Micellar sensitized catalytic kinetic spectrophotometry for highly accurate and reproducible determination of V（IV） and V（V）

A highly accurate and reproducible micellar sensitized kinetic method was proposed for determination of V（VI）. The method is based on its catalytic effect on the oxidation of Coomassie brilliant blue R 250 （CBB＋） by bromate at pH 2.0. The reaction was monitored spectro- photometrically by measuring absorbance change with a fixed-time method of 5 min at 594 and 552 nm with and without surfactant. The variables influencing the calibra- tion sensitivity were extensively investigated, and the optimal conditions were established. The linear calibration range was 10-1,600 μg.L-1 with a relative SD ranging from 0.35 % to 3.35 % （for five replicate measurements of 75, 500, 1,000, and 1,500 μg.L-1） and a detection limit of 3.8 μg.L-1. The selectivity was also investigated, and greatly enhanced by suitable masking agents. The method was successfully applied to the analysis of V（IV） in pre- sence of excess V（V） up to 25 fold in environmental waters with the recoveries of 100.0 %-102.8 % for V（IV） and 95.7 %-99.7 % for total V. Its accuracy was validated by analysis of certified reference material via the present kinetic method and standard flame atomic absorption spectrometric method after extractive preconcentration with good agreement between certified and found values.     

Preparation and properties of W–Cu–Zn alloy with low W–W contiguity

The W–Cu–Zn alloy with a-brass matrix and low W–W contiguity was prepared by method of electroless copper plating combined with spark plasma sintering(SPS) method.The effects of process and parameters on the microstructure and mechanical properties of the alloy were investigated.The W–Cu–Zn alloy with a relative density of 96 % and a W–W contiguity of about 10 % was prepared by original fine tungsten particles combined with wet mixing method and SPS solid-state sintering method at 800 °C for 10 min.The microstructure analysis shows that Cu–Zn matrix consists of nano-sized a-brass grains,and the main composition is Cu_3Zn electride.The nano-sized Cu was coated on the surface of tungsten particles by electroless copper plating method,and the fairly low consolidation temperature and short solid-state sintering time result in the nano-sized matrix phase.The dynamic compressive strength of the W–Cu–Zn alloy achieves to1000 MPa,but the alloy shows poor ductility due to the formation of the hard and brittle Cu_3Zn electrides.The fine-grain strengthening and the solution strengthening of the Cu–Zn matrix phase are responsible for the high Vickers microhardness of about 300 MPa for W–Cu–Zn alloy.     

Solid-phase extraction of trace Au(Ⅲ) with SDG and determination by the catalytic spectrophotometric method

The new catalytic kinetic spectrophotometric method for Au(Ⅲ) determination was developed and validated.It was based on the catalytic effect of gold on the oxidation of sudan red Ⅲ by ammonium peroxodisulfate ((NH4)2S2O8) with nitrilo triaeetic acid as an activator in microemulsion and H2SO4 medium.Under optimum conditions,there was the linearity of the calibration curve in the concentration range from 0 to 20 μg/L Au(Ⅲ) at 520 nm.The relative standard deviation was 3.0% with a correlation coefficient of 0.9986.The detection limit achieved was 9.75×10-5 μg/mL.A new method using a column packed with sulfhydryl dextrose gel (SDG) as a solid-phase extraetant has been developed for the preeoncentration and separation of Au(Ⅲ) ions.The method has been applied to the determination of trace gold with satisfactory results.     

A novel indicator system for catalytic spectrophotometric determination and speciation of inorganic selenium species (Se(Ⅳ), Se(Ⅵ)) at trace levels in natural lake and river water samples

A novel catalytic kinetic method is proposed for the determination of Se(Ⅳ), Se(Ⅵ), and total inorganic selenium in water based on the catalytic effect of Se(Ⅳ) on the reduction of Celestine blue by sodium sulfide at pH 7.0 phosphate buffer. The fixed-time method was adopted for the determination and speciation of inorganic selenium. Under the optimum conditions, the two calibration graphs are linear with a good correlation coefficient in the range 2-20 and 20-200 μg·L-1 of Se(Ⅳ) for the fixed-time method a...     

Solid-phase extraction of trace Au（Ⅲ） with SDG and determination by the catalytic spectrophotometric method

The new catalytic kinetic spectrophotometric method for Au(III) determination was developed and validated. It was based on the catalytic effect of gold on the oxidation of sudan red III by ammonium peroxodisulfate ((NH4)2S2O8) with nitrilo triacetic acid as an activator in mi- croemulsion and H2SO4 medium. Under optimum conditions, there was the linearity of the calibration curve in the concentration range from 0 to 20 μg/L Au(III) at 520 nm. The relative standard deviation was 3.0% with a correlation coefficient of 0.9986. The detection limit achieved was 9.75 × 10-5 μg/mL. A new method using a column packed with sulfhydryl dextrose gel (SDG) as a solid-phase extractant has been developed for the preconcentration and separation of Au(III) ions. The method has been applied to the determination of trace gold with satisfactory results.     

Determination of trace amounts of silver(I) in the presence of an activator with a kinetic method

A simple and sensitive kinetic-spectrophotometric method was developed for the determination of trace amounts of silver, based on its catalytic effect on the oxidation of azocarmine G by peroxydisulfate in sulfuric acid medium and at 30 °C in the presence of 1,10-phenantroline as activator. The absorbance was measured at 525 nm with the fixed-time method. The optimization of the operating conditions regarding concentrations of the reagents, temperature, ionic strength, and interferences was also investigated. The calibration curve is linear over the concentration range 0.3–50.0 ng ml-1of silver with good precision and accuracy, and the detection limit is down to0.125 ng ml-1. The relative standard deviation for a standard solution of 25.0 ng ml-1of silver is 1.36 %(n = 10).The proposed method proves to be highly sensitive,selective, and relatively rapid for the assay of silver at lowlevel range of 0.3–50.0 ng ml-1without any pre-concentration and separation step. The method was applied for the determination of silver in river water and white photographic film. The analytic results of the real samples are in excellent agreement with atomic absorption spectrometry analysis. The analytical results obtained are satisfactory.     

Hot Deformation and Dynamic Recrystallization Behavior of Austenite-Based Low-Density Fe–Mn–Al–C Steel

The hot deformation and dynamic recrystallization(DRX) behavior of austenite-based Fe–27Mn–11.5Al–0.95 C steel with a density of 6.55 g cm-3were investigated by compressive deformation at the temperature range of900–1150 °C and strain rate of 0.01–10 s-1. Typical DRX behavior was observed under chosen deformation conditions and yield-point-elongation-like effect caused by DRX of d-ferrite. The flow stress characteristics were determined by DRX of the d-ferrite at early stage and the austenite at later stage, respectively. On the basis of hyperbolic sine function and linear fitting, the calculated thermal activation energy for the experimental steel was 294.204 k J mol-1. The occurrence of DRX for both the austenite and the d-ferrite was estimated and plotted by related Zener–Hollomon equations. A DRX kinetic model of the steel was established by flow stress and peak strain without considering dynamic recovery and d-ferrite DRX. The effects of deformation temperature and strain rate on DRX volume fraction were discussed in detail. Increasing deformation temperature or strain rate contributes to DRX of both the austenite and the d-ferrite, whereas a lower strain rate leads to the austenite grains growth and the d-ferrite evolution, from banded to island-like structure.     

Dual-wavelength dual-indicator catalytic kinetic spectrophotometry for determination of trace Ru(III)

A new dual-wavelength dual-indicator catalytic kinetic spectrophotometric method for the determination of trace Ru(III)was studied.This method was based on Ru(III)-catalyzing oxidation of Arsenazo I and indigo carmine by potassium bromate in sulfuric acid.The absorbances of the catalytic and noncatalytic systems were measured at 510 and610 nm,respectively.Under the optimum conditions,the linear range of determination is 0–0.12 lgáml-1and the detection limit is 1.21 9 10-4lgáml-1.The method was applied for the determination of trace Ru(III)in ore samples with satisfactory results.     

Non-isothermal decomposition kinetics and lifetime of Tb2(0-MBA)6(PHEN)2

The thermal decomposition of Tb2(O-MBA)6(PHEN)2 (O-MBA: o-methylbenzoate; PHEN: 1,10-phenanthroline) and its kinetics were studied under the non-isothermal condition by thermogravimetry-derivative thermogravimetry (TG-DTG) techniques. Kinetic parameters were obtained from analysis of TG-DTG curves by the Achar method and the Madhusudanan-Krishnan-Ninan (MKN) method. The most probable mechanism function was suggested by comparing the kinetic parameters. The kinetic equation for the first stage can be expressed as dcddt = Aexp(-E/RT) 3(1 - α)2/3 The lifetime equation at mass loss of 10% was deduced as lnr= -28.7429 + 19797.795/Tby isothermal thermogravimetric analysis.     

Effect of Rare Earth Doping on Impedance,Modulus and Conductivity Properties of Multiferroic Composites:0.5(BiLa_xFe_(1-x)O_3)–0.5(PbTiO_3)

The Lanthanum-doped bismuth ferrite–lead titanate compositions of 0.5(Bi LaxFe1-xO3)–0.5(Pb Ti O3)(x = 0.05,0.10,0.15,0.20)(BLxF1-x-PT) were prepared by mixed oxide method.Structural characterization was performed by X-ray diffraction and shows a tetragonal structure at room temperature.The lattice parameter c/a ratio decreases with increasing of La(x = 0.05–0.20) concentration of the composites.The effect of charge carrier/ion hopping mechanism,conductivity,relaxation process and impedance parameters was studied using an impedance analyzer in a wide frequency range(102–106Hz) at different temperatures.The nature of Nyquist plot confirms the presence of bulk effects only,and non-Debye type of relaxation processes occurs in the composites.The electrical modulus exhibits an important role of the hopping mechanism in the electrical transport process of the materials.The ac conductivity and dc conductivity of the materials were studied,and the activation energy found to be 0.81,0.77,0.76 and 0.74 e V for all compositions of x = 0.05–0.20 at different temperatures(200–300 °C).     

Analysis of trace mercury in water by solid phase extraction using dithizone modified nanometer titanium dioxide and cold vapor atomic absorption spectrometry

A new method for analysis of trace mercury in water samples was developed, based on the combination of preconcentration/separation using dithizone-modified nanometer titanium dioxide (TiO2) as a solid phase extractant and determination by cold vapor atomic adsorption spectrometry (CVAAS). Dithizone was dissolved with alcohol and loaded on the surface of nano-sized TiO2 powders by stirring. The static adsorption behavior of Hg2 on the dithizone-modified nanoparticles was investigated in detail. It was found that excellent adsorption ratio for Hg2 could be obtained in the pH range of 7-8 with an oscillation time of 15 min, and a 5 mL of 3.5 mol·L-1 HCl solution could quantitatively elute Hg2 from nanometer TiO2 powder. Common coexisting ions caused no obvious influence on the determination of mercury. The mechanisms for the adsorption and desorption were discussed. The detection limit (3σ) for Hg2 was calculated to be 5 ng·L-1. The proposed method was applied to the determination of Hg2 in a mineral water sample and a Zhujiang River water sample. By the standard addition method, the average recoveries were found to be 94.4%-108.3% with RSD (n = 5) of 2.9%-3.5%.     

Determination of trace gadolinium by catalytic kinetic fluorimetry

There was a significant catalytic effect of trace Gd(III) ions on the oxidative reaction of potassium persulfate with Saffron T in the acetic acid–sodium acetate buffer solution. Thus, a catalytic kinetic fluorimetry method for the determination of trace Gd(III) ions was established. The factors such as acidity, concentration of reagents, reaction time, and temperature as well as influence of coexisting ions were discussed. The optimum reaction conditions were established. The apparent rate constant and apparent activation energy of the reaction were determined. The linear range is 0.02–0.10 lgáml-1,and the detection limit is 7.27 9 10-4lgáml-1. This method was used for the determination of gadolinium in the samples of lanthanum acetate with RSD of 0.9 %–3.1 %.     

Microstructure and Properties of the Cr–Si–N Coatings Deposited by Combining High-Power Impulse Magnetron Sputtering(HiPIMS) and Pulsed DC Magnetron Sputtering

The Cr–Si–N coatings were prepared by combining system of high-power impulse magnetron sputtering and pulsed DC magnetron sputtering. The Si content in the coating was adjusted by changing the sputtering power of the Si target.By virtue of electron-probe microanalysis, X-ray diffraction analysis and scanning electron microscopy, the influence of the Si content on the coating composition, phase constituents, deposition rate, surface morphology and microstructure was investigated systematically. In addition, the change rules of micro-hardness, internal stress, adhesion, friction coefficient and wear rate with increasing Si content were also obtained. In this work, the precipitation of silicon in the coating was found.With increasing Si content, the coating microstructure gradually evolved from continuous columnar to discontinuous columnar and quasi-equiaxed crystals; accordingly, the coating inner stress first declined sharply and then kept almost constant. Both the coating hardness and the friction coefficient have the same change tendency with the increase of the Si content, namely increasing at first and then decreasing. The Cr–Si–N coating presented the highest hardness and average friction coefficient for an Si content of about 9.7 at.%, but the wear resistance decreased slightly due to the high brittleness.The above phenomenon was attributed to a microstructural evolution of the Cr–Si–N coatings induced by the silicon addition.     

Strain Hardening Associated with Dislocation,Deformation Twinning,and Dynamic Strain Aging in Fe–20Mn–1.3C–(3Cu) TWIP Steels

The effects of Cu on stacking fault energy,dislocation slip,mechanical twinning,and strain hardening in Fe–20Mn–1.3C twinning-induced plasticity(TWIP) steels were systematically investigated.The stacking fault energy was raised with an average slope of 2 mJ/m2 per 1 wt% Cu.The Fe–20Mn–1.3C–3Cu steel exhibited superior tensile properties,with the ultimate tensile strength reached at 2.27 GPa and elongation up to 96.9% owing to the high strain hardening that occurred.To examine the mechanism of this high strain hardening,dislocation density determination by XRD was calculated.The dislocation density increased with the increasing strain,and the addition of Cu resulted in a decrease in the dislocation density.A comparison of the strain-hardening behavior of Fe–20Mn–1.3C and Fe–20Mn–1.3C–3Cu TWIP steels was made in terms of modified Crussard–Jaoul(C–J) analysis and microstructural observations.Especially at low strains,the contributions of all the relevant deformation mechanisms—slip,twinning,and dynamic strain aging—were quantitatively evaluated.The analysis revealed that the dislocation storage was the leading factor to the increase of the strain hardening,while dynamic strain aging was a minor contributor to strain hardening.Twinning,which interacted with the matrix,acted as an effective barrier to dislocation motion.     

Catalytic spectrophotometric determination of trace vanadium in fly ash and coal gangue by Triton X-100 enhancing effect

Trace V(V) catalyzes mightily the decolorization reaction of arsenazo Ⅲ(AsA Ⅲ) by oxidizing with H2O2 in a pH 4.0 HAc-NaAc buffer solution, and the addition of Triton X-100 can further increase the sensitivity of the reaction and its catalytic extent is linear with the content of V(V). A catalytic spectrophotometric procedure for determining trace V(V)was developed. The results show that the maximun absorption of the color solution is at 560 nm and the detection limit of the method for V(V) is 0.014 mg.L-1. Beer's law is obeyed for V(V) in the range of 0.00-0.20 mg.L-1. The recoveries are 99.0%-104.6%, and the relative standard deviations (RSD) are 2.7%-3.7%. Combined with ion-exchange resin, the method has been applied to the determination of trace vanadium in fly ash and coal gangue with satisfactory results.     

4-methoxy-2,6-bis(3,5-dimethylpyrazoyl)-1,3,5-triazine modified carbon paste electrode for trace Cu(Ⅱ) determination by differential pulse volt-ammetry

A differential pulse voltammetric method was developed for the sensitive and selective determination of Cu(Ⅱ) at 4-methoxy-2,6-bis(3,5-dimethylpyrazoyl)-l,3,5-triazine modified carbon paste electrode in 0.05 mol/L KHC8H4O4 solution (pH = 4.02). The oxidation peak of Cu(Ⅱ) was observed at 0.065 V(vs Ag/AgCl) by scanning the potential in positive direc-tion. The analysis procedure consisted of an open circuit accumulation step in stirred sample solution. It was followed by medium exchange to a clean solution and subsequently an anodic potential scan was affected to obtain the voltammetric peak. The current was proportional to the concentration of the Cu(Ⅱ) ion in a range of 1× 10-7-1×10-4 mol/L for 6 min accumulation; the most of metal ions did not interfere with the determination. The developed method was applied to Cu(Ⅱ) determination in coal-ash sample, the results agreed with that of atomic adsorption spectroscopy(AAS).     

Non-isothermal kinetics of synthesizing vanadium nitride by one-step method

Vanadium nitride was synthesized by one-step method using V2O5 and carbon black as raw materials in nitrogen atmosphere. The phases of different reaction products prepared in different reaction temperatures were analyzed by X-ray diffraction(XRD), and the dynamic behavior of the process of synthesizing vanadium nitride(VN) by one-step method was studied with non-isothermal thermogravimetry. The mechanism function and kinetic parameters of reaction process were calculated by thermal gravimetric analyses(TGA), and the reaction rate equation was established. The XRD results show that for the samples tested with minimal VN after holding for 4 h at 1273 K, the main phase of products is VN at 1476 K, while some vanadium nitrides transform into vanadium carbides again over 1573 K. It is found that N2 is beneficial to stimulate reduction and proceed carbonization reaction,and the reduction and nitridation reaction can occur simultaneously. The activation energy of preparing VN by one-step method is 104.005 kJ·mol-1, and the frequency factor is 470.52 at 1280–1358 K, and 150.052 kJ·mol-1 and 2.35 9 104 at 1358–1426 K, respectively.     

Synthesis of vanadium and chromium carbides(V_8C_7–Cr_3C_2) nanocomposite via an in situ precursor method

In situ synthesis method was used to prepare V8C7–Cr3C2nanocomposite.Ammonium vanadate, ammonium dichromate and nanometer carbon black were used as raw materials.The products were characterized by X-ray diffractometry(XRD), scanning electron microscopy(SEM), transmission electron microscopy(TEM), thermogravimetric and differential scanning calorimetry(TGDSC) and X-ray photoelectron spectroscopy(XPS) techniques.The results show that V8C7–Cr3C2nanocomposite with an average crystallite size of 25.4 nm can be synthesized at 1200 °C for 1 h.The synthesis temperature required by the method is at least 200 °C lower than that required by the conventional approaches for preparing vanadium and chromium carbides.The powders show good dispersion and are mainly composed of spherical or nearly spherical particles with a mean diameter of about 30 nm.The weight loss ratio of the precursor throughout the reaction process reaches 58 wt%.Three exothermic peaks and four endothermic peaks occur during the reaction.The surface of the specimen is mainly composed of V, Cr, C and O elements.     

Synthesis,characterization,and thermostability of bis(2,2,6,6-tetramethyl-3,5-heptanedionato)copper(Ⅱ)

Owing to the adaptability to large scale processing,excellent composition control and film uniformity,the metal-organic chemical vapor deposition(MOCVD)technique is a promising process for high-temperature superconductor YBa2Cu3O7-δ(YBCO)preparation.In this technique,the evaporation characteristics and thermostability of adopted precursors in whole process will decide the quality and reproducible results of YBCO film.In the present report,bis(2,2,6,6-tetramethyl-3,5-heptanedionato)copper(Ⅱ)(Cu(TMHD)2)was synthesized by the interaction of copper acetate hydrate with TMHD in methanol solution,and its structure was identified by FTIR,1H NMR,and EI-MS spectroscopy.Subsequently,thermal property and the kinetics of decomposition were systematically investigated by nonisothermal thermogravimetric analysis methods(TGA)at different heating rates in streams of N2,and the average apparent activation energy of evaporation process was evaluated by the Ozawa,Kissinger,and Friedman methods.The possible conversion function was estimated through the Coats-Redfern method to characterize the evaporation patterns and followed a phase boundary reaction mechanism by the contracting area equation with average activation energy of 85.1 kJ·mol-1.     

Thermal decomposition kinetics and lifetime of the complex of Tb2（BA）6（PHEN）2

The thermal behavior of Tb2(BA)6(PHEN)2 (BA: benzoate, and PHEN: 1,10-phenanthroline) in a static air atmospbere was investigated by TG-DTG, SEM and IR techniques. By the kinetic method of processing thermal analysis data put forward by Malek et al., it is defined that the kinetic model for the first-step thermal decomposition is SB(m, n). The activation energy E for this step reaction is 99.07 kJ/mol, the entropy of activation ΔS^≠ is -84.72 J/mol, the enthalpy of activation ΔH^≠ is 94.26 kJ/mol, the free energy of activation ΔG^≠ is 144.77 kJ/mol and the pre-exponential factor lnA is 20.93.The lifetime equation at mass-loss of 10% was deduced as lnτ = -29.0312 19760.83/T by isothermal thermogravimetric analysis.