In Situ Measurement of the Aerosol Size Distribution in Stratospheric Solid Rocket Motor Exhaust Plumes

The concentration and size distribution of aerosol in the stratospheric exhaust plumes of two Space Shuttle rockets and one Titan IV rocket were measured using a two component aerosol sampling system carried aboard a WB‐57F aircraft. Aerosol size distribution in the 0.01 µm to 4 µm diameter size range was measured using a two component sampling system. The measured distributions display a trimodal form with modes near 0.005 µm, 0.09 µm, and 2.03 µm and are used to infer the relative mass fractionation among the three modes. While the smallest mode has been estimated to contain as much as 10% of the total mass of SRM exhaust alumina, we find show that the smallest mode contains less than 0.05% of the alumina mass. This fraction is so small so as to significantly reduce the likelihood that heterogeneous reactions on the SRM alumina surfaces could produce a significant global impact on stratospheric chemistry

Failure mechanisms of single-crystal silicon electrodes in lithium-ion batteries

Long-term durability is a major obstacle limiting the widespread use of lithium ion batteries (LIBs) in heavy-duty applications and others demanding extended lifetime. As one of the root causes of degradation and failure of battery performance, the electrode failure mechanisms are still unknown. Here, we reveal the fundamental fracture mechanisms of single-crystal silicon electrodes over extended lithiation/delithiation cycles, using electrochemical testing, microstructure characterization, fracture mechanics, and finite element analysis. Anisotropic lithium invasion causes crack initiation perpendicular to the electrode surface, followed by growth through the electrode thickness. The low fracture energy of the lithiated/unlithiated silicon interface provides a weak microstructural path for crack deflection, accounting for the crack patterns and delamination observed after repeated cycling. Based on this physical understanding, we demonstrate how electrolyte additives can heal electrode cracks and provide strategies to enhance the fracture resistance in future LIBs from surface chemical, electrochemical, and material science perspectives.Comment: 8 pages, 5 figure

Thermal Stability of LiPF6 Salt and Li-ion Battery ElectrolytesContaining LiPF6

The thermal stability of the neat LiPF6 salt and of 1 molal solutions of LiPF6 in prototypical Li-ion battery solvents was studied with thermogravimetric analysis (TGA) and on-line FTIR. Pure LiPF6 salt is thermally stable up to 380 K in a dry inert atmosphere, and its decomposition path is a simple dissociation producing LiF as solid and PF5 as gaseous products. In the presence of water (300 ppm) in the carrier gas, its decomposition onset temperature is lowered as a result of direct thermal reaction between LiPF6 and water vapor to form POF3 and HF. No new products were observed in 1 molal solutions of LiPF6 in EC, DMC and EMC by on-line TGA-FTIR analysis. The storage of the same solutions in sealed containers at 358 K for 300 420 hrs. did not produce any significant quantity of new products as well. In particular, noalkylflurophosphates were found in the solutions after storage at elevated temperature. In the absence of either an impurity like alcohol or cathode active material that may (or may not) act as a catalyst, there is no evidence of thermally induced reaction between LiPF6 and the prototypical Li-ion battery solvents EC, PC, DMC or EMC

Real-time observation of the dry oxidation of the Si(100) surface with ambient pressure x-ray photoelectron spectroscopy

We have applied ambient-pressure x-ray photoelectron spectroscopy with Si 2p chemical shifts to study the real-time dry oxidation of Si(100), using pressures in the range of 0.01-1 Torr and temperatures of 300-530 ??C, and examining the oxide thickness range from 0 to ???25 A. The oxidation rate is initially very high (with rates of up to ???225 Ah) and then, after a certain initial thickness of the oxide in the range of 6-22 A is formed, decreases to a slow state (with rates of ???1.5-4.0 Ah). Neither the rapid nor the slow regime is explained by the standard Deal-Grove model for Si oxidation.open171

In situ observation of wet oxidation kinetics on Si(100) via ambient pressure x-ray photoemission spectroscopy

e initial stages of wet thermal oxidation of Si (100) - (2??1) have been investigated by in situ ambient pressure x-ray photoemission spectroscopy, including chemical-state resolution via Si 2p core-level spectra. Real-time growth rates of silicon dioxide have been monitored at 100 mTorr of water vapor. This pressure is considerably higher than in any prior study using x-ray photoemission spectroscopy. Substrate temperatures have been varied between 250 and 500 ??C. Above a temperature of ???400 ??C, two distinct regimes, a rapid and a quasisaturated one, are identified, and growth rates show a strong temperature dependence which cannot be explained by the conventional Deal-Grove model.open7

A Study of Electrochemical Reduction of Ethylene and Propylene Carbonate Electrolytes on Graphite Using ATR-FTIR Spectroscopy

We present results testing the hypothesis that there is a different reaction pathway for the electrochemical reduction of PC versus EC-based electrolytes at graphite electrodes with LiPF6 as the salt in common. We examined the reduction products formed using ex-situ Fourier Transform Infrared (FTIR) spectroscopy in attenuated total reflection (ATR) geometry. The results show the pathway for reduction of PC leads nearly entirely to lithium carbonate as the solid product (and presumably ethylene gas as the co-product) while EC follows a path producing a mixture of organic and inorganic compounds. Possible explanations for the difference in reaction pathway are discussed

Clinical actionability of comprehensive genomic profiling for management of rare or refractory cancers

Background. The frequency with which targeted tumor sequencing results will lead to implemented change in care is unclear. Prospective assessment of the feasibility and limitations of using genomic sequencing is critically important. Methods. A prospective clinical study was conducted on 100 patients with diverse-histology, rare, or poor-prognosis cancers to evaluate the clinical actionability of a Clinical Laboratory Improvement Amendments (CLIA)-certified, comprehensive genomic profiling assay (FoundationOne), using formalin-fixed, paraffin-embedded tumors. The primary objectives were to assess utility, feasibility, and limitations of genomic sequencing for genomically guided therapy or other clinical purpose in the setting of a multidisciplinary molecular tumor board. Results. Of the tumors from the 92 patients with sufficient tissue, 88 (96%) had at least one genomic alteration (average 3.6, range 0–10). Commonly altered pathways included p53 (46%), RAS/RAF/MAPK (rat sarcoma; rapidly accelerated fibrosarcoma; mitogen-activated protein kinase) (45%), receptor tyrosine kinases/ligand (44%), PI3K/AKT/mTOR (phosphatidylinositol-4,5-bisphosphate 3-kinase; protein kinase B; mammalian target of rapamycin) (35%), transcription factors/regulators (31%), and cell cycle regulators (30%). Many low frequency but potentially actionable alterations were identified in diverse histologies. Use of comprehensive profiling led to implementable clinical action in 35% of tumors with genomic alterations, including genomically guided therapy, diagnostic modification, and trigger for germline genetic testing. Conclusion. Use of targeted next-generation sequencing in the setting of an institutional molecular tumor board led to implementable clinical action in more than one third of patients with rare and poor-prognosis cancers. Major barriers to implementation of genomically guided therapy were clinical status of the patient and drug access. Early and serial sequencing in the clinical course and expanded access to genomically guided early-phase clinical trials and targeted agents may increase actionability. Implications for Practice: Identification of key factors that facilitate use of genomic tumor testing results and implementation of genomically guided therapy may lead to enhanced benefit for patients with rare or difficult to treat cancers. Clinical use of a targeted next-generation sequencing assay in the setting of an institutional molecular tumor board led to implementable clinical action in over one third of patients with rare and poor prognosis cancers. The major barriers to implementation of genomically guided therapy were clinical status of the patient and drug access both on trial and off label. Approaches to increase actionability include early and serial sequencing in the clinical course and expanded access to genomically guided early phase clinical trials and targeted agents