In situ measurement of dissolved inorganic carbon speciation in natural waters, pH, pC02, TA, & TC02, Honolulu, Hawaii, February 16-18, 2005: workshop proceedings

The Alliance for Coastal Technology (ACT) convened a workshop on the in situ measurement of dissolved inorganic carbon species in natural waters in Honolulu, Hawaii, on February 16, 17, and 18, 2005. The workshop was designed to summarize existing technologies for measuring the abundance and speciation of dissolved inorganic carbon and to make strategic recommendations for future development and application of these technologies to coastal research and management. The workshop was not focused on any specific technology, however, most of the attention of the workshop was on in situ pC02 sensors given their recent development and use on moorings for the measurement of global carbon fluxes. In addition, the problems and limitations arising from the long-term deployment of systems designed for the measurement of pH, total dissolved inorganic carbon (DIC), and total alkalinity (TA) were discussed. Participants included researchers involved in carbon biogeochemistry, industry representatives, and coastal resource managers. The primary questions asked during the workshop were: I. What are the major impediments to transform presently used shipboard pC02 measurement systems for use on cost-eficient moorings? 2. What are the major technical hurdles for the in situ measurement of TA and DIC? 3. What specific information do we need to coordinate efforts for proof of concept' testing of existing and new technologies, inter-calibration of those technologies, better software development, and more precise knowledge quantzjjing the geochemistry of dissolved inoeanic carbon species in order to develop an observing system for dissolved inorganic carbon? Based on the discussion resulting from these three questions, the following statements were made: Statement No. 1 Cost-effective, self-contained technologies for making long-term, accurate measurements of the partial pressure of C02 gas in water already exist and at present are ready for deployment on moorings in coastal observing systems. Statement No. 2 Cost-effective, self-contained systems for the measurement of pH, TA, and DIC are still needed to both fully define the carbonate chemistry of coastal waters and the fluxes of carbon between major biogeochemical compartments (e.g., air-sea, shelf-slope, water column-sediment, etc.). (pdf contains 23 pages)

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The mechanism of PEO process on Al–Si alloys with the bulk primary silicon

This study focuses on mechanism of ceramic coating on Al-Si alloys with bulk primary Si using plasma electrolytic oxidation (PEO) technology. Al-Si alloys with 27-32% Si in weight were used as substrates. The morphologies, composition and microstructure of PEO coatings were investigated by scanning electron microscopy (SEM) with energy dispersive X-ray system (EDX). Results showed that the PEO process had four different stages. The effect of bulk Si is greatly on the morphology and composition of coatings at first three stages. Anodic oxide films formed on Al and Si phases, respectively. When the voltage exceeded 40 V, glow appeared and concentrated on the localized zone of interface of Al and Si phase. Al-Si-O compounds formed and covered on the dendrite Si phase surface, and the coating on bulk Si, which was silicon oxide, was rougher than that on other phase. If the treatment time was long enough, the coatings with uniform surface morphologies and elements distribution will be obtained but the microstructure of inner layer is looser due to the bulk Si.

Compact 120 TW Ti: sapphire laser system with a high gain final amplifier

A 120TW/36fs laser system based on Ti:sapphire chirped-pulse amplification (CPA) has been successfully established in our lab. The final four pass Ti:sapphire amplifier pumped by an energetic single-shot Nd:YAG-Nd:glass laser was designed and optimized. With 24J/8ns pump energy at 532 nm, 300 mJ/220 ps chirped pulse was amplified to 5.98 J in this amplifier, and a total saturated gain of similar to 20 was achieved. The focused intensity of compressed beam could reach to 10(20) W/cm(2) with the M-2 of similar to 2.0. (c) 2005 Elsevier Ltd. All rights reserved.

Electronic structure and phonon thermodynamics of iron alloys

Inelastic neutron scattering (INS) and nuclear-resonant inelastic x-ray scattering (NRIXS) were used to measure phonon spectra of FeV as a B2- ordered compound and as a bcc solid solution. Contrary to the behavior of ordering alloys studied to date, the phonons in the B2-ordered phase are softer than in the solid solution. Ordering increases the vibrational entropy, which stabilizes the ordered phase to higher temperatures. Ab initio calculations show that the number of electronic states at the Fermi level increases upon ordering, enhancing the screening between ions, and reducing the interatomic force constants. The effect of screening is larger at the V atomic sites than at the Fe atomic sites.

The phonon spectra of Au-rich alloys of fcc Au-Fe were also measured. The main effect on the vibrational entropy of alloying comes from a stiffening of the Au partial phonon density of states (DOS) with Fe concentration that increases the miscibility gap temperature. The magnitude of the effect is non- linear and it is reduced at higher Fe concentrations. Force constants were calculated for several compositions and show a local stiffening of Au–Au bonds close to Fe atoms, but Au–Au bonds that are farther away do not show this effect. Phonon DOS curves calculated from the force constants reproduced the experimental trends. The Au–Fe bond is soft and favors ordering, but a charge transfer from the Fe to the Au atoms stiffens the Au–Au bonds enough to favor unmixing. The stiffening is attributed to two main effects comparable in magnitude: an increase in electron density in the free-electron-like states, and stronger sd-hybridization.

INS and NRIXS measurements were performed at elevated temperatures on B2-ordered FeTi and NRIXS measurements were performed at high pressures. The high-pressure behavior is quasi- harmonic. The softening of the phonon DOS curves with temperature is strongly nonharmonic. Calculations of the force constants and Born-von Karman fits to the experimental data show that the bonds between second nearest neighbors (2nn) are much stiffer than those between 1nn, but fits to the high temperature data show that the former softens at a faster rate with temperature. The Fe–Fe bond softens more than the Ti–Ti bond. The unusual stiffness of the 2nn bond is explained by the calculated charge distribution, which is highly aspherical and localized preferentially in the t2g orbitals. Ab initio molecular dynamics (AIMD) simulations show a charge transfer from the t2g orbitals to the eg orbitals at elevated temperatures. The asphericity decreases linearly with temperature and is more severe at the Fe sites.

Bis(thiophenolate)pyridine pincer ligands and trivalent zirconocene complexes relevant to early transition metal polymerization catalysts

Two major topics are covered: the first chapter is focused on the development of post-metallocene complexes for propylene polymerization. The second and third chapters investigate the consequences of diisobutylaluminum hydride (HAlⁱBu₂) additives in zirconocene based polymerization systems.

The synthesis, structure, and solution behavior of early metal complexes with a new tridentate LX₂ type ligand, bis(thiophenolate)pyridine ((SNS) = (2-C₆H₄S)₂-2,6-C₅H₃N) are investigated. SNS complexes of Ti, Zr, and Ta having dialkylamido coligands were synthesized and structurally characterized. The zirconium complex, (SNS)Zr(NMe₂)₂, displays C₂ symmetry in the solid state. Solid-state structures of tantalum complexes (SNS)Ta(NMe₂)₃ and (SNS)TaCl(NEt₂)₂ also display pronounced C₂ twisting of the SNS ligand. 1D and 2D NMR experiments show that (SNS)Ta(NMe₂)₃ is fluxional with rotation about the Ta N(amide) bonds occurring on the NMR timescale. The fluxional behavior of (SNS)TaCl(NEt₂)₂ in solution was also studied by variable temperature ¹H NMR. Observation of separate signals for the diastereotopic protons of the methylene unit of the diethylamide indicates that the complex remains locked on the NMR timescale in one diastereomeric conformation at temperatures below -50 °C.

Reduction of Zr(IV) metallocenium cations with sodium amalgam (NaHg) produces EPR signals assignable to Zr(III) metallocene complexes. Thus, chloro-bridged heterobinuclear ansa-zirconocenium cation [((SBI))Zr(μ-Cl)₂AlMe₂]⁺B(C₆F₅)_4¯ (SBI = rac-dimethylsilylbis(1-indenyl)), gives rise to an EPR signal assignable to the complex (SBI)Zr^III(μ-Cl)₂AlMe₂, while (SBI)Zr^III-Me and (SBI)Zr^III(-H)2AlⁱBu₂ are formed by reduction of [(SBI)Zr(μ-Me)₂AlMe₂]⁺B(C₆F₅)_4¯ and [(SBI)Zr(μ-H)₃(AlⁱBu₂)₂]⁺B(C₆F₅)4¯, respectively. These products are also formed, along with (SBI)Zr^III-ⁱBu and [(SBI)Zr^III]⁺ AlR4¯ when (SBI)ZrMe₂ reacts with HAlⁱBu₂, eliminating isobutane en route to the Zr(III) complex. Studies concerning the interconversion reactions between these and other (SBI)Zr(III) complexes and reaction mechanisms involved in their formation are also reported.

The addition of HAlⁱBu₂ to precatalyst [(SBI)Zr(µ-H)₃(AlⁱBu₂)₂]⁺ significantly slows the polymerization of propylene and changes the kinetics of polymerization from 1st to 2nd order with respect to propylene. This is likely due to competitive inhibition by HAlⁱBu₂. When the same reaction is investigated using [(ⁿBuCp)₂Zr(μ-H)₃(AlⁱBu₂)₂]⁺, hydroalumination between propylene and HAlⁱBu₂ is observed instead of propylene polymerization.