Isothermal melt and cold crystallization kinetics of poly(aryl ether ether ketone ketone) (PEEKK)

Isothermal melt and cold crystallization kinetics of PEEKK have been investigated by differential scanning calorimetry in two temperature regions. During the primary crystallization process, the relative crystallinity develops with a time dependence described by the Avrami equation, with exponent n = 2 for both melt and cold crystallization. The activation energies are -544.5 and 466.7 kJ/mol for crystallization from the melt and amorphous glassy state, respectively. The equilibrium melting point T-m(o) is estimated to be 371 degrees C by using the Hoffman-Weeks approach. The lateral and end surface free energies derived from the Lauritzen-Hoffman spherulitic growth rate equation are sigma=10 erg/cm(2) and sigma(e) = 60 erg/cm(2), respectively. The work of chain folding q is determined as 3.98 kcal/mol. These observed crystallization kinetic characteristics of PEEKK are compared with those of PEEK. (C) 1997 Elsevier Science Ltd.

Electrochemical behavior of Nd3+ and Ho3+ in LiCl-KCl eutectic melt

The electrochemical behavior of Nd3+ and Ho3+ ions on molybdenum electrode in the LiCl-KCl eutectic melts has been studied by cyclic voltammetry and open-circuit potentiometry. The results show that the reduction process of Nd3+ and Ho3+ ions on molybdenum electrode is one-step three electron reversible reaction. The diffusion coefficients of Nd3+ and Ho3+ ions are 1.13 x 10(-6) cm(2).s(-1)(450 degrees C) and 2.142 x 10(-5) cm(2).s(-1)(450 degrees C), respectively. The measured standard electrode potential of Ho3+/Ho is 2.987 V(vs. Cl/Cl-), being more negative than the theoretical one, the reason of which is also discussed.

Melt functionalization of ethylene-propylene copolymer: Structural investigation

An ethylene-propylene copolymer (EPM) has been functionalized with acrylic acid (AA) by means of a radical-initiated melt process. Different degrees of grafting have been obtained by varying the overall composition of the reaction mixture. The influence of the grafting degree on the structure has been investigated by differential scanning calorimetry (DSC), Fourier-transform infrared analysis (FTIR), and wide-angle x-ray scattering (WAXS) techniques. The results of the structural investigations suggest that the grafting preferentially occurs onto the ethylene sequences of EPM. After acrylic acid was grafted onto EPM, the grafted AA acted as nucleation agent; it caused an increase of crystallization temperature of propylene sequences of EPM-g-AA.

Nonisothermal melt and cold crystallization kinetics of poly(aryl ether ether ketone ketone)

Analysis of the nonisothermal melt and cold crystallization kinetics of poly(aryl ether ether ketone ketone) (PEEKK) was performed by using differential scanning calorimetry (DSC). The Avrami equation modified by Jeziorny could describe only the primary stage of nonisothermal crystallization of PEEKK. And, the Ozawa analysis, when applied to this polymer system, failed to describe its nonisothermal crystallization behavior. A new and convenient approach for the nonisothermal crystallization was proposed by combining the Avrami equation with the Ozawa equation. By evaluating the kinetic parameters in this approach, the crystallization behavior of PEEKK was analyzed. According to the Kissinger method, the activation energies were determined to be 189 and 328 kJ/mol for nonisothermal melt and cold crystallization, respectively.

ELECTROCHEMICAL-BEHAVIOR OF YTTRIUM ION IN LICL-KCL-NACL EUTECTIC MELT

The electrochemical reduction of yttrium ion on a molybdenum electrode in a LiCl-KCl-NaCl eutectic melt at 723 K was found to be almost reversible and to proceed by a one-step three electron reaction. The diffusion coefficient D of the Y(III) ion was measured to be (3.3 +/- 0.4) x 10(-6) cm2 s-1 by cyclic voltammetry, (5.0 +/- 0.9) x 10(-6) cm2 s-1 by the rotating disk electrode method, and (7.1 +/- 0.7) x 10(-6) cm2 s-1 by chronopotentiometry. The D values obtained by the latter two methods are in fairly good agreement with each other. The rather low D value obtained by cyclic voltammetry might be attributed to the fact that yttrium metal can dissolve slightly in the chloride melt. The standard potential of Y(III)/Y(0) couple was determined to be (-3.174 +/- 0.006) V (vs. Cl2/Cl-) by open-circuit potentiometry, (-3.15 +/- 0.02) V (vs. Cl2/Cl-) by the rotating disk electrode method and (-3.16 +/- 0.02) V (vs. Cl2/Cl) by chronopotentiometry. These three values are in good agreement with each other. Several types of Ni-Y intermetallic compounds were found to be formed on a nickel electrode.

Deep Fractionation of Clinopyroxene in the East Pacific Rise 13 degrees N: Evidence from High MgO MORB and Melt Inclusions

Mid-ocean ridge basalts (MORBs) from East Pacific Rise (EPR) 13 degrees N are analysed for major and trace elements, both of which show a continuous evolving trend. Positive MgO-Al2O3 and negative MgO-Sc relationships manifest the cotectic crystallization of plagioclase and olivine, which exist with the presence of plagioclase and olivine phenocrysts and the absence of clinopyroxene phenocrysts. However, the fractionation of clinopyroxene is proven by the positive correlation of MgO and CaO. Thus, MORB samples are believed to show a "clinopyroxene paradox". The highest magnesium-bearing MORB sample E13-3B (MgO = 9.52%) is modelled for isobaric crystallization with COMAGMAT at different pressures. Observed CaO/Al2O3 ratios can be derived from E13-3B only by fractional crystallization at pressure > 4 +/- 1 kbar, which necessitates clinopyroxene crystallization and is not consistent with cotectic crystallization of olivine plus plagioclase in the magma chamber (at pressure similar to 1 kbar). The initial compositions of the melt inclusions, which could represent potential parental magmas, are reconstructed by correcting for post-entrapment crystallization (PEC). The simulated crystallization of initial melt inclusions also produce observed CaO/Al2O3 ratios only at > 4 +/- 1 kbar, in which clinopyroxene takes part in crystallization. It is suggested that MORB magmas have experienced clinopyroxene fractionation in the lower crust, in and below the Moho transition zone. The MORB magmas have experienced transition from clinopyroxene+plagioclase+olivine crystallization at > 4 +/- 1 kbar to mainly olivine+plagioclase crystallization at < 1 kbar, which contributes to the explanation of the "clinopyroxene paradox".

Generation and evolution of magma beneath the East Pacific Rise: Constraints from U-series disequilibrium and plagioclase-hosted melt inclusions

Mid-ocean ridge basalt (MORB) samples from the East Pacific Rise (EPR 12 degrees 50'N) were analyzed for U-series isotopes and compositions of plagioclase-hosted melt inclusions. The Ra-226 and Th-230 excesses are negatively correlated; the Ra-226 excess is positively correlated with Mg# and Sm/Nd, and is negatively correlated with La/Sm and Fe-8; the Th-230 excess is positively correlated with Fe-8 and La/Sm and is negatively correlated with Mg# and Sm/Nd. Interpretation of these correlations is critical for understanding the magmatic process. There are two models (the dynamic model and the "two-porosity" model) for interpreting these correlations, however, some crucial parameters used in these models are not ascertained. We propose instead a model to explain the U-series isotopic compositions based on the control of melt density variation. For melting either peridotite or the "marble-cake" mantle, the FeOt content, Th-230 excess and La/Sm ratio increases and Sm/Nd decreases with increasing pressure. A deep melt will evolve to a higher density and lower Mg# than a shallow melt, the former corresponds to a long residence time, which lowers the Ra-226 excess significantly. This model is supported by the existence of low Ra-226 excesses and high Th-230 excesses in MORBs having a high Fe-8 content and high density. The positive correlation of Ra-226 excess and magma liquidus temperature implies that the shallow melt is cooled less than the deep melt due to its low density and short residence time. The correlations among Fe-8, Ti-8 and Ca-8/Al-8 in plagioclase-hosted melt inclusions further prove that MORBs are formed from melts having a negative correlation in melting depths and degrees. The negative correlation of Ra-226 excess vs. chemical diversity index (standard deviation of Fe-8, Ti-8 and Ca-8/Al-8) of the melt inclusions is in accordance with the influence of a density-controlled magma residence time. We conclude that the magma density variation exerts significant control on residence time and U-series isotopic compositions. (c) 2010 Elsevier B.V. All rights reserved.

XRD and XPS studies on the ultra-uniform Raney-Ni catalyst prepared from the melt-quenching alloy

We present a novel method for preparing an ultra-uniform Raney-Ni catalyst, which includes melt-quenching, hydrogen treatment and leaching in an alkali solution. The resultant catalyst shows superior activity in the reaction of cyclohexanone hydrogenation. X-ray diffraction (XRD) and XPS have been employed to characterize the catalysts. As demonstrated, the pretreatment with hydrogen caused a distinct phase transfer of the Ni-Al alloys, forming more of the Ni2Al3 component. In the subsequent leaching process, the Ni2Al3 component shows high activity and the resultant catalyst exhibits high surface areas and small pores. Moreover, metallic Al in the hydrogen-pretreated alloy appeared to be leached more easily and thus the aluminium species remaining on the catalyst surface is aluminium oxide predominantly, which serves as a matrix to stabilize active Ni species on the surface. Copyright (C) 2001 John Wiley & Sons, Ltd.