Microstructures, mechanical properties and corrosion behavior of high-pressure die-cast Mg-4Al-0.4Mn-xPr (x=1, 2, 4, 6) alloys

Mg-4Al-0.4Mn-xPr (x = 1, 2, 4 and 6 wt.%) magnesium alloys were prepared successfully by the high-pressure die-casting technique. The microstructures, mechanical properties, corrosion behavior as well as strengthening mechanism were investigated. The die-cast alloys were mainly composed of small equiaxed dendrites and the matrix. The fine rigid skin region was related to the high cooling rate and the aggregation of alloying elements, such as Pr. With the Pr content increasing, the alpha-Mg grain sizes were reduced gradually and the amounts of the Al2Pr phase and All, Pr-3 phase which mainly concentrated along the grain boundaries were increased and the relative volume ratio of above two phases was changed. Considering the performance-price ratio, the Pr content added around 4 wt.% was suitable to obtain the optimal mechanical properties which can keep well until 200 degrees C as well as good corrosion resistance. The outstanding mechanical properties were mainly attributed to the rigid casting surface layer, grain refinement, grain boundary strengthening obtained by an amount of precipitates as well as solid solution strengthening.

Surface-enhanced resonance Raman spectroscopy and spectroscopy study of redox-induced conformational equilibrium of cytochrome c adsorbed on DNA-modified metal electrode

The redox-induced conformational equilibrium of cytochrome c (cyt c) adsorbed on DNA-modified metal electrode and the interaction mechanism of DNA with cyt c have been studied by electrochemical, spectroscopic and spectroelectrochemical techniques. The results indicate that the external electric field induces potential-dependent coordination equilibrium of the adsorbed cyt c between its oxidized state (with native six-coordinate low-spin and non-native five-coordinate high-spin heme configuration) and its reduced state (with native six-coordinate low-spin heme configuration) on DNA-modified metal electrode. The strong interactions between DNA and cyt c induce the self-aggregation of cyt c adsorbed on DNA. The orientational distribution of cyt c adsorbed on DNA-modified metal electrode is potential-dependent, which results in the deviation from an ideal Nernstian behavior of the adsorbed cyt c at high electrode potentials. The electric-field-induced increase in the activation barrier of proton-transfer steps attributed to the rearrangement of the hydrogen bond network and the self-aggregation of cyt c upon adsorption on DNA-modified electrode strongly decrease the interfacial electron transfer rate.

Determination of ethenzamide and acetoaminophen in quaternary powdered samples by near infrared spectroscopy and searching combination moving window partial least squares algorithm: effects of spectral resolution and signal-to-noise ratio

The present study reports an application of the searching combination moving window partial least squares (SCMWPLS) algorithm to the determination of ethenzamide and acetoaminophen in quaternary powdered samples by near infrared (NIR) spectroscopy. Another purpose of the study was to examine the instrumentation effects of spectral resolution and signal-to-noise ratio of the Buchi NIRLab N-200 FT-NIR spectrometer equipped with an InGaAs detector. The informative spectral intervals of NIR spectra of a series of quaternary powdered mixture samples were first located for ethenzamide and acetoaminophen by use of moving window partial least squares regression (MWPLSR). Then, these located spectral intervals were further optimised by SCMWPLS for subsequent partial least squares (PLS) model development. The improved results are attributed to both the less complex PLS models and to higher accuracy of predicted concentrations of ethenzamide and acetoaminophen in the optimised informative spectral intervals that are featured by NIR bands. At the same time, SCMWPLS is also demonstrated as a viable route for wavelength selection.

Electroactive gold nanoparticles protected by 4-ferrocene thiophenol monolayer

Numerous reports have focused on ferrocene-terminated electroactive self-assembled monolayers (SAMs) on a flat An surface but only a few on ferrocene SAMs on An colloid. In this paper, we employ 4-ferrocene thiophenol as a novel capping agent to produce electroactive gold nanoparticles in consideration of the peculiar pi-conjugated structure. Transmission electron microscopy shows the narrow-dispersed gold core with an average core diameter of ca. 2.5 nm. UV/vis spectra examine the pi-conjugated structure of 4-ferrocene thiophenol and surface plasmon absorbance of the indicated gold nanoparticles. X-ray photoelectron spectroscopy reveals electronic properties of the An core and thiol ligands. Electrochemical measurement shows that the oxidation peak current is proportional to the scan rate, indicating the electrode process is controlled by adsorbed layer reaction. The formal potential of the Fc-MPCs is compared with that of free ferrocene in MeCN solution and the Fc-SAMs. The shifts are attributed to the phenyl moiety in the 4-ferrocene thiophenol and dielectric constant of the solvation environment.

Improved efficiency of PPV due to bulky tetraphenylmethane pendants

A PPV derivative containing bulky tetraphenylmethane side chains was synthesised. Its optical properties were examined. Compared to its parent PPV polymer, its UV-Vis absorption and PL showed less red-shift from solution to film, its PL showed much less concentration quenching effect and higher efficiency, its EL device showed 9-fold enhanced efficiency. These improvements were attributed to weakened inter-chain interaction caused by the tetraphenylmethane group.

Influence of the size of ultrafine CaCO3 powder on PP crystallization

The effects of CaCO3 on the crystallization behavior of polypropylene (PP) were studied by means of DSC and WAXD. The average sizes of the CaCO3 powders used were 0.1 mum (UC) and 0.5 mum (GC), respectively. The PP/CaCO3 composites at compositions of 1 phr and 10 phr were investigated. The results showed that the addition of CaCO3 reduced the supercooling, the rate of nucleation and the overall rate of crystallization (except for the 10 phr UC/PP sample). The crystallinity of PP was increased and the size distribution of the crystallites of alpha -PP; was: broadened. On the other hand,the crystallization rate of 10 phr UC/PP is 1.5 times higher than that of neat PP. It has an overall rate of crystallization 2 times as much as that of the neat PP and has the maximum crystallinity. The sizes of crystallites and the unit cell parameters of alpha -PP were varied by the addition of CaCO3. beta -PP was formed by addition of Ge and was not detected by addition of UC. The differences of crystallization behaviors of PP might be attributed to the combined effects of the content and size of CaCO3 filled.

Kinetic isotope effects of proton transfer reaction for amines by ultrasonic relaxation methods: Unexpected evidence from the results in ethylamine solutions

Ultrasonic absorption coefficients for ethylamine in heavy water (D2O) and in light water (H2O) have been measured in the frequency range from 0.8 to 220 MHz at 25 degrees C. A single relaxational process has been observed in these two kinds of solutions. From the concentration dependence of the ultrasonic relaxation parameters, and following the reaction mechanism proposed by Eigen et al. for ethylamine in H2O, the causes of the relaxations have been attributed to a perturbation of an equilibrium associated with a deuteron or proton transfer reaction. The rate and equilibrium constants have been estimated from deuterioxide or hydroxide ion concentration dependence of the relaxation frequency, and the kinetic isotope effects have been determined. In addition, the standard volume changes of the reactions have been calculated from the concentration dependence of the maximum absorption per wavelength, and the adiabatic compressibility has also been determined from the density and sound velocity for ethylamine in D2O and in H2O, respectively. These results are compared with those for propylamine and butylamine and are discussed in relation to the different kinetic properties between D2O and H2O, the reaction radii derived by Debye theory, and the structural properties of the reaction intermediate.

Isotope effect in proton-transfer and association-dissociation reactions for butylamine by ultrasonic relaxation methods

Ultrasonic absorption coefficients were measured for butylamine in heavy water (D2O) in the frequency range from 0.8 to 220 MHz and at concentrations from 0.0278 to 2.5170 mol dm(-3) at 25 degrees C; two kinds of relaxation processes were observed. One was found in relatively dilute solutions (up to 0.5 mol dm(-3)), which was attributed to the hydrolysis of butylamine. In order to compare the results, absorption measurements were also carried out in light water (H2O). The rate and thermodynamic parameters were determined from the concentration dependence of the relaxation frequency and the maximum absorption per wavelength. The isotope effects on the diffusion-controlled reaction were estimated and the stability of the intermediate of the hydrolysis was considered while comparing it with the results for propylamine in H2O and D2O. Another relaxation process was observed at concentrations greater than 1 mol dm(-3) in D2O. In order to examine the solution characteristics, proton NMR measurements for butylamine were also carried out in D2O. The chemical shifts for the gamma- and delta-proton in butylamine molecule indicate the existence of an aggregate. From profiles of the concentration dependence of the relaxation frequency and the maximum absorption per wavelength of sound absorption, the source of the relaxation was attributed to an association-dissociation reaction, perhaps, associated with a hydrophobic interaction. The aggregation number, the forward and reverse rate constants and the standard volume change of the reaction were determined. It was concluded from a comparison with the results in H2O that the hydrophobic interaction of butylamine in D2O is stronger than that in H2O. Also, the isotope effect on this reaction was interpreted in terms of the solvent structure.

Ultrasonic relaxation kinetics on fast deuteron transfer reaction

Propylamine has been selected to investigate the isotope effect of a fast deuteron transfer reaction by ultrasonic relaxation method. Ultrasonic absorption coefficients of propylamine in heavy water (D2O) at 25 degrees C in the concentration range from 0.0107 to 0.6300 mol dm(-3) have been measured by pulse and resonance methods over the frequency range from 0.8 to 220 MHz. A Debye-type single relaxation absorption has been observed in the solution. From the dependence of the ultrasonic relaxation parameters on the concentration and solution pH, the source of the observed relaxation has been attributed to a perturbation of the chemical equilibrium associated with the deuteron transfer reaction. The rate and equilibrium constants have been determined by the measurement of the deuteroxyl ion concentration dependence of the relaxation frequency. Also the standard volume change of the reaction has been determined from the concentration dependence of the maximum absorption per wavelength and the adiabatic compressibility has been calculated from the density and the sound velocity in the solution. These results have then been compared with those obtained for propylamine in light water (H2O). The forward rate constant is greater and the reverse rate constant is smaller in DO than in H2O. The standard volume change for deuteron transfer is greater than that for proton transfer reaction, and the adiabatic compressibility shows a similar trend. These data support an argument that there exists a stronger hydrogen bond in D2O than in H2O. The difference of the stability in the intermediate states, R-ND3+... OD- and R-NH3+... OH-, has also been considered from the results of the isotope effects.

The crystal structure and drawing-induced polymorphism in poly(aryl ether ketone)s .2. Poly(ether ether ketone ketone), PEEKK

The crystal structure, morphology and polymorphism induced by uniaxial drawing of poly(ether ether ketone ketone) [PEEKK] have been studied by transmission electron microscopy (TEM), electron diffraction (ED) and wide angle X-ray diffraction (WAXD). On the basis of WAXD and ED patterns,the crystal structure of unoriented PEEKK is determined to have two-chain orthorhombic packing with unit cell parameters of a 0.772 nm, b = 0.600 nm, c = 1.004 nm (form I), A stress-induced crystal modification (form II) is identified and found to possess a two-chain orthorhombic lattice with unit cell dimensions of a = 0.461 nm, b = 1.074 nm, c = 1.080 nm. The 7.5% increase in c-axis dimension for form II is attributed to an overextended chain conformation, arising from extensional deformation during uniaxial drawing and fixed ''in-situ'' through strain-induced crystallization. The average ether-ketone bridge bond angles in form II crystal are determined to be 148.9 degrees by using standard bond lengths. The crystal morphology of PEEKK bears a great similarity to that of PEEK. The crystals grow in the form of spherulites and have the b-axis of unit cell radial. The effects of draw rate on strain-induced crystallization and induction of form II structure are also discussed.

Thermal analysis of ethylene-propylene copolymer-grafted-glycidyl methacrylate

The thermal properties of ethylene-propylene copolymer grafted with glycidyl methacrylate (EP-g-GMA) were investigated by using differential scanning calorimetry (DSC). Compared to the plain ethylene-propylene copolymer (EP), peak values of melting temperature (T-m) of the propylene sequences in the grafted EP changed a little, crystallization temperature (T-c) increased about 8-12 degrees C, and melting enthalpy (Delta H-m) increased about 4-6 J/g. The isothermal and nonisothermal crystallization kinetics of grafted and ungrafted samples was carried out by DSC. Within the scope of the researched crystallization temperature, the Avrami exponent (n) of ungrafted sample is 1.6-1.8, and those of grafted samples are all above 2. The crystallization rates of propylene sequence in EP-g-GMA were faster than that in the plain EP and increased with increasing of grafted monomer content. It might be attributed to the results of rapid nucleation rate. (C) 1996 John Wiley & Sons, Inc.

Conversion from electronic conducting phase to redox conducting phase of polypyrrole

Square-wave voltommetry is used to study the oxidation of polypyrrole doped with dodecylsulfate. The net current curve in this experiment shows why the oxidation current does not display the capacitive-like shape common in cyclic voltammetry. In cyclic voltammetry, the redox behavior of polypyrrole is attributed to the size of dodecylsulfate, irreversible incorporation and the complete consumption of dodecylsulfate. After the polypyrrole film was scanned in aqueous NaCl solution, square wave voltammetric measurements show different results, indicating the change of the polymer nature with regard to the charge transport. This is explained by anion replacement, exclusion and the change of the charge transport mechanism.

Effect of physical aging on phenolphthalein polyethersulfone/poly(phenylene sulfide) blend .1. Mechanical properties

The effect of physical aging at 210 degrees C on the mechanical properties of phenolphthalein polyether sulfone (PES-C) and a PES-C/poly(phenylene sulfide) (PPS) blend, with 5% content of PPS, were studied using DMA, tensile experiments, an instrumented impact tester, and SEM observations. The blend shows good mechanical properties in comparison with the corresponding PES-C. The mechanical properties of both materials exhibit characteristics of physical aging, with only the aging rate of the blend relatively slower, which should be attributed to the constraint effect of PPS particles and the good interfacial adhesion. The morphology of the PPS phase in the blend did not change with aging time. The principal role of PPS particles is to induce crazes, which dissipate energy, under applied loading; thus, the blend shows good toughness. On the other hand, the multiple crazing mechanism depends on the molecular mobility or structural state of the matrix. (C) 1996 John Wiley & Sons, Inc.

EFFECT OF CODOPING SB AND V TO THE BIPBSRCACUO SYSTEM

With XRD, R- T curves, and a.c chi measurements, the doping and codoping effects of Sb and V to a Cu-deficient Pb-doped Bi system have been studied. A sample singly doped with V possesses a T(c) about 2 K lower than that of a sample singly doped with Sb. This is attributed to the different sites of their substitution. It was observed that for promoting 2223 phase formation, Sb and V works cooperatively, and the codoping of Sb may enhance the 2223 phase formed. With a low doping level of Sb, the optimum doping amount of V is 0.3, i.e., with a nominal composition of Bi1.5Pb0.3Sb0.06Sr2Ca2Cu2.4V0.3Oy. A sample in which the 2223 phase is the dominant phase and which has a zero resistance transition temperature of 105 K has been obtained.

Potential of the seaweed Gracilaria lemaneiformis for integrated multi-trophic aquaculture with scallop Chlamys farreri in North China

In this study the red alga, Gracilaria lemaneiformis, was cultivated with the scallop Chlamys farreri in an integrated multi-trophic aquaculture (IMTA) system for 3 weeks at the Marine Aquaculture Laboratory of the Institute of Oceanology, Chinese Academy of Sciences (IOCAS) in Qingdao, Shandong Province, North China. The nutrient uptake rate and nutrient reduction efficiency of ammonium and phosphorus from scallop excretion were determined. The experiment included four treatments each with three replicates, and three scallop monoculture systems served as the control. Scallop density (407.9 +/- 2.84 g m(-3)) remained the same in all treatments while seaweed density differed. The seaweed density was set at four levels (treatments 1, 2, 3, 4) with thallus wet weight of 69.3 +/- 3.21, 139.1 +/- 3.80, 263.5 +/- 6.83, and 347.6 +/- 6.30 g m(-3), respectively. There were no significant differences in the initial nitrogen and phosphorus concentration between each treatment and the control group (ANOVA, p > 0.05). The results showed that at the end of the experiment, the nitrogen concentration in the control group and treatment 1 was significantly higher than in the other treatments. There was also a significant difference in phosphorus concentration between the control group and the IMTA treatments (ANOVA, p < 0.05). Growth rate, C and N content of the thallus, and mortality of scallop was different between the IMTA treatments. The nutrient uptake rate and nutrient reduction efficiency of ammonium and phosphorus changed with different cultivation density and time. The maximum reduction efficiency of ammonium and phosphorus was 83.7% and 70.4%, respectively. The maximum uptake rate of ammonium and phosphorus was 6.3 and 3.3 A mu mol g(-1) DW h(-1). A bivalve/seaweed biomass ratio from 1:0.33 to 1:0.80 (treatments 2, 3, and 4) was preferable for efficient nutrient uptake and for maintaining lower nutrient levels. Results indicate that G. lemaneiformis can efficiently absorb the ammonium and phosphorus from scallop excretion and is a suitable candidate for IMTA.