Stability of Electrode-Electrolyte Interfaces during Charging in Lithium Batteries

In this thesis we study the growth of a Li electrode-electrolyte interface in the presence of an elastic prestress. In particular, we focus our interest on Li-air batteries with a solid electrolyte, LIPON, which is a new type of secondary or rechargeable battery. Theoretical studies and experimental evidence show that during the process of charging the battery the replated lithium adds unevenly to the electrode surface. This phenomenon eventually leads to dendrite formation as the battery is charged and discharged numerous times. In order to suppress or alleviate this deleterious effect of dendrite growth, we put forth a study based on a linear stability analysis. Taking into account all the mechanisms of mass transport and interfacial kinetics, we model the evolution of the interface. We find that, in the absence of stress, the stability of a planar interface depends on interfacial diffusion properties and interfacial energy. Specifically, if Herring-Mullins capillarity-driven interfacial diffusion is accounted for, interfaces are unstable against all perturbations of wavenumber larger than a critical value. We find that the effect of an elastic prestress is always to stabilize planar interfacial growth by increasing the critical wavenumber for instability. A parametric study results in quantifying the extent of the prestress stabilization in a manner that can potentially be used in the design of Li-air batteries. Moreover, employing the theory of finite differences we numerically solve the equation that describes the evolution of the surface profile and present visualization results of the surface evolution by time. Lastly, numerical simulations performed in a commercial finite element software validate the theoretical formulation of the interfacial elastic energy change with respect to the planar interface.

Development of roll waves in open channels

This study is concerned with some of the properties of roll waves that develop naturally from a turbulent uniform flow in a wide rectangular channel on a constant steep slope . The wave properties considered were depth at the wave crest, depth at the wave trough, wave period, and wave velocity . The primary focus was on the mean values and standard deviations of the crest depths and wave periods at a given station and how these quantities varied with distance along the channel.

The wave properties were measured in a laboratory channel in which roll waves developed naturally from a uniform flow . The Froude number F (F = u_n/√gh_n, u_n = normal velocity , h_n = normal depth, g =acceleration of gravity) ranged from 3. 4 to 6. 0 for channel slopes S_o of . 05 and . 12 respectively . In the initial phase of their development the roll waves appeared as small amplitude waves with a continuous water surface profile . These small amplitude waves subsequently developed into large amplitude shock waves. Shock waves were found to overtake and combine with other shock waves with the result that the crest depth of the combined wave was larger than the crest depths before the overtake. Once roll waves began to develop, the mean value of the crest depths h_nmax increased with distance . Once the shock waves began to overtake, the mean wave period T_av increased approximately linearly with distance.

For a given Froude number and channel slope the observed quantities h^-_max/h_n , T' (T' = S_o T_av √g/h_n), and the standard deviations of h^-_max/h_n and T', could be expressed as unique functions of l/h_n (l = distance from beginning of channel) for the two-fold change in h_n occurring in the observed flows . A given value of h^-_max/h_n occurred at smaller values of l/h_n as the Froude number was increased. For a given value of h /hh^-_max/h_n the growth rate of δh^-_max/h^-_maxδl of the shock waves increased as the Froude number was increased.

A laboratory channel was also used to measure the wave properties of periodic permanent roll waves. For a given Froude number and channel slope the h^-_max/h_n vs. T' relation did not agree with a theory in which the weight of the shock front was neglected. After the theory was modified to include this weight, the observed values of h^-_max/h_n were within an average of 6.5 percent of the predicted values, and the maximum discrepancy was 13.5 percent.

For h^-_max/h_n sufficiently large (h^-_max/h_n > approximately 1.5) it was found that the h^-_max/h_n vs. T' relation for natural roll waves was practically identical to the h^-_max/h_n vs. T' relation for periodic permanent roll waves at the same Froude number and slope. As a result of this correspondence between periodic and natural roll waves, the growth rate δh^-_max/h^-_maxδl of shock waves was predicted to depend on the channel slope, and this slope dependence was observed in the experiments.

Single cell proteomics microchip to profile immune function, with applications in stem cell biology, translational disease mechanism study and clinical therapeutics monitoring

In response to infection or tissue dysfunction, immune cells develop into highly heterogeneous repertoires with diverse functions. Capturing the full spectrum of these functions requires analysis of large numbers of effector molecules from single cells. However, currently only 3-5 functional proteins can be measured from single cells. We developed a single cell functional proteomics approach that integrates a microchip platform with multiplex cell purification. This approach can quantitate 20 proteins from >5,000 phenotypically pure single cells simultaneously. With a 1-million fold miniaturization, the system can detect down to ~100 molecules and requires only ~104 cells. Single cell functional proteomic analysis finds broad applications in basic, translational and clinical studies. In the three studies conducted, it yielded critical insights for understanding clinical cancer immunotherapy, inflammatory bowel disease (IBD) mechanism and hematopoietic stem cell (HSC) biology.

To study phenotypically defined cell populations, single cell barcode microchips were coupled with upstream multiplex cell purification based on up to 11 parameters. Statistical algorithms were developed to process and model the high dimensional readouts. This analysis evaluates rare cells and is versatile for various cells and proteins. (1) We conducted an immune monitoring study of a phase 2 cancer cellular immunotherapy clinical trial that used T-cell receptor (TCR) transgenic T cells as major therapeutics to treat metastatic melanoma. We evaluated the functional proteome of 4 antigen-specific, phenotypically defined T cell populations from peripheral blood of 3 patients across 8 time points. (2) Natural killer (NK) cells can play a protective role in chronic inflammation and their surface receptor – killer immunoglobulin-like receptor (KIR) – has been identified as a risk factor of IBD. We compared the functional behavior of NK cells that had differential KIR expressions. These NK cells were retrieved from the blood of 12 patients with different genetic backgrounds. (3) HSCs are the progenitors of immune cells and are thought to have no immediate functional capacity against pathogen. However, recent studies identified expression of Toll-like receptors (TLRs) on HSCs. We studied the functional capacity of HSCs upon TLR activation. The comparison of HSCs from wild-type mice against those from genetics knock-out mouse models elucidates the responding signaling pathway.

In all three cases, we observed profound functional heterogeneity within phenotypically defined cells. Polyfunctional cells that conduct multiple functions also produce those proteins in large amounts. They dominate the immune response. In the cancer immunotherapy, the strong cytotoxic and antitumor functions from transgenic TCR T cells contributed to a ~30% tumor reduction immediately after the therapy. However, this infused immune response disappeared within 2-3 weeks. Later on, some patients gained a second antitumor response, consisted of the emergence of endogenous antitumor cytotoxic T cells and their production of multiple antitumor functions. These patients showed more effective long-term tumor control. In the IBD mechanism study, we noticed that, compared with others, NK cells expressing KIR2DL3 receptor secreted a large array of effector proteins, such as TNF-α, CCLs and CXCLs. The functions from these cells regulated disease-contributing cells and protected host tissues. Their existence correlated with IBD disease susceptibility. In the HSC study, the HSCs exhibited functional capacity by producing TNF-α, IL-6 and GM-CSF. TLR stimulation activated the NF-κB signaling in HSCs. Single cell functional proteome contains rich information that is independent from the genome and transcriptome. In all three cases, functional proteomic evaluation uncovered critical biological insights that would not be resolved otherwise. The integrated single cell functional proteomic analysis constructed a detail kinetic picture of the immune response that took place during the clinical cancer immunotherapy. It revealed concrete functional evidence that connected genetics to IBD disease susceptibility. Further, it provided predictors that correlated with clinical responses and pathogenic outcomes.

Interpretation of lunar topography : impact cratering and surface roughness

This work seeks to understand past and present surface conditions on the Moon using two different but complementary approaches: topographic analysis using high-resolution elevation data from recent spacecraft missions and forward modeling of the dominant agent of lunar surface modification, impact cratering. The first investigation focuses on global surface roughness of the Moon, using a variety of statistical parameters to explore slopes at different scales and their relation to competing geological processes. We find that highlands topography behaves as a nearly self-similar fractal system on scales of order 100 meters, and there is a distinct change in this behavior above and below approximately 1 km. Chapter 2 focuses this analysis on two localized regions: the lunar south pole, including Shackleton crater, and the large mare-filled basins on the nearside of the Moon. In particular, we find that differential slope, a statistical measure of roughness related to the curvature of a topographic profile, is extremely useful in distinguishing between geologic units. Chapter 3 introduces a numerical model that simulates a cratered terrain by emplacing features of characteristic shape geometrically, allowing for tracking of both the topography and surviving rim fragments over time. The power spectral density of cratered terrains is estimated numerically from model results and benchmarked against a 1-dimensional analytic model. The power spectral slope is observed to vary predictably with the size-frequency distribution of craters, as well as the crater shape. The final chapter employs the rim-tracking feature of the cratered terrain model to analyze the evolving size-frequency distribution of craters under different criteria for identifying "visible" craters from surviving rim fragments. A geometric bias exists that systematically over counts large or small craters, depending on the rim fraction required to count a given feature as either visible or erased.