Klaus G. Nickel

Empirical geothermobarometry for garnet peridotites and implications for the nature of the lithosphere, kimberlites and diamonds

Abstract As a result of a study on the influence of Cr on geothermometry and geobarometry empirical garnet-orthopyroxene geobarometry has been refined. The applicability to simple and complex systems is demonstrated and the modelling procedure briefly outlined. The suitability of some geothermometers for application to garnet lherzolite xenoliths and their limits of precision are discussed. Fields of pressure-temperature estimates for garnet lherzolites from various provinces are shown. Low-temperature xenoliths ( 1050°C) give near-isobaric estimates for a range of temperatures. The depth of this “temperature discontinuity” is shallower for off-craton than for on-craton suites. Similar patterns are indicated for suites from U.S.A. and the U.S.S.R. The temperature discontinuity is interpreted as a geologically short-lived transient state, where the deepest parts of the lithosphere are in the process of adjustment to higher heat flux from below. At the highest temperatures recorded by those suites “wet” peridotitic solidi are intersected and thus the xenoliths record events, were P,T conditions may have allowed the formation of kimberlitic or strongly undersaturated magmas at about the depths of this discontinuity. This process is inferred to lead to thermal erosion of the base of the lithosphere. The generation and subsequent crystallization of magmas at the base of the lithosphere is inferred to be the source for diamond formation. The distinctive pattern of high- and low-temperature xenoliths in relation to the diamond stability field shows the existence of a rather small “diamond window” between about 900 and 1300°C at 40–55 kb. This window exists only underneath old, stable continents with a thick lithosphere. If recent age determinations on diamonds are correct, this implies the existence of thick continental lithosphere with similar characteristics to present-day lithosphere in the Archean. A model is presented arguing for hot, upwelling convection streams as a possible source of heat. The model implies differences in lithospheric development according to the speed of plates, carrying a continent: Continuous lithospheric thinning by thermal erosion for steady or very slow moving plates with the break-up of a continent and the formation of an ocean as one extreme, the continuous repetition of thermal erosion and growth on cooling (underplating) of the continental lithosphere as the other extreme for fast moving plates. The latter may be the cause of a number of complexities and heterogeneities both within the deep continental lithosphere as well as in the convecting mantle.

Phase transformations of silicon caused by contact loading

Combining hardness indentation tests and micro-Raman spectroscopy it is shown that metallic Si-II is produced near the interface of a diamond indenter and silicon to a depth of about 0.5 μm, where the highest stresses (hydrostatic and deviatoric) exist. At fast unloading rates Si-II transforms to the amorphous state, whereas a mixture of the r8 high pressure polymorph Si-XII and the bc8 phase Si-III forms upon a slow load release. The region of Si-III+Si-XII is surrounded by the wurtzite structured Si-IV, where the stresses during the indentation had not been high enough to cause the transition to the metallic state. Thus, because of shear deformation a direct transformation to Si-IV takes place. Outside the phase-transformed regions the classical aspects of indentation-induced deformation by dislocation glide, twinning and crack formation are observed. Annealing of the high pressure phases leads to the formation of Si-IV at moderate temperatures and to the reversal to the original diamond structure (Si-I...

Cyclic Nanoindentation and Raman Microspectroscopy Study of Phase Transformations in Semiconductors

This paper supplies new interpretation of nanoindentation data for silicon, germanium, and gallium arsenide based on Raman microanalysis of indentations. For the first time, Raman microspectroscopy analysis of semiconductors within nanoindentations is reported. The given analysis of the load-displacement curves shows that depth-sensing indentation can be used as a tool for identification of pressure-induced phase transformations. Volume change upon reverse phase transformation of metallic phases results either in a pop-out (or a kink-back) or in a slope change (elbow) of the unloading part of the load-displacement curve. Broad and asymmetric hysteresis loops of changing width, as well as changing slope of the elastic part of the loading curve in cyclic indentation can be used for confirmation of a phase transformation during indentation. Metallization pressure can be determined as average contact pressure (Meyers hardness) for the yield point on the loading part of the load-displacement curve. The pressure of the reverse transformation of the metallic phase can be measured from pop-out or elbow on the unloading part of the diagram. For materials with phase transformations less pronounced than in Si, replotting of the loaddisplacement curves as average contact pressure versus relative indentation depth is required to determine the transformation pressures and/or improve the accuracy of data interpretation.

RAMAN MICROSPECTROSCOPY OF NANOCRYSTALLINE AND AMORPHOUS PHASES IN HARDNESS INDENTATIONS

During hardness indentation, materials are subjected to highly l highly localized stresses. These stresses not only cause crack formation and plastic deformation by dislocation gliding, but a complete change of the crystal structure and formation of amorphous phases or high-pressure polymorphs can occur in the zone of maximum contact stresses. Such contact-induced phase transformations were observed in hard and brittle materials including semiconductors (Si, Ge, GaAs and InSb) and common ceramic materials such as SiC and SiO2 (α-quartz and silica glass). A prime tool for their investigation is the Raman microspectroscopy of hardness indentations. In Si and Ge, there is an initial transformation to metallic high-pressure phases upon hardness indentation and a subsequent formation of crystalline, nanocrystalline, or amorphous phases depending on the conditions of the hardness test, in particular the unloading rate. A phase transformation occurs also in InSb, whereas the results for GaAs do not give sufficient evidence for phase transformations. Indentation-induced amorphization has been observed in SiC and quartz. Even diamond has been shown to undergo amorphization and phase transformation under nonhydrostatic stress conditions imposed by indentation tests. Copyright

Transformation of diamond to graphite

Despite almost forty years of trying, no one has managed to transform diamond into graphite under pressure, or find out what the pressure limit for diamond might be. If diamond were to behave like other group IV elements, such as silicon, germanium or tin, it would transform under compressive indentation to the β-tin structure, but it does not. Here we use micro-Raman spectroscopy to determine what happens to diamond when it is subjected to high contact compression as a result of pressing a sharp diamond indenter against its surface. We find that, under this non-hydrostatic compression, diamond at the point of indentation is transformed into disordered graphite. This discovery may eventually lead to the more efficient machining of diamond.

Silica on Silicon Carbide

Silicon carbide (SiC) as both the most important non-oxide ceramic and promising semiconductor material grows stoichiometric SiO 2 as its native oxide. During passive oxidation, a surface transformation of SiC into silica takes place causing bulk volume and bulk mass increase. This review summarizes state-of-the-art information about the structural aspects of silicon carbide, silica, and SiC–SiO 2 interfaces and discusses physicochemical properties and kinetics of the processes involved. A special section describes the electronic properties of carbide–oxide interfaces, which are inferior compared to Si–SiO 2 interfaces, limiting the use of SiC-based electronics. In the oxidation of SiC there is a variety of parameters (e.g., porosity, presence of sintering aids, impurities, crystallographic orientation, surface treatment, and atmospheric composition) influencing the process. Therefore, the kinetics can be complex and will be discussed in detail. Nonetheless, a general linear-parabolic time-law can be found for most SiC materials for passive oxidation, thus indicating a mainly diffusion-controlled mechanism. The pronounced anisotropy of SiC expresses itself by quite different oxidation rates for the various crystallographic faces. Manifold impact factors are reflected by oxidation rate-constants for silicon carbide that vary over orders of magnitude. The understanding of SiC oxidation and silica formation is still limited; therefore, different oxidation models are presented and evaluated in the light of current knowledge.

PRESSURE-INDUCED PHASE TRANSFORMATIONS IN DIAMOND

The stability of diamond under pressure and the structure of hypothetical high-pressure phases have been a controversial issue for a long time. “Will diamond transform under megabar pressures?” asked Yin and Cohen in the title of their paper [Phys. Rev. Lett. 50, 2006 (1983)] which attempted to predict an answer to this question 15 years ago. Before and after that, many other scientists tried to find the answer doing both modeling and experiments. However, the cubic structure of diamond seems to be experimentally stable up to the highest static pressures that the modern high-pressure technology can achieve. We addressed the problem by decreasing the contact area of pressurization instead of increasing the total load. Experimentally this can be easily done in indentation tests using a sharp diamond indenter. In addition to hydrostatic stresses, such a test creates shear stresses as well. Here deformations may be realized, which are either impossible or would require much higher pressures when utilizing onl...

Orthopyroxene-clinopyroxene equilibria in the system CaO-MgO-Al2O3-SiO2 (CMAS): new experimental results and implications for two-pyroxene thermometry

AbstractA new set of reversal experiments for coexisting ortho- and clinopyroxenes in the system CMAS at conditions between 1,000–1,570° C and 30 to 50 kb is presented and combined with literature data. Pyroxene behaviour, particularly that of clinopyroxene, is very complicated and different styles of Al incorporation into the pyroxene structure for low and high concentrations of Al are indicated, strongly influencing the exchange of the enstatite component between ortho- and clinopyroxene. Thermodynamic modelling of this exchange is problematic because of the large number of unknown coefficients compared to the number of experiments. Thermometry based on such models becomes very dependent on accuracy of experimental data and analyses of small quantities of elements. Despite this complexity very simple empirical thermometric equations are capable of reproducing experimental conditions in the systems CMS and CMAS over a wide range of P, T conditions. We derived the equation

Subsolidus orthopyroxene-clinopyroxene systematics in the system CaO-MgO-SiO2 to 60 kb: a re-evaluation of the regular solution model

T^\circ {\text{ C}} = {\text{1,617}} + {\text{287}}{\text{.9}}*{\text{ln }}K_D + 2.933*P