Liquid-liquid extraction with long-chain quaternary Ammonium Halides

The extraction of anionic chloro-complexes of certain metal ions using various long-chain quaternary ammonium halides in toluene and chloroform is described. The investigation has concerned itself mainly with coualt(II) and iron(III); a few extractions have also been carried out with indium(III) and gallium(in). The ion association of chloro-anionic complexes of iron, cobalt, indium and gallium in aqueous chloride media (hydrochloric acid or lithium chloride) with the quaternary ammonium ion in the organic phase is responsible for the extraction of the metal ion into the organic phase. Tlic extraction efficiency varies with the nature of the metal ion system involved as well as with the distribution of the quaternary compound and the size, shape and nature of the organic groups substituted in the quaternary compound.     

Synthesis and structural studies of some first row transition metal complexes of acetone nicotinoyl hydrazone

Summary Acetone nicotinoyl hydrazone (ANII) complexes of the types M(ANH)Cl₂ · nEtOH and M(ANH-H)₂ H₂O (where M = Mn^II Fe^II, Co^II, Ni^II, Cu^II or Zn^II and n = 0,1 or 2) have been prepared and their structures studied by molar conductance, i.r. and electronic spectra, and room temperature magnetic measurements. All the complexes arc nonionic in a 0.001 M solution of formic acid. Magnetic and electronic spectral studies show that all the complexes are spin-free regular or distorted octahedra except Mn(ANH)Cl₂ and Co(ANH)CI₂ which are tetrahedral. The distorted octahedral geometry of Cu(ANH-H)₂ · H2O has also been confirmed from its sold state e.s.r spectrum at 77 K. From i.r. spectral studies, ANH has been found to act as a tridentate ligand in all the complexes except Mn(ANH)Cl₂ where it behaves as a bidentate ligand.     

Photodissociation dynamics of acetoxime in gas phase

The dynamics of photodissociation of acetoxime at 193 nm, leading to the formation of (CH3)2C=N and OH fragments, has been investigated. The nascent OH radicals, which are both rotationally and vibrationally excited, were probed by laser photolysis-laser induced fluorescence technique. OH fragments in both v" = 1 and v" = 0 vibrational states were detected with a ratio of population in the higher to lower level of 0.07+/-0.01. The rotational temperatures of v" = 0 and 1 levels of OH radicals are 2650+/-150 K and 1290+/-20 K, respectively. More than 30% of the available energy, i.e., 115+/-21 kJ mol(-1) is partitioned into the relative translational energy of the fragments. The results of excited electronic state and transition state calculations at the configuration interaction with single electronic excitation level suggest that the dissociation takes place with an exit barrier of approximately 126 kJ mol(-1) at the triplet state (T2) potential energy surface, formed by internal conversions/intersystem crossing from the initially populated S2 state. Using the calculated transition state geometry and its energy, the observed energy distribution pattern can be reproduced by the hybrid model within experimental uncertainties. The presence of an exit barrier is further supported by the observation of N-OH dissociation upon 248 nm excitation, where the relative translational energy of the fragments is found to be approximately 96 kJ mol(-1). The photodissociation dynamics of acetoxime is compared with C-OH dissociation in enols and carboxylic acid and N-OH dissociation in nitrous acid. The observed emission (lambda(max)=430 nm) and the N-OH dissociation dynamics indicate crossing of the initially populated state to an emissive state of acetoxime, which is different from the dissociative state.     

Metal–Polymer Composite Interconnections for Ultra Fine-Pitch Wafer Level Packaging

The decrease in feature sizes of microelectronic devices has underlined the need for higher number of input-outputs (I/Os) in order to increase its functionality. This has spurred a great interest in developing electronic packages with fine and ultra fine pitches (20-100 mum). Most of the compliant interconnects that are currently being developed have inductance and resistance higher than desirable. This paper presents a novel low-temperature fabrication process that combines polymer structures with electroless copper plating to create low stress composite structures for extremely fine-pitch wafer level packages. Analytical models for these structures justify the stress reduction at the interfaces and superior reliability as integrated circuit (IC)-package interconnects. Low coefficient of thermal expansion (CTE) polyimide structures with ultra-low stress, high toughness, and strength were fabricated using plasma etching. The dry etching process was tuned to yield a wall angle above 80deg. The etching process also leads to roughened sidewalls for selective electroless copper plating on the sidewalls of polymer structures. This work also describes a selective electroless plating synthesis route to develop thin IC-package bonding interfaces with lead-free solder. Lead-free alloy films were deposited from aqueous plating solutions consisting of suitable metal salts and reducing agents at 45degC. The lead-free solder composition was controlled by altering the plating bath formulation. Solder film formed from the above approach was demonstrated to bond the metal-coated polymer interconnects with the copper pads on the substrate using a standard reflow process. Metal-coated polymer structures in conjunction with the thin solder bonding films can provide low-cost high-performance solutions for wafer-level packaging.     

Hierarchical Forecasting of Web Server Workload Using Sequential Monte Carlo Training

Internet service utilities host multiple server applications on a shared server cluster (server farm). One of the essential tasks of the hosting service provider is to allocate servers to each of the websites to maintain a certain level of quality of service for different classes of incoming requests at each point of time, and optimize the use of server resources, while maximizing its profits. Such a proactive management of resources requires accurate prediction of workload, which is generally measured as the amount of service requests per unit time. As a time series, the workload exhibits not only short time random fluctuations but also prominent periodic (daily) patterns that evolve randomly from one period to another. We propose a solution to the Web server load prediction problem based on a hierarchical framework with multiple time scales. This framework leads to adaptive procedures that provide both long-term (in days) and short-term (in minutes) predictions with simultaneous confidence bands which accommodate not only serial correlation but also heavy-tailedness, and nonstationarity of the data. The long-term load is modeled as a dynamic harmonic regression (DHR), the coefficients of which evolve according to a random walk, and are tracked using sequential Monte Carlo (SMC) algorithms; whereas the short-term load is predicted using an autoregressive model, whose parameters are also estimated using SMC techniques. We evaluate our method using real-world Web workload data     

Crystal structure of nimbin

The crystal structure of nimbin has been determined. The crystals are orthorhombic, space groupP2₁2₁2₁ witha=6.790(2),b=14.875(4),c=27.160(8) Å andZ=4. The packing of the molecules in the lattice is due to C?H…O type of hydrogen bonds.     

Polyimide-epoxy alloys prepared via micro-modification: Water sorption and diffusion

A novel polyimide-epoxy or PI-EP alloys are prepared by the modification of polyamic acid in the concentration range of 1.54×10⁻⁶ to 1.54×10⁻² mol/L. The methanol sorption for these alloys at 24 hrs and at equilibrium conditions are determined and the residual solvent in fully cyclized polyimides were calculated. The presence of the residual solvent is visualized in fully imidized polymer and a structure containing partly imidized amic acid moiety is proposed and their concentration (in percentage) is calculated. The water sorption for these alloys at 24 hrs and at equilibrium conditions and the values of the water diffusion coefficient are determined from absorption isotherms. The PI-EP alloys have shown comparatively lower water sorption and higher diffusion coefficient than the unmodified polyimide. The mechanistic aspects of water sorption and diffusion are discussed.     

Expression of Chirality by Achiral Coadsorbed Molecules in Chiral Monolayers Observed by STM

The supramolecular packing mode of physisorbed monolayers built up by chiral isophthalic acid derivatives and coadsorbed achiral solvent molecules was imaged at the liquid/graphite interface with scanning tunneling microscopy (STM). The picture on the right shows the submolecularly resolved STM image of an enantiomorphous domain composed of the R enantiomer of the isophthalic acid derivative studied and 1-heptanol molecules; the latter express the chirality of the monolayer. Upon adsorption a racemic mixture is separated into enantiomorphous domains.     

Biosourced Antioxidants for Chemical Durability Enhancement of Perfluorosulfonic Acid Membrane

The chemical durability of perfluorosulfonic acid (PFSA) membranes is a topic of growing interest to meet Department of Energy (DOE) durability targets for heavy-duty vehicle (HDV) applications. State-of-the-art membranes like Nafion, rely on the use of cerium, heteropolyacids, and other inorganic additives to increase PFSA chemical durability. A less explored avenue for the oxidative stabilization of PFSA and hydrocarbon membranes is the use of organic antioxidants. No reversible organic antioxidant has been demonstrated to date which can enhance membrane lifetime by factors comparable to cerium. Here, ellagic acid (EA) is demonstrated as a promising radical scavenger for PFSA's. It is found that the incorporation of EA enhances the chemical durability of Nafion by 160%. EA, when incorporated with cerium as an electron donorenhances Nafion durability by at least 80% compared to a membrane incorporated with just cerium in DOE-defined durability tests. EA is found to be reversible in acidic conditions like those of fuel cells and its reversibility could be further enhanced by the use of suitable co-antioxidants.     

Effect of Oxygen Partial Pressure on the Nucleation Kinetics of Orthorhombic YBCO

Effect of oxygen partial pressure on the nucleation kinetics of orthorhombic YBCO from tetragonal phase has been studied using classical nucleation theory. The free energy of formation of orthorhombic YBCO has been evaluated as a function of oxygen partial pressure.