A new miniature gasketed diamond anvil high pressure cell has been constructed to perform optical and x-ray diffraction studies on single crystals under hydrostatic pressure. For x-ray studies the cell is mounted on a standard goniometer head which may be attached to either a standard precession camera or single crystal orienter taking advantage of counting methods. The pressure cell has been used successfully in the study of the two high pressure phases of calcium carbonate, CaCO3(II) and CaCO3(III).

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A new style of diamond anvil cell (DAC) has been designed and built for conducting research in fluids at pressures to 2.5 GPa and temperatures from-190 to 1200 "C. The new DAC has been used for optical microscope observations and synchrotron x-ray diffraction studies. Fringes produced by interference of laser light reflected from top and bottom anvil faces and from top and bottom sample faces provide a very sensitive means of monitoring the volume of sample chamber and for observing volume and refractive index changes in samples that have resulted from transitions and reactions. X-ray diffraction patterns of samples under hydrothermal conditions have been made by the energy dispersive method using synchrotron radiation. The new DAC has individual heaters and individual thermocouples for the upper and lower anvils that can be controlled and can maintain temperatures with an accuracy of ho.5 "C. Low temperatures are achieved by introducing liquid nitrogen directly into the DAC. The equation of state of Hz0 and the a-0 quartz transition are used to determine pressure with an accuracy of f 1% in the aqueous samples. The new DAC has been used to redetermine five isochores of Hz0 as well as the dehydration curves of brucite, Mg(OH)z, and muscovite, Kkl,(Si,Al)O,,(OH),.-2340 Rev. Sci. Instrum.

Assemblies of 3.5 nm PbS nanoparticles (NPs) nucleate in three dominant superlattice polymorphs: amorphous, body-centered-cubic (bcc) and face-centered-cubic (fcc) phase. This superlattice relationship can be controlled by the inter-NP distance without changing the NP size. Upon increase of inter-NP distance, the packing density decreases, and the capping molecules at NP surfaces change in structure and accordingly modify the surface energy. The driving force for NP assembly develops from an entropic maximization to a reduction of total free energy through multiple interactions between surface molecules and NPs and resulting variation of surface molecules. Upon long-term aging and additional thermal treatment, fcc undergoes a tetragonal distortion and subsequently transforms to bcc phase, and simultaneously, the NPs embedded in supercrystals reduce surface energy primarily in {200} facets. Linking molecule-NP interactions with a series of changes of packing density and surface lattice spacings of NPs allows for an interpretation of principles governing the nucleation, structure stability, and transformation of PbS NP-assembled supercrystals.

Two-dimensional single-crystal PbS nanosheets were synthesized by deviatoric stress-driven orientation and attachment of nanoparticles (NPs). In situ small- and wide-angle synchrotron X-ray scattering measurements on the same spot of the sample under pressure coupled with transmission electron microscopy enable reconstruction of the nucleation route showing how enhanced deviatoric stress causes ordering NPs into single-crystal nanosheets with a lamellar mesostructure. At the same time that deviatoric stress drives SC(110) orientation in a face-centered-cubic supercrystal (SC), rocksalt (RS) NPs rotate and align their RS(200) and RS(220) planes within the SC(110) plane. When NPs approach each other along the compression axis, enhanced deviatoric stress drives soft ligands passivated at RS(200) and RS(220) surfaces to reorient from a group of SC(110) in-planes to the interspace of SC[110]-normal planes. While the internal NP structure starts a rocksalt-to-orthorhombic transition at 7.1 GPa, NPs become aligned on RS(220) and RS(200) and thus become attached at those faces. The transition-catalyzed surface atoms accelerate the inter-NP coalescing process and the formation of low-energy structure nanosheet. Above 11.6 GPa, the nucleated single-crystal nanosheets stack into a lamellar mesostructure that has a domain size comparable to the starting supercrystal.

Large scale three-dimensional supercrystals were grown by controlling evaporation of truncate PbS nanocrystal (NC) dispersed hexane suspensions. Electron microscopy analysis confirmed the nature of single supercrystal with a face-centered cubic (fcc) lattice. Synchrotron small/wide angle scattering (SAXS/WAXS) images from three typical crystallographic projections allowed ultimate reconstruction of shape orientations of NCs at different crystallographic sites. Position exchange of distinctly oriented NCs between crystallographic sites produces two nondegeneration shape-related pseudo-polymorphs of superlattice that accordingly reduce symmetry from Oh to C4h and C2h with various facet-to-facet arrangements, respectively. In situ SAXS measurements of NC-assembled supercrystal and lead oleate and oleic acid upon pressurization provide additional insights into surface ligand density and the nature of ligand-NC interactions and resulting interface structure. These results allow for feasible evaluation of both NC shape and ligand conformation enabled effects that govern the formation and stability of truncate NC assemblies with various superlattice polymorphs and associated NC-ligand interactions in solvent-mediated assembled processes.

High‐pressure, high‐temperature properties of MgSiO3, (Fe0.1Mg0.9)SiO3, and (Fe0.2Mg0.8)SiO3 perovskites have been investigated using a newly developed X ray diffraction technique involving monochromatic synchrotron radiation. The first direct measurements of unit cell distortions and equation‐of‐state parameters of the orthorhombic perovskite as functions of composition and simultaneous high pressure and high temperature were obtained. The experiments were conducted under hydrostatic pressure up to 30 GPa, into the stability field of the perovskite. The results demonstrate that the perovskite is elastically anisotropic, with the lattice parameter b being 25% less compressible than a and c. Under increasing pressures the orthorhombic perovskite is distorted further away from the ideal cubic structure in agreement with theoretical predictions. The 298‐K isothermal equations of state of the three perovskites are indistinguishable within the uncertainty limits of the experiment. The zero‐pressure bulk modulus KT0 = 261 (±4) GPa with its pressure derivative KT0′ = 4 is close to that determined in previous static high pressure measurements. The thermal expansion obtained from the high P ‐ T experiments are consistent with previous measurements carried out at zero pressure but shows a strong volume dependence. The temperature derivative of the isothermal bulk modulus at constant pressure (∂KT/∂T)p is −6.3(±0.5)×10−2 GPa/K. Analyses of the high‐temperature data give a value for the Anderson‐Grüneisen parameter δT of 6.5–7.5, which is significantly higher than that used in recent lower mantle models.

Lattice parameters of the bcc and hcp phases of iron have been determined as a function of pressure up to 300 kbar at 23°±3°C by means of x-ray diffraction techniques. The c/a ratio for hcp iron has been determined to be 1.603±0.001 at pressures between 80 and 300 kbar and is independent of pressure. Based upon the extrapolation of the high-pressure data using an exponential form of the Murnaghan equation of state, the volume of hcp iron at zero pressure is 6.72±0.06 cm3/mole. The volume change for the bcc-hcp transformation at 130 kbar is −0.34±0.01 cm3/mole. This value satisfies the triple point conditions for the bcc-hcp-fcc triple point when published values for the other phase transformations are used.