Real-time measurement of stress and damage evolution during initial lithiation of crystalline silicon

Crystalline to amorphous phase transformation during initial lithiation in (100) Si wafers is studied in an electrochemical cell with Li metal as the counter and reference electrode. During initial lithiation, a moving phase boundary advances into the wafer starting from the surface facing the lithium electrode, transforming crystalline Si into amorphous Li(x)Si. The resulting biaxial compressive stress in the amorphous layer is measured in situ, and it was observed to be ca. 0.5 GPa. High-resolution TEM images reveal a very sharp crystalline-amorphous phase boundary, with a thickness of ～1 nm. Upon delithiation, the stress rapidly reverses and becomes tensile, and the amorphous layer begins to deform plastically at around 0.5 GPa. With continued delithiation, the yield stress increases in magnitude, culminating in a sudden fracture of the amorphous layer into microfragments, and the cracks extend into the underlying crystalline Si.     

Preparation and evaluation of carbon coated alumina as a high surface area packing material for high performance liquid chromatography

The retention of polar compounds, the separation of structural isomers and thermal stability make carbonaceous materials very attractive stationary phases for liquid chromatography (LC). Carbon clad zirconia (C/ZrO₂), one of the most interesting, exhibits unparalleled chemical and thermal stability, but its characteristically low surface area (20–30 m²/g) limits broader application as a second dimension separation in two-dimensional liquid chromatography (2DLC) where high retentivity and therefore high stationary phase surface area are required. In this work, we used a high surface area commercial HPLC alumina (153 m²/g) as a support material to develop a carbon phase by chemical vapor deposition (CVD) at elevated temperature using hexane vapor as the carbon source. The loading of carbon was varied by changing the CVD time and temperature, and the carbon coated alumina (C/Al₂O₃) was characterized both physically and chromatographically. The resulting carbon phases behaved as a reversed phase similar to C/ZrO₂. At all carbon loadings, C/Al₂O₃ closely matched the unique chromatographic selectivity of carbon phases, and as expected the retentivity was increased over C/ZrO₂. Excess carbon – the amount equivalent to 5 monolayers – was required to fully cover the oxide support in C/Al₂O₃, but this was less excess than needed with C/ZrO₂. Plate counts were 60,000–76,000/m for 5 μm particles. Spectroscopic studies (XPS and FT-IR) were also conducted; they showed that the two materials were chemically very similar.     

Molecular weight control of polyacrylamide with sodium formate as a chain‐transfer agent: Characterization via size exclusion chromatography/multi‐angle laser light scattering and determination of chain‐transfer constant

We discuss the synthesis and characterization of polyacrylamide (PAM) homopolymers with carefully controlled molecular weights (MWs). PAM was synthesized via free‐radical solution polymerization under conditions that yield highly linear polymer with minimal levels of hydrolysis. The MW of the PAM homopolymers was controlled by the addition of sodium formate (NaOOCH) to the polymerization medium as a conventional chain‐transfer agent. MWs and polydispersity indices (PDIs) were determined via size exclusion chromatography/multi‐angle laser light scattering analysis; for polymerizations carried out to high conversion, PAM MWs ranged from 0.23 to 6.19 × 10⁶ g/mol, with most samples having PDI ≈2.0. Zero‐shear intrinsic viscosities of the polymers were determined via low‐shear viscometry in 0.514 M NaCl at 25 °C. Data derived from the polymer characterization were used to determine the chain‐transfer constant to NaOOCH under the given polymerization conditions and to calculate Mark–Houwink–Sakurada K and a values for PAM in 0.514 M NaCl at 25 °C. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 560–568, 2003     

Protection of flows under targeted attacks

We present a new robust optimization model for the problem of maximizing the amount of flow surviving the attack of an interdictor. Given some path flow, our model allows the interdictor to specify the amount of flow removed from each path individually. In contrast to previous models, for which no efficient algorithms are known, the most important basic variants of our model can be solved in poly-time. We also consider extensions where there is a budget to set the interdiction costs.     

Sensitizing the Sensitizer: The Synthesis and Photophysical Study of Bodipy-Pt(II)(diimine)(dithiolate) Conjugates

The dyads 3, 4, and 6, combining the Bodipy chromophore with a Pt(bpy)(bdt) (bpy = 2,2'-bipyridine, bdt = 1,2-benzenedithiolate, 3 and 6) or a Pt(bpy)(mnt) (mnt = maleonitriledithiolate, 4) moiety, have been synthesized and studied by UV-vis steady-state absorption, transient absorption, and emission spectroscopies and cyclic voltammetry. Comparison of the absorption spectra and cyclic voltammograms of dyads 3, 4, and 6 and those of their model compounds 1a, 2, 5, and 7 shows that the spectroscopic and electrochemical properties of the dyads are essentially the sum of their constituent chromophores, indicating negligible interaction of the constituent chromophores in the ground state. However, emission studies on 3 and 6 show a complete absence of both Bodipy-based fluorescence and the characteristic luminescence of the Pt(bpy)(bdt) unit. Dyad 4 shows a weak Pt(mnt)-based emission. Transient absorption studies show that excitation of the dyads into the Bodipy-based (1)ππ* excited state is followed by singlet energy transfer (SEnT) to the Pt(dithiolate)-based (1)MMLL'CT (mixed metal-ligand to ligand charge transfer) excited state ([Formula: see text] = 0.6 ps, [Formula: see text] = 0.5 ps, and [Formula: see text] = 1.6 ps), which undergoes rapid intersystem crossing to the (3)MMLL'CT state due to the heavy Pt(II) ion. The (3)MMLL'CT state is then depopulated by triplet energy transfer (TEnT) to the low-lying Bodipy-based (3)ππ* excited state ([Formula: see text] = 8.2 ps, [Formula: see text] = 5 ps, and [Formula: see text] = 160 ps). The transition assignments are supported by TD-DFT calculations. Both energy-transfer processes are shown to proceed via a Dexter electron exchange mechanism. The much longer time constants for dyad 6 relative to 3 are attributed to the significantly poorer coupling and resonance of charge-separated species that are intermediates in the electron exchange process.     

Few-body form factor measurements in Hall A of JLab

There is an active program of few-body form factor measurements in Hall A of Thomas Jefferson National Accelerator Facility (Jefferson Laboratory). Recent measurements of the deuteron elastic electric, A(Q²), and magnetic, B(Q²), structure functions will be presented. Planned measurements of the form factors of ³He and ⁴He will also be discussed.     

Penalty function versus non-penalty function methods for constrained nonlinear programming problems

The relative merits of using sequential unconstrained methods for solving: minimizef(x) subject tog _i (x) 0, i = 1, , m, h _j (x) = 0, j = 1, , p versus methods which handle the constraints directly are explored. Nonlinearly constrained problems are emphasized. Both classes of methods are analyzed as to parameter selection requirements, convergence to first and second-order Kuhn-Tucker Points, rate of convergence, matrix conditioning problems and computations required.This paper was presented at the 7th Mathematical Programming Symposium 1970, The Hague, The Netherlands.