can be subducted into the deep mantle, and have provided us with a new window for probing deep carbon cycling.

The Minimum Stable Pressure and Geological Significants of Supersilic Garnet in Continental Felsic Rocks: Constraints from HT-HP Experiments

A lot of previous experimental studies on ultramafic rocks(SiO2 unsaturated system)(Ringwood and Major, 1971;Irifune et al., 1986;Gasparik, 1989;Ono and Yasuda, 1996) have demonstrated that characteristics of Si-rich and Al-deficient in garnet are resulted from coupled substitution of SiⅥ+MⅥ=AlⅥ+AlⅥ and SiⅥ+NaⅧ=AlⅥ+MⅧ(M=Mg, Fe, Ca) at ultrahigh pressures(UHP)(>5 GPa). The degree of substitution will be enhanced by increasing pressure which has a positive correlation with the content of SiⅥ, but a negative correlation with the content of AlⅥ in supersilic garnet. These experimental results established a theoretical foundation for further understanding the formation mechanism of the exsolution of pyroxene in garnet observed in deep mantle xenoliths and some ultrahigh pressure rocks, and also for estimating the pressure conditions of the formation of supersilic garnet before exsolution(Haggerty and Sautter, 1990;Sautter et al., 1991;van Roermund et al., 1998;Ye et al., 2000). Although some experimental studies on SiO2 saturated system have been reported(Irifune et al., 1994;Ono., 1998;Dobrazhinetskya and Green.,2007;Wu et al., 2009), the stability conditions of supersilic garnet are still lack of unified understanding. Therefore, HP-HT experiments were carried out on felsic rocks under conditions of 6–12 GPa and 1000℃–1400℃. Combined with previous experimental data, we try to figure out the minimum stable pressure and geological significants of supersilic garnet in SiO2 saturated system. Our experimental results from SiO2 saturated system show the minimum stable pressure of supersilic garnet should be ≥10 GP of stishovite stability field. These results are similar as that from experiments using starting composition similar to average upper continental crust reported by Irifune et al(1994) who yielded that garnet gradually became supersilic and Al-deficient as pressures increased above 10 GPa, especially in a pressure interval between 13 and 18 GPa. Moreover, experiments with different starting materials(Ono, 1998;Dobrazhinetskya and Green, 2007;Wu et al. 2009) also indicate the stable pressure condition of supersilic garnet is mainly ≥9 –10 GPa in SiO2 saturated system if data of small-size grains at low temperature are ignored due to measuring errors. Thus, it can be concluded that the minimum stable pressure of supersilic garnet in SiO2 saturated system is distinctly different from that in SiO2 unsaturated ultramafic rock system. The minimum pressure of the former is ≥9–10 GPa of stishovite stability field, while that of the latter is >5 GPa. Therefore, whether independent SiO2 phase exist or rock system is SiO2 saturated must be taken into considered when estimating the peak pressure of exsolutions in supersilic garnet in UHP rocks. Furthermore, pressure of >5 GPa directly estimated by supersilic garnet based on conclusion from SiO2 unsaturation system rather than SiO2 saturation in previous sdudies may have been underestimated and need to be re-estimated. Supersilic garnets have been recognized by interior exsolutions of clinopyroxene in garnet pyroxene from Yinggelisayi South Altyn(Liu et al., 2005), and exsolutions of rodlike quartz+rutile in felsic gneiss from Songshugou North Qinling(Liu et al., 2003). According to the experimental results from SiO2 unsaturated system, the peak metamorphic pressure of the both SiO2 saturated rocks have been estimated to be >7 Gpa and >5 Gpa, respectively. However, combined with the new experimental results above, we re-estimated that the peak metamorphic pressure of these SiO2 saturated rocks should be≥9–10 GPa at least, implying an ultra-deep subduction to mantle depth of stishovite stability field. This research, together with previous findings(Liu et al., 2007, 2018), shows that continental subduction to mantle depth(300 km) of stishovite stability field and then exhumation to the surface is obviously more common than previously thought, and the rock types are also diverse. At the same time, it provides a new indicator and thought for recognizing the subduction to the mantle depth of stishovite stability field in UHP metamorphic belt.

SiO_2 Solubility in Rutile at High Temperature and High Pressure

Silicon-bearing rutile has been found in chromitite from the Luobusa （罗布莎） ophiolite, Tibet. However, the extent of SiO2 solubility in rutile and the nature of its origin are still unclear. At high pressure, SiO2 takes a rutile structure with Si in 6-fold coordination. Thus, high pressures may enhance its solubility in rutile because of possible isovalent exchange in the octahedral site. In this study, we report new experimental results on SiO2 solubility in rutile up to 23 GPa and 2 000℃. Starting materials were mixtures of powdered pure rutile and pure quartz, with compositions of （Ti0.5Si0.5）O2, （Ti0.93Si0.07）O2, and （Ti0.75Si0.25）O2. The mixtures were loaded into either platinum capsules （for a 10/5 assembly） or rhenium capsules （for an 8/3 assembly）. The experiments were carried out using multi-anvil high-pressure apparatus with a rhenium resistance heater. Sample temperatures were measured with a W5%Re-W26%Re thermocouple and were controlled within ±1 ℃ of the set temperature. TiO2-rich and SiO2-rich phases were produced in all the quenched samples. Microprobe analyses of the phases show that the solubility of SiO2 in rutile increases with increasing pressure, from 1.5 wt.% SiO2 at 10 GPa to 3.8 wt.% SiO2 at 23 GPa at a temperature of 1 800 ℃. The solubility also increases with increasing temperature from 0.5 wt.% SiO2 at 1 500 ℃ to 4.5 wt.% SiO2 at 2 000 ℃ at a pressure of 18 GPa. On the other hand, the solubility of TiO2 in coesite or stishovite is very limited, with an average of 0.6 wt.% TiO2 over the experimental P-T ranges. Temperature has a much larger effect on the solubility of SiO2 in ruffle than pressure. At high pressure, the melting point of SiO2 is definitely higher than that of TiO2 and the eutectic point moves towards SiO2 in the TiO2-SiO2 system. Lower oxygen fugacity decreases the solubility of SiO2 in ruffle, whereas water has little effect on the solubility. Our experimental data are extremely useful for determining the depth of origin of the SiO2-bearing rutfle found in nature.