Chemical and mineralogical characterization of micro-inclusions in diamonds

Secondary-ion mass spectrometry (SIMS), electron probe analysis (EPMA), analytical scanning electron microscopy (SEM) and infrared (IR) spectroscopy were used to determine the chemical composition and the mineralogy of sub-micrometer inclusions in cubic diamonds and in overgrowths (coats) on octahedral diamonds from Zaire, Botswana, and some unknown localities.

The inclusions are sub-micrometer in size. The typical diameter encountered during transmission electron microscope (TEM) examination was 0.1-0.5 µm. The micro-inclusions are sub-rounded and their shape is crystallographically controlled by the diamond. Normally they are not associated with cracks or dislocations and appear to be well isolated within the diamond matrix. The number density of inclusions is highly variable on any scale and may reach 10^(11) inclusions/cm^3 in the most densely populated zones. The total concentration of metal oxides in the diamonds varies between 20 and 1270 ppm (by weight).

SIMS analysis yields the average composition of about 100 inclusions contained in the sputtered volume. Comparison of analyses of different volumes of an individual diamond show roughly uniform composition (typically ±10% relative). The variation among the average compositions of different diamonds is somewhat greater (typically ±30%). Nevertheless, all diamonds exhibit similar characteristics, being rich in water, carbonate, SiO_2, and K_2O, and depleted in MgO. The composition of micro-inclusions in most diamonds vary within the following ranges: SiO_2, 30-53%; K_2O, 12-30%; CaO, 8-19%; FeO, 6-11%; Al_2O_3, 3-6%; MgO, 2-6%; TiO_2, 2-4%; Na_2O, 1-5%; P_2O_5, 1-4%; and Cl, 1-3%. In addition, BaO, 1-4%; SrO, 0.7-1.5%; La_2O_3, 0.1-0.3%; Ce_2O_3, 0.3-0.5%; smaller amounts of other rare-earth elements (REE), as well as Mn, Th, and U were also detected by instrumental neutron activation analysis (INAA). Mg/(Fe+Mg), 0.40-0.62 is low compared with other mantle derived phases; K/ AI ratios of 2-7 are very high, and the chondrite-normalized Ce/Eu ratios of 10-21 are also high, indicating extremely fractionated REE patterns.

SEM analyses indicate that individual inclusions within a single diamond are roughly of similar composition. The average composition of individual inclusions as measured with the SEM is similar to that measured by SIMS. Compositional variations revealed by the SEM are larger than those detected by SIMS and indicate a small variability in the composition of individual inclusions. No compositions of individual inclusions were determined that might correspond to mono-mineralic inclusions.

IR spectra of inclusion- bearing zones exhibit characteristic absorption due to: (1) pure diamonds, (2) nitrogen and hydrogen in the diamond matrix; and (3) mineral phases in the micro-inclusions. Nitrogen concentrations of 500-1100 ppm, typical of the micro-inclusion-bearing zones, are higher than the average nitrogen content of diamonds. Only type IaA centers were detected by IR. A yellow coloration may indicate small concentration of type IB centers.

The absorption due to the micro-inclusions in all diamonds produces similar spectra and indicates the presence of hydrated sheet silicates (most likely, Fe-rich clay minerals), carbonates (most likely calcite), and apatite. Small quantities of molecular CO_2 are also present in most diamonds. Water is probably associated with the silicates but the possibility of its presence as a fluid phase cannot be excluded. Characteristic lines of olivine, pyroxene and garnet were not detected and these phases cannot be significant components of the inclusions. Preliminary quantification of the IR data suggests that water and carbonate account for, on average, 20-40 wt% of the micro-inclusions.

The composition and mineralogy of the micro-inclusions are completely different from those of the more common, larger inclusions of the peridotitic or eclogitic assemblages. Their bulk composition resembles that of potassic magmas, such as kimberlites and lamproites, but is enriched in H_2O, CO_3, K_2O, and incompatible elements, and depleted in MgO.

It is suggested that the composition of the micro-inclusions represents a volatile-rich fluid or a melt trapped by the diamond during its growth. The high content of K, Na, P, and incompatible elements suggests that the trapped material found in the micro-inclusions may represent an effective metasomatizing agent. It may also be possible that fluids of similar composition are responsible for the extreme enrichment of incompatible elements documented in garnet and pyroxene inclusions in diamonds.

The origin of the fluid trapped in the micro-inclusions is still uncertain. It may have been formed by incipient melting of a highly metasomatized mantle rocks. More likely, it is the result of fractional crystallization of a potassic parental magma at depth. In either case, the micro-inclusions document the presence of highly potassic fluids or melts at depths corresponding to the diamond stability field in the upper mantle. The phases presently identified in the inclusions are believed to be the result of closed system reactions at lower pressures.

Dynamic characterization of micro-particle systems

Ordered granular systems have been a subject of active research for decades. Due to their rich dynamic response and nonlinearity, ordered granular systems have been suggested for several applications, such as solitary wave focusing, acoustic signals manipulation, and vibration absorption. Most of the fundamental research performed on ordered granular systems has focused on macro-scale examples. However, most engineering applications require these systems to operate at much smaller scales. Very little is known about the response of micro-scale granular systems, primarily because of the difficulties in realizing reliable and quantitative experiments, which originate from the discrete nature of granular materials and their highly nonlinear inter-particle contact forces.

In this work, we investigate the physics of ordered micro-granular systems by designing an innovative experimental platform that allows us to assemble, excite, and characterize ordered micro-granular systems. This new experimental platform employs a laser system to deliver impulses with controlled momentum and incorporates non-contact measurement apparatuses to detect the particles’ displacement and velocity. We demonstrated the capability of the laser system to excite systems of dry (stainless steel particles of radius 150 micrometers) and wet (silica particles of radius 3.69 micrometers, immersed in fluid) micro-particles, after which we analyzed the stress propagation through these systems.

We derived the equations of motion governing the dynamic response of dry and wet particles on a substrate, which we then validated in experiments. We then measured the losses in these systems and characterized the collision and friction between two micro-particles. We studied wave propagation in one-dimensional dry chains of micro-particles as well as in two-dimensional colloidal systems immersed in fluid. We investigated the influence of defects to wave propagation in the one-dimensional systems. Finally, we characterized the wave-attenuation and its relation to the viscosity of the surrounding fluid and performed computer simulations to establish a model that captures the observed response.

The findings of the study offer the first systematic experimental and numerical analysis of wave propagation through ordered systems of micro-particles. The experimental system designed in this work provides the necessary tools for further fundamental studies of wave propagation in both granular and colloidal systems.

Effects of injection nozzle configuration on secondary injection into supersonic flow

Gaseous nitrogen and argon were injected into a primary stream of air moving at Mach 2.56. The gases were injected at secondary to primary total pressure ratios from 3.2 to 28.6 through four different nozzles. Two nozzles, one sonic and one supersonic (M = 3.26), injected normal to the primary stream; and two sonic nozzles injected at 45° angles to the primary flow, one injecting upstream and the other downstream. Data consisted of static pressure measurements on the wall near the injector, total pressure profiles in the wake of the injectant plume, and concentration measurements downstream of the flow. Scale parameters were calculated based upon an analytical model of the flow field and their validity verified by experimental results. These scale heights were used to compare normalized wall side forces for the different nozzles and to compare the mixing of the two streams.

I. The attenuation and dispersion of sound in a condensing medium. II. The flow of a gas-particle mixture downstream of a normal shock in a nozzle

I. The attenuation of sound due to particles suspended in a gas was first calculated by Sewell and later by Epstein in their classical works on the propagation of sound in a two-phase medium. In their work, and in more recent works which include calculations of sound dispersion, the calculations were made for systems in which there was no mass transfer between the two phases. In the present work, mass transfer between phases is included in the calculations.

The attenuation and dispersion of sound in a two-phase condensing medium are calculated as functions of frequency. The medium in which the sound propagates consists of a gaseous phase, a mixture of inert gas and condensable vapor, which contains condensable liquid droplets. The droplets, which interact with the gaseous phase through the interchange of momentum, energy, and mass (through evaporation and condensation), are treated from the continuum viewpoint. Limiting cases, for flow either frozen or in equilibrium with respect to the various exchange processes, help demonstrate the effects of mass transfer between phases. Included in the calculation is the effect of thermal relaxation within droplets. Pressure relaxation between the two phases is examined, but is not included as a contributing factor because it is of interest only at much higher frequencies than the other relaxation processes. The results for a system typical of sodium droplets in sodium vapor are compared to calculations in which there is no mass exchange between phases. It is found that the maximum attenuation is about 25 per cent greater and occurs at about one-half the frequency for the case which includes mass transfer, and that the dispersion at low frequencies is about 35 per cent greater. Results for different values of latent heat are compared.

II. In the flow of a gas-particle mixture through a nozzle, a normal shock may exist in the diverging section of the nozzle. In Marble’s calculation for a shock in a constant area duct, the shock was described as a usual gas-dynamic shock followed by a relaxation zone in which the gas and particles return to equilibrium. The thickness of this zone, which is the total shock thickness in the gas-particle mixture, is of the order of the relaxation distance for a particle in the gas. In a nozzle, the area may change significantly over this relaxation zone so that the solution for a constant area duct is no longer adequate to describe the flow. In the present work, an asymptotic solution, which accounts for the area change, is obtained for the flow of a gas-particle mixture downstream of the shock in a nozzle, under the assumption of small slip between the particles and gas. This amounts to the assumption that the shock thickness is small compared with the length of the nozzle. The shock solution, valid in the region near the shock, is matched to the well known small-slip solution, which is valid in the flow downstream of the shock, to obtain a composite solution valid for the entire flow region. The solution is applied to a conical nozzle. A discussion of methods of finding the location of a shock in a nozzle is included.

I. The effect of droplet solidification upon two-phase flow in a rocket nozzle. II. A kinetic theory investigation of some condensation-evaporation phenomena by a moment method

Part I:

The perturbation technique developed by Rannie and Marble is used to study the effect of droplet solidification upon two-phase flow in a rocket nozzle. It is shown that under certain conditions an equilibrium flow exists, where the gas and particle phases have the same velocity and temperature at each section of the nozzle. The flow is divided into three regions: the first region, where the particles are all in the form of liquid droplets; a second region, over which the droplets solidify at constant freezing temperature; and a third region, where the particles are all solid. By a perturbation about the equilibrium flow, a solution is obtained for small particle slip velocities using the Stokes drag law and the corresponding approximation for heat transfer between the particle and gas phases. Singular perturbation procedure is required to handle the problem at points where solidification first starts and where it is complete. The effects of solidification are noticeable.

Part II:

When a liquid surface, in contact with only its pure vapor, is not in the thermodynamic equilibrium with it, a net condensation or evaporation of fluid occurs. This phenomenon is studied from a kinetic theory viewpoint by means of moment method developed by Lees. The evaporation-condensation rate is calculated for a spherical droplet and for a liquid sheet, when the temperatures and pressures are not too far removed from their equilibrium values. The solutions are valid for the whole range of Knudsen numbers from the free molecule to the continuum limit. In the continuum limit, the mass flux rate is proportional to the pressure difference alone.

Understanding Micro- and Macro-Mechanics of Soil Liquefaction: A Necessary Step for Field-Scale Assessment

Liquefaction is a devastating instability associated with saturated, loose, and cohesionless soils. It poses a significant risk to distributed infrastructure systems that are vital for the security, economy, safety, health, and welfare of societies. In order to make our cities resilient to the effects of liquefaction, it is important to be able to identify areas that are most susceptible. Some of the prevalent methodologies employed to identify susceptible areas include conventional slope stability analysis and the use of so-called liquefaction charts. However, these methodologies have some limitations, which motivate our research objectives. In this dissertation, we investigate the mechanics of origin of liquefaction in a laboratory test using grain-scale simulations, which helps (i) understand why certain soils liquefy under certain conditions, and (ii) identify a necessary precursor for onset of flow liquefaction. Furthermore, we investigate the mechanics of liquefaction charts using a continuum plasticity model; this can help in modeling the surface hazards of liquefaction following an earthquake. Finally, we also investigate the microscopic definition of soil shear wave velocity, a soil property that is used as an index to quantify liquefaction resistance of soil. We show that anisotropy in fabric, or grain arrangement can be correlated with anisotropy in shear wave velocity. This has the potential to quantify the effects of sample disturbance when a soil specimen is extracted from the field. In conclusion, by developing a more fundamental understanding of soil liquefaction, this dissertation takes necessary steps for a more physical assessment of liquefaction susceptibility at the field-scale.