Thermal decomposition of ethylene diamine diperchlorate

Thermal decomposition of ethylene diamine diperchlorate (EDDP) has been studied by differential-thermal analysis (DTA), thermogravimetric analysis (TGA), isothermal weight-loss measurements and mass-spectrometric analysis of the decomposition products. It has been observed that EDDP decomposes in two temperature regions. The low-temperature decomposition stops at about 35 to 40 percent weight loss below 250°C. The reason for the low-temperature cessation may be the adsorption of excess ethylene diamine on the crystal surface of EDDP. An overall activation energy of 54 kcal per mole has been calculated for the thermal decomposition of EDDP. Mass-spectrometric analysis shows that the decomposition products are mainly CO2, H2O, HCl and N2. The following stoichiometry has been proposed for the thermal decomposition of EDDP: (−CH2NH3CIO4)2→2CO2O+2HCl+N2

Performance prediction and loss analysis of low specific speed submersible pumps

A performance prediction procedure is presented for low specific speed submersible pumps with a review of loss models given in the literature. Most of the loss theories discussed in this paper are one dimensional and improvements are made with good empiricism for the prediction to cover the entire range of operation of the low specific speed pumps. Loss correlations, particularly in the low flow range, are discussed. Prediction of the shape of efficiency-capacity and total head-capacity curves agrees well with the experimental results in almost the full range of operating conditions. The approach adopted in the present analysis, of estimating the losses in the individual components of a pump, provides means for improving the performance and identifying the problem areas in existing designs of the pumps. The investigation also provides a basis for selection of parameters for the optimal design of the pumps in which the maximum efficiency is an important design parameter. The scope for improvement in the prediction procedure with the nature of flow phenomena in the low flow region has been discussed in detail.

Electron energy loss spectroscopic study of Cr(CO)6, Mo(CO)6 and W(CO)6 in the vapour phase

Electron energy loss spectra (EELS) of Cr, Mo and W hexacarbonyls in the vapour phase are reported. Most of the bands observed are similar to those in optical spectra, but the two high energy transitions in the 9·8–11·2 eV region are reported here for the first time. Based on the orbital energies from the ultraviolet photoelectron spectra and the electronic transition energies from EELS and earlier optical studies, the molecular energy level schemes of these molecules are constructed.

Metal-Insulator Transitions in Anion-Excess LaMnO3+? Controlled by the Mn4+ Content

LaMnO3+? samples with Mn4+ content up to 50% have been prepared by different methods. The structure of LaMnO3+? changes from orthorhombic to cubic (via rhombohedral) with increase in the Mn4+ content. LaMnO3+? samples containing greater than 20% Mn4+ are ferromagnetic and show resistivity maxima at a temperature Tt which is close to the ferromagnetic Curie temperature. The resistivity maximum is due to the occurrence of a metal-insulator transition. In samples heated to the same temperature, the value of Tt increases with % Mn4+. For a given sample, Tt increases with the temperature of heat treatment due to the increase in particle size. The onset of ferromagnetism in LaMnO3+? accompanied by an insulator-metal transition is similar to that found in La1-xCaxMnO3 and La1-xSrxCoO3.

Quantification of enantiomeric excess by H-1-detected heteronuclear refocusing and homonuclear multiple quantum NMR experiments

The omega(1)-heterodecoupled-C-13-filtered proton detected NMR experiments are reported for the accurate quantification of enantiomeric excess in chiral molecules embedded in chiral liquid crystal. The differential values of both H-1-H-1 and C-13-H-1 dipolar couplings in the direct dimension and only H-1-H-1 dipolar couplings in the indirect dimension enable unraveling of overlapped enantiomeric peaks. The creation of unequal C-13-bound proton signal for each enantiomer in the INEPT block and non-uniform excitation of coherences in homonuclear multiple quantum experiments do not yield accurate quantification of enantiomeric excess. In circumventing these difficulties, a coupling dependent intensity correction factor has been invoked. (C) 2010 Elsevier B.V. All rights reserved.

The Reaction of a Nitro-Capped Cobalt(III) Cage Complex With Base: the Crystal Structure of a Contracted Cage Complex, and the Mechanism of Its Formation

The synthesis, properties and crystal structure of the cage complex (1-hydroxy-8-methyl-3,6,10,13,15,18-hexaazabicyclo[6.6.5]nonadecane)cobalt(III) chloride hydrate ([Co(Me,OH-absar)] C13.H2O) are reported. The mechanism of the formation of this contracted cavity cage from a nitro-capped hexaazabicycloicosane type cage has been investigated. Treatment of (1-methyl-8-nitro-3,6,10,13,16,19-hexaazabicyclo[6.6.6]icosane)cobalt(III) chloride ([Co(Me,NO2-sar)] 3+) with excess base in aqueous solution leads initially to rapid (t1/2 < 1 ms) and reversible deprotonation of one coordinated secondary amine. This species undergoes a retro-Mannich type reaction and imine hydrolysis (t1/2 almost-equal-to 90 s). Quenching the reaction with acid gives rise to a pair of isomeric intermediate species which have been isolated and characterized. They have a pendant arm macrocyclic structure, resulting from the loss of a methylene unit from one of the arms of the cap. Heating either isomer in aqueous solution gives the new cage compound with the contracted cap. It is postulated that this occurs through a Nef reaction, resulting in the formation of a ketone which then condenses with the coordinated primary amine. A comparison with the corresponding bicycloicosane analogue indicates a reduced chromophoric cavity size for the contracted cage. The reduction potential of the cobalt(III)/cobalt(II) couple is 170 mV more negative for the smaller cage, and, in the electronic spectrum of the cobalt(III) complex, the d-d transitions are both shifted to higher energy, corresponding to a stronger ligand field.

Anomalous viscous loss in emulsions

We propose a model for concentrated emulsions based on the speculation that a macroscopic shear strain does not produce an affine deformation in the randomly close-packed droplet structure. The model yields an anomalous contribution to the complex dynamic shear modulus that varies as the square root of frequency. We test this prediction using a novel light scattering technique to measure the dynamic shear modulus, and directly observe the predicted behavior over six decades of frequency and a wide range of volume fractions.

Dielectric function and optical conductivity of TiOx (0.8loss spectroscopy

Reflection electron energy-loss spectra are reported for the family of compounds TiOx over the entire homogeneity range (0.8 < a: < 1.3). The spectra exhibit a plasmon feature on the low-energy side, while several interband transitions are prominent at higher energies. The real and imaginary parts of dielectric functions and optical conductivity for these compounds are determined using the Kramers-Kronig analysis. The results exhibit systematic behavior with varying oxygen stoichiometry.

Constraint loss under dynamic loading in rate independent plastic solids

The objectives of this paper are to examine the loss of crack tip constraint in dynamically loaded fracture specimens and to assess whether it can lead to enhancement in the fracture toughness at high loading rates which has been observed in several experimental studies. To this end, 2-D plane strain finite element analyses of single edge notched (tension) specimen and three point bend specimen subjected to time varying loads are performed. The material is assumed to obey the small strain J(2) flow theory of plasticity with rate independent behaviour. The results demonstrate that a valid J-Q field exists under dynamic loading irrespective of the crack length and specimen geometry. Further, the constraint parameter Q becomes strongly negative at high loading rates, particularly in deeply cracked specimens. The variation of dynamic fracture toughness K-dc with stress intensity rate K for cleavage cracking is predicted using a simple critical stress criterion. It is found that inertia-driven constraint loss can substantially enhance K-dc for (K) over dot > 10(5) MPa rootm/s.

Efficient algorithms for learning kernels from multiple similarity matrices with general convex loss functions

In this paper we consider the problem of learning an n × n kernel matrix from m(1) similarity matrices under general convex loss. Past research have extensively studied the m = 1 case and have derived several algorithms which require sophisticated techniques like ACCP, SOCP, etc. The existing algorithms do not apply if one uses arbitrary losses and often can not handle m > 1 case. We present several provably convergent iterative algorithms, where each iteration requires either an SVM or a Multiple Kernel Learning (MKL) solver for m > 1 case. One of the major contributions of the paper is to extend the well knownMirror Descent(MD) framework to handle Cartesian product of psd matrices. This novel extension leads to an algorithm, called EMKL, which solves the problem in O(m2 log n 2) iterations; in each iteration one solves an MKL involving m kernels and m eigen-decomposition of n × n matrices. By suitably defining a restriction on the objective function, a faster version of EMKL is proposed, called REKL,which avoids the eigen-decomposition. An alternative to both EMKL and REKL is also suggested which requires only an SVMsolver. Experimental results on real world protein data set involving several similarity matrices illustrate the efficacy of the proposed algorithms.

Synthesis of acicular hydrogoethite (alpha-FeOOH center dot xH(2)O; 0.1 < x < 0.22) particles using morphology controlling cationic additives and magnetic properties of maghemite derived from hydrogoethite

A method for the preparation of acicular hydrogoethite (alpha -FeOOH.xH(2)O, 0.1 < x < 0.22) particles of 0.3-1 mm length has been optimized by air oxidation of Fe( II) hydroxide gel precipitated from aqueous (NH4)(2)Fe(SO4)(2) solutions containing 0.005-0.02 atom% of cationic Pt, Pd or Rh additives as morphology controlling agents. Hydrogoethite particles are evolved from the amorphous ferrous hydroxide gel by heterogeneous nucleation and growth. Preferential adsorption of additives on certain crystallographic planes thereby retarding the growth in the perpendicular direction, allows the particles to acquire acicular shapes with high aspect ratios of 8-15. Synthetic hydrogoethite showed a mass loss of about 14% at similar to 280 degreesC, revealing the presence of strongly coordinated water of hydration in the interior of the goethite crystallites. As evident from IR spectra, excess H2O molecules (0.1- 0.22 per formula unit) are located in the strands of channels formed in between the double ribbons of FeO6 octahedra running parallel to the c- axis. Hydrogoethite particles constituted of multicrystallites are formed with Pt as additive, whereas single crystallite particles are obtained with Pd (or Rh). For both dehydroxylation as well as H-2 reduction, a lower reaction temperature (similar to 220 degreesC) was observed for the former (Pt treated) compared to the latter (Pd or Rh) (similar to 260 degreesC). Acicular magnetite (Fe3O4) was prepared either by reducing hydrogoethite (magnetite route) or dehydroxylating hydrogoethite to hematite and then reducing it to magnetite (hematite- magnetite route). According to TEM studies, preferential dehydroxylation of hydrogoethite along < 010 > leads to microporous hematite. Maghemite (gamma -Fe2O3 (-) (delta), 0 < < 0.25) was obtained by reoxidation of magnetite. The micropores are retained during the topotactic transformation to magnetite and finally to maghemite, whereas cylindrical mesopores are formed due to rearrangement of the oxygen sublattice from hexagonal to cubic close packing during the conversion of hydrogoethite to magnetite and then to maghemite. Accordingly, three different types of maghemite particles are realized: strongly oriented multicrystalline particles, single crystalline acicular particles with micropores or crystallites having mesopores. Higher values of saturation magnetization ((s) = 74 emu g(-1)) and coercivity (H-c = 320 Oe) are obtained for single crystalline mesoporous particles. In the other cases, the smaller size of particles and larger distribution of micropores decreases sigma (s) considerably ( < 60 emu g(-1)) due to relaxation effects of spins on the surface atoms as revealed by Mossbauer spectroscopy.

The effect of mischmetal addition on the structure and mechanical properties of a cast Al-7Si-0.3Mg alloy containing excess iron (up to 0.6 Pct)

The effect of Fe content (0.2 to 0.6 pct) on the microstructure and mechanical properties of a cast Al-7Si-0.3Mg (LM 25/356) alloy has been investigated. Further, 1 pct mischmetal (MM) additions (a mixture of rare-earth (RE) elements) were made to these alloys, and their mechanical properties at room and at elevated temperatures (up to 200 degreesC) were evaluated. A structure-property correlation on this alloy was attempted using optical microstructure analysis, fractographs, X-ray diffraction, energy-dispersive analysis of X-rays (EDX), and quantitative metallography by image analysis. An increase in Fe content increased the volume percentage of Fe-bearing intermetallic compounds (beta and pi phases), contributing to the lower yield strength (YS), ultimate tensile strength (UTS), percentage elongation, and higher hardness. An addition of 1 pct MM to the alloys containing 0.2 and 0.6 pct Fe was found to refine the microstructure; modify the eutectic silicon and La, Ce, and Nd present in the MM; form different intermetallic compounds with Al, Si, Fe, and Mg; and improve the mechanical properties of the alloys both at room and elevated temperatures.

Hyper-activation of the TCP4 transcription factor in Arabidopsis thaliana accelerates multiple aspects of plant maturation

Plant organs are initiated as primordial outgrowths, and require controlled cell division and differentiation to achieve their final size and shape. Superimposed on this is another developmental program that orchestrates the switch from vegetative to reproductive to senescence stages in the life cycle. These require sequential function of heterochronic regulators. Little is known regarding the coordination between organ and organismal growth in plants. The TCP gene family encodes transcription factors that control diverse developmental traits, and a subgroup of class II TCP genes regulate leaf morphogenesis. Absence of these genes results in large, crinkly leaves due to excess division, mainly at margins. It has been suggested that these class II TCPs modulate the spatio-temporal control of differentiation in a growing leaf, rather than regulating cell proliferation per se. However, the link between class II TCP action and cell growth has not been established. As loss-of-function mutants of individual TCP genes in Arabidopsis are not very informative due to gene redundancy, we generated a transgenic line that expressed a hyper-activated form of TCP4 in its endogenous expression domain. This resulted in premature onset of maturation and decreased cell proliferation, leading to much smaller leaves, with cup-shaped lamina in extreme cases. Further, the transgenic line initiated leaves faster than wild-type and underwent precocious reproductive maturation due to a shortened adult vegetative phase. Early senescence and severe fertility defects were also observed. Thus, hyper-activation of TCP4 revealed its role in determining the timing of crucial developmental events, both at the organ and organism level.