Chuanlong Lin

Online remote control systems for static and dynamic compression and decompression using diamond anvil cells

The ability to remotely control pressure in diamond anvil cells (DACs) in accurate and consistent manner at room temperature, as well as at cryogenic and elevated temperatures, is crucial for effective and reliable operation of a high-pressure synchrotron facility such as High Pressure Collaborative Access Team (HPCAT). Over the last several years, a considerable effort has been made to develop instrumentation for remote and automated pressure control in DACs during synchrotron experiments. We have designed and implemented an array of modular pneumatic (double-diaphragm), mechanical (gearboxes), and piezoelectric devices and their combinations for controlling pressure and compression/decompression rate at various temperature conditions from 4 K in cryostats to several thousand Kelvin in laser-heated DACs. Because HPCAT is a user facility and diamond cells for user experiments are typically provided by users, our development effort has been focused on creating different loading mechanisms and frames for a variety of existing and commonly used diamond cells rather than designing specialized or dedicated diamond cells with various drives. In this paper, we review the available instrumentation for remote static and dynamic pressure control in DACs and show some examples of their applications to high pressure research.

New developments in micro-X-ray diffraction and X-ray absorption spectroscopy for high-pressure research at 16-BM-D at the Advanced Photon Source

The monochromator and focusing mirrors of the 16-BM-D beamline, which is dedicated to high-pressure research with micro-X-ray diffraction (micro-XRD) and X-ray absorption near edge structure (XANES) (6-45 keV) spectroscopy, have been recently upgraded. Monochromatic X-rays are selected by a Si (111) double-crystal monochromator operated in an artificial channel-cut mode and focused to 5 μm × 5 μm (FWHM) by table-top Kirkpatrick-Baez type mirrors located near the sample stage. The typical X-ray flux is ∼5 × 10(8) photons/s at 30 keV. The instrumental resolution, Δq/qmax, reaches to 2 × 10(-3) and is tunable through adjustments of the detector distance and X-ray energy. The setup is stable and reproducible, which allows versatile application to various types of experiments including resistive heating and cryogenic cooling as well as ambient temperature compression. Transmission XANES is readily combined with micro-XRD utilizing the fixed-exit feature of the monochromator, which allows combined XRD-XANES measurements at a given sample condition.

Developments in time-resolved high pressure x-ray diffraction using rapid compression and decompression

Complementary advances in high pressure research apparatus and techniques make it possible to carry out time-resolved high pressure research using what would customarily be considered static high pressure apparatus. This work specifically explores time-resolved high pressure x-ray diffraction with rapid compression and/or decompression of a sample in a diamond anvil cell. Key aspects of the synchrotron beamline and ancillary equipment are presented, including source considerations, rapid (de)compression apparatus, high frequency imaging detectors, and software suitable for processing large volumes of data. A number of examples are presented, including fast equation of state measurements, compression rate dependent synthesis of metastable states in silicon and germanium, and ultrahigh compression rates using a piezoelectric driven diamond anvil cell.

A metastable liquid melted from a crystalline solid under decompression

A metastable liquid may exist under supercooling, sustaining the liquid below the melting point such as supercooled water and silicon. It may also exist as a transient state in solid–solid transitions, as demonstrated in recent studies of colloidal particles and glass-forming metallic systems. One important question is whether a crystalline solid may directly melt into a sustainable metastable liquid. By thermal heating, a crystalline solid will always melt into a liquid above the melting point. Here we report that a high-pressure crystalline phase of bismuth can melt into a metastable liquid below the melting line through a decompression process. The decompression-induced metastable liquid can be maintained for hours in static conditions, and transform to crystalline phases when external perturbations, such as heating and cooling, are applied. It occurs in the pressure–temperature region similar to where the supercooled liquid Bi is observed. Akin to supercooled liquid, the pressure-induced metastable liquid may be more ubiquitous than we thought.

Experimental evidence of low-density liquid water upon rapid decompression

Significance To understand water’s anomalous behavior, a two-liquid model with a high-density liquid and a low-density liquid (LDL) has been proposed from theoretical simulations, and is gradually gaining ground. However, it has been experimentally challenging to probe the region of the phase diagram of H2O where the LDL phase is expected to occur. We overcome the experimental challenge by using a technique of rapid decompression integrated with fast synchrotron measurements, and show that the region of LDL is accessible via decompression of a high-pressure crystal. We report the experimental evidence of the LDL from in situ X-ray diffraction and its crystallization process, providing a kinetic pathway for the appearance of LDL as an intermediate phase in the crystal–crystal transformation upon decompression. Water is an extraordinary liquid, having a number of anomalous properties which become strongly enhanced in the supercooled region. Due to rapid crystallization of supercooled water, there exists a region that has been experimentally inaccessible for studying deeply supercooled bulk water. Using a rapid decompression technique integrated with in situ X-ray diffraction, we show that a high-pressure ice phase transforms to a low-density noncrystalline (LDN) form upon rapid release of pressure at temperatures of 140–165 K. The LDN subsequently crystallizes into ice-Ic through a diffusion-controlled process. Together with the change in crystallization rate with temperature, the experimental evidence indicates that the LDN is a low-density liquid (LDL). The measured X-ray diffraction data show that the LDL is tetrahedrally coordinated with the tetrahedral network fully developed and clearly linked to low-density amorphous ices. On the other hand, there is a distinct difference in structure between the LDL and supercooled water or liquid water in terms of the tetrahedral order parameter.

Kinetics of the B1-B2 phase transition in KCl under rapid compression

Kinetics of the B1-B2 phase transition in KCl has been investigated under various compression rates (0.03–13.5 GPa/s) in a dynamic diamond anvil cell using time-resolved x-ray diffraction and fast imaging. Our experimental data show that the volume fraction across the transition generally gives sigmoidal curves as a function of pressure during rapid compression. Based upon classical nucleation and growth theories (Johnson-Mehl-Avrami-Kolmogorov theories), we propose a model that is applicable for studying kinetics for the compression rates studied. The fit of the experimental volume fraction as a function of pressure provides information on effective activation energy and average activation volume at a given compression rate. The resulting parameters are successfully used for interpreting several experimental observables that are compression-rate dependent, such as the transition time, grain size, and over-pressurization. The effective activation energy (Qeff) is found to decrease linearly with the logari...

Effect of stress on melting of rhombohedral bismuth

Pressure-induced melting of rhombohedral bismuth (Bi-I) has been investigated in the solid pressure medium of NaCl and the hydrostatic medium of neon at high temperatures by in-situ synchrotron x-ray diffraction. Upon compression from ∼0.7 GPa to 3.2 GPa at (or below) 489 K, Bi-I melts into a liquid between ∼1.2 and 1.6 GPa in the solid pressure medium and then crystallizes into Bi-IV at ∼2.9 GPa. However, at the same temperature of 489 K, Bi-I transforms to a crystalline phase (Bi-II′ or Bi-II) at ∼1.8 GPa under hydrostatic conditions, followed by a transformation to Bi-IV at 2.5 GPa. Our x-ray diffraction results indicate that the melting of Bi-I at (or below) 489 K is due to the stress. There is a stress effect on the structural deformation of Bi-I when the solid pressure medium is used, viz., pressure-dependent c/a for Bi-I in the solid pressure medium is larger or smaller than that under hydrostatic conditions. According to the classical nucleation theory, the stress provides an additional driving fo...

Pressure-induced transformations of multiferroic relaxor PbFe0.5Nb0.5O3

The effects of hydrostatic pressure at ambient temperature on the structural and dielectric properties of PbFe0.5Nb0.5O3 (PFN) were investigated using second harmonic generation (SHG) and powder x-ray diffraction measurements to 31 GPa. The results demonstrate that PFN undergoes a pressure-induced structural transition from the R3m ferroelectric to the R 3 ¯ m paraelectric phase. SHG measurements showed a continuous decrease in the signal with pressure and complete disappearance at 7.1 GPa. Effective nonlinear optical coefficients were determined from the SHG data, and their pressure behavior was used to infer the nature of the transition. The loss of the SHG signal is accompanied by drastic changes in line widths of Bragg reflections, but no discontinuous change in volume was observed. The pressure-volume data were fit to various equations of state, and a bulk modulus K0 = 136 (±2) GPa, bulk modulus pressure derivative K0′ = 4.0 (±0.2), and initial volume V0 = 64.5 (±0.1) A3 were obtained.