Advancing Chemical Separations: Unraveling the Structure and Dynamics of Phase Splitting in Liquid-Liquid Extraction.

Liquid-liquid extraction (LLE), the go-to process for a variety of chemical separations, is limited by spontaneous organic phase splitting upon sufficient solute loading, called third phase formation. In this study we explore the applicability of critical phenomena theory to gain insight into this deleterious phase behavior with the goal of improving separations efficiency and minimizing waste. A series of samples representative of rare earth purification were constructed to include each of one light and one heavy lanthanide (cerium and lutetium) paired with one of two common malonamide extractants (DMDOHEMA and DMDBTDMA). The resulting postextraction organic phases are chemically complex and often form rich hierarchical structures whose statics and dynamics near the critical point were probed herein with small-angle X-ray scattering and high-speed X-ray photon correlation spectroscopy. Despite their different extraction behaviors, all samples show remarkably similar critical behavior with exponents well described by classical critical point theory consistent with the 3D Ising model, where the critical behavior is characterized by fluctuations with a single diverging length scale. This unexpected result indicates a significant reduction in relevant chemical parameters at the critical point, indicating that the underlying behavior of phase transitions in LLE rely on far fewer variables than are generally assumed. The obtained scalar order parameter is attributed to the extractant fraction of the extractant/diluent mixture, revealing that other solution components and their respective concentrations simply shift the critical temperature but do not affect the nature of the critical fluctuations. These findings point to an opportunity to drastically simplify studies of liquid-liquid phase separation and phase diagram development in general while providing insights into LLE process improvement.

Nanoscale Critical Phenomena in a Complex Fluid Studied by X-Ray Photon Correlation Spectroscopy.

The advent of high-speed x-ray photon correlation spectroscopy now allows the study of critical phenomena in fluids to much smaller length scales and over a wider range of temperatures than is possible with dynamic light scattering. We present an x-ray photon correlation spectroscopy study of critical fluctuation dynamics in a complex fluid typical of those used in liquid-liquid extraction (LLE) of ions, dodecane-DMDBTDMA with extracted aqueous Ce(NO_{3})_{3}. We observe good agreement with both static and dynamic scaling without the need for significant noncritical background corrections. Critical exponents agree with 3D Ising values, and the fluctuation dynamics are described by simple exponential relaxation. The form of the dynamic master curve deviates somewhat from the Kawasaki result, with a more abrupt transition between the critical and noncritical asymptotic behavior. The concepts of critical phenomena thus provide a quantitative framework for understanding the structure and dynamics of LLE systems and a path forward to new LLE processes.

Design and measurements of low power multichannel chip for recording and stimulation of neural activity.

A 64-channel Neuro-Stimulation-Recording chip named NRS64 for neural activity measurements has been designed and tested. The NRS64 occupies 5×5 mm² of silicon area and consumes only 25 µW/channel. A low cut-off frequency can be tuned in the 60 mHz-100 Hz range while a high cut-off frequency can be set to 4.7 kHz or 12 kHz. A voltage gain can be set to 139 V/V or 1100 V/V. A measured input referenced noise is 3.7 µV rms in 100 Hz-12 kHz band and 7.6 µV rms in 3 Hz-12 kHz band. A digital correction is used in each channel to tune the low cut-off frequency and offset voltage. Each channel is equipped additionally with a stimulation circuit with an artifact cancellation circuit. The stimulation circuit can be set with 8-bit resolution in six different ranges from 500 nA-512 µA range.

Design and measurements of 64-channel ASIC for neural signal recording.

This paper presents the design and measurements of a low noise multi-channel front-end electronics for recording extra-cellular neuronal signals using microelectrode arrays. The integrated circuit contains 64 readout channels and was fabricated in CMOS 0.18 microm technology. A single readout channel is built of an AC coupling circuit at the input, a low noise preamplifier, a band-pass filter and a second amplifier. In order to reduce the number of output lines, the 64 analog signals from readout channels are multiplexed to a single output by an analog multiplexer. The chip is optimized for low noise and matching performance with the possibility of cut-off frequencies tuning. The low cut-off frequency can be tuned in the 1 Hz-60 Hz range and the high cut-off frequency can be tuned in the 3.5 kHz-15 kHz range. For the nominal gain setting at 44 dB and power dissipation per single channel of 220 microW the equivalent input noise is in the range from 6 microV-11 microV rms depending on the band-pass filter settings. The chip has good uniformity concerning the spread of its electrical parameters from channel to channel. The spread of gain calculated as standard deviation to mean value is about 4.4% and the spread of the low cut-off frequency is on the same level. The chip occupies 5x2.3 mm(2) of silicon area.