Devitrification process in rapidly solidified Al-Ni-Cu-Nd metallic glass

In the present study, rapidly solidified ribbons of A187 Ni7 Cu3 Nd3 metallic glass was prepared by using melt spinning. Devitrification process of the totally amorphous ribbons was investigated by high temperature X-ray diffraction analysis, combining with differential scanning calorimetry, under continuous and isothermal heating regime. The X-ray diffraction intensity and full width at the half maximum (FWHM) were analyzed to investigate the increase of crystallized amount and growth of α-Al crystal particles. The results show that under continuous heating regime, the metallic glass devitrifies via two main stages: primary crystallization, resulting in two-phase mixture of α-Al plus residual amorphous phase, and secondary crystallization, corresponding to rapid precipitation of some inter-metallic phases in the form of dispersion or eutectic mixture. Under isothermal heating regime, only Al crystal precipitates from the Al-rich amorphous matrix at low temperature, and when heating at 280 ℃ only Al     

Microscopic phase-field simulation of Cr atom substitution character during formation of Ll2 and DO22 phases in Ni-Cr-Al alloy

The simulations of Cr atom substitution character during the formation of L12 and DO22 phases in Ni-Cr-Al alloy were performed at 873 K based on microscopic phase-field model. It is found that the substitution of Cr is affected by Cr and Al contents and limits of occupation probabilities of Cr atom in L12 phase are present. The precipitate is single L12 phase when the component is less than the limit, Cr atoms substitute the Al sublattices in Ll2 phase, and both of atoms Al and Cr occupy the β-sites and complex phases Ni3（Al1-xCrx） are formed; Cr atoms enter Ni sites when Al and Cr contents exceed the limit, and substitute β-sites or both of α- and β-sites. The DO22 phase is formed at the boundary of Ll2 phase.     

Si3N4-doped Zr50Al15Ni10Cu25 glassy alloy by mechanical alloying and sintering process

Zr₅₀Al₁₅Ni₁₀Cu₂₅ amorphous powder was synthesized by mechanical alloying. The effect of Si₃N₄ addition on the crystallization behavior of the alloy during sintering process was studied. Thermal stability of the powders was performed by differential scanning calorimetry (DSC). The phase and microstructure of the powders and bulk specimens sintered were determined by X-ray diffractometry (XRD) and scanning electron microscopy (SEM). The results show that, introducing 0.05% (mass fraction) Si₃N₄ can enhance the crystallization activation energy of the Zr₅₀Al₁₅Ni₁₀Cu₂₅ amorphous powders, which indicates that Si₃N₄ addition has hindrance effect on forming crystals from Zr₅₀Al₁₅Ni₁₀Cu₂₅ amorphous powder. However, 0.10% Si₃N₄ results in the decrease of the crystallization activation energy, which makes its crystallization process easy to occur.     

The electronic structure and grain boundary segregation by boron addition

The electronic structure and grain boundary segregation caused by boron addition to Ni₃Al have been studied by X-ray photoelectron spectroscopy and Auger electron spectroscopy, respectively. The obtained results show that the Ni2p_3/2 electron binding energy rises gradually in the sequence of pure Ni<Ni₇₆Al₂₄<Ni₇₄Al₂₆<Ni₇₅Al₂₅, while it reduces monotonously with an increase in boron addition to Ni₃Al. Besides, it is found that the grain boundary segregation of boron occurring in Ni₃Al is a combined equilibrium and non-equilibrium type in nature. Based on the concept of the bonding environmental inhomogeneity, measured by the shift in Ni2p_3/2 electron binding energy from the nickel atoms in the simple substance nickel to those in the intermetallic compound Ni₃Al (ΔE _B), being responsible for the brittle behavior of the alloy, a binding energy shifting criterion for the brittle-ductile fracture transition in Ni₃Al is presented; when ΔE _B>0, the brittle failure occurs in Ni₃Al; when δE _B<0, the ductile one appears. Combined with the above experimental rules, the criterion predicts that pure Ni₃Al is brittle, and there exist the stoichiometric effect and concentration effect in the ductilization process for Ni₃Al by boron addition. Hence the criterion can be taken as a theoretical guide to alloy design in developing ductile intermetallics. Project supported by the National Natural Science Foundation of China.     

Properties of Al-doped Copper Nitride Films Prepared by Reactive Magnetron Sputtering

Cu3N and Al Cu3N films were prepared with reactive magnetron sputtering method. The two films were deposited on glass substrates at 0.8 Pa N2 partial pressure and 100 ℃ substrate temperature by using a pure Cu and AI target, respectively. X-ray diffraction （XRD） measurements show that the un-doped film was composed of Cu3N crystallites with anti-ReO3 structure and adopted [111] preferred orientation. XRD shows that the growth of Al-doped copper nitride films （AlxCu3N） was affected strongly by doping AI, the intensity of [111] peak decreases with increasing the concentration of Al and the high concentration of Al could prevent the Cu3N from crystallization. AFM shows that the surface of AlCu3N film is smoother than that of Cu3N film. Compared with the Cu3N films, the resistivities of the Al-doped copper nitride films （AlxCu3N） have been reduced, and the microhardness has been enhanced.     

Crystallization kinetics of amorphous Nd3.6 Pr5.4 Fe83Co3B5 and preparation of α-Fe/Nd2Fe14B nanocomposite magnets by controlled melt-solidification technique

The crystallization kinetics of amorphous Nd3. 6 Pr5.4 Fe83 Co3 B5 and the preparation of α-Fe/Nd2 Fe14 B nanocomposite magnets by controlled melt-solidification of Nd3.6Pr5.4Fe83Co3B5 was investigated by employing DTA, XRD, and TEM. The results show that a metastable intermediate phase Nd8Fe27B24 prior to α-Fe and Nd2 Fe14 B phases is crystallized as the amorphous Nd3.6 Pr5.4 Fe83 Co3 B5 is heated to 1 223 K. The crystallization activation energy of α-Fe and Nd8 Fe27324 phases is larger at the beginning stage of crystallization, and then it decreases with crystallized fraction x for the former and has little change when x is below 70% for the latter, which essentially results in an α-Fe/Nd2 Fe14 B microstructure with a relatively coarse grain size about 20-60 nm and a non-uniform distribution of grain size in the annealed alloy. The a-Fe/Nd2 Fe14 B nanocomposite magnets with a small average grain size about 14 nm and a quite uniform grain size distribution were prepared by controlled melt-solidification of nealing the amorphous Nd3. 6 Pr5. 4 Fe83 Co3 B5 precursor alloy.     

Densification and sintering dynamics of 10NiO-NiFe2O4 composites doped with CaO

The effects of CaO content in the range from 0 to 4.0%, and sintering temperature on the phase composition, relative density and electrical conductivity of 10NiO-NiFe2O4 composites doped with CaO were studied. The results show that there is no change of structure for NiO or NiFe2O4; there is apparent oxygen absorbing and releasing behavior during the heating process in air for 10NiO-NiFe2O4 composites. Introduction of CaO can accelerate the densification of 10NiO-NiFe2O4 composites. The maximum value of relative density is 98.75% for composite doped with 2.0% CaO and sintered at 1 200 ℃, which is beyond about 20% for the undoped composites. The sintering activated energy of sample containing 2% CaO decreases by 15.87 kJ/mol, compared with that of the undoped sample.     

Isolation, identification and characterization of cadmium-resistant Pseudomonas aeruginosa strain E1

Strain E₁ with resistance to 18 mmol/L cadmium (Cd), isolated from Cd-contaminated soil was identified by morphological observation, biochemical and physiological characterization and 16S rDNA sequence analysis. The resistance to heavy metals Cd, Cu, Co, Mn, Pb, Zn and 12 antibiotics was examined. The ability of removing Cd from solution was studied. The characterizations show that strain E₁ is affiliated to Pseudomonas aeruginosa (P. aeruginosa). Strain E₁ has high resistance to heavy metals and the order is found to be Cd>Mn>Zn>Cu>Pb>Co in solid media. Strain E₁ also exhibits the resistance to 12 antibiotics. Both living and non-living cells of strain E₁ can remove Cd from solution, and living cell has better biosorption than non-living cell. Foundation item: Project (50621063) supported by the National Natural Science Foundation of China; Project (2004CB619204) supported by the Major State Basic Research and Development Program of China     

Modification of nano-TiO2 by Al2O3 in-situ coating

A novel technology of in-situ coating Al₂O₃ on the surface of H₄TiO₄ was developed to prevent the aggregation of nano-TiO₂ powders and improve the dispersibility and thermal stability in the way of forming a uniform coating layer. The heterogeneous nucleation was conducted to prepare the precursor of nano-TiO₂ and then Al₂O₃ was coated on the surface of precursor. The effects of Al₂O₃ in-situ coating on the properties of nano-TiO₂ were investigated. The results show that H₄TiO₄ can be dispersed well under alkaline condition (pH 8.5) and the heterogeneous nucleation can be controlled easily. The optimized uniform coating layer is obtained by adding 5% (mass fraction) and 10% of Al₂O₃ and the aggregation of nano-TiO₂ powders is effectively inhibited and the dispersibility is obviously improved. The crystal sizes of TiO₂ powders are 12.3, 11.4 and 8.7 nm after coating 0,5% and 10% of Al₂O₃ respectively. Al₂O₃ on the surface of particulates in amorphous phase could increase the thermal stability of nano-particles after calcined at 550 °C. Foundation item: Project(04GK2007) supported by Hunan Industrial Key Project of Science and Technology     

Crystallization kinetics of lithium aluminum germanium phosphate glass by DSC technique

The crystallization kinetics of Li2O-Al2O3-GeO2-P2O5 (LAGP) glass fabricated via the conventional melt-quenching method was studied by differential scanning calorimetry (DSC) under non-isothermal condition at different heating rates. The activation energy of glass transition Eg is 634.4 kJ/mol, indicating that LAGP glass is easy to crystallize at an elevated temperature. The activation energy of crystallization Ec and Avrami index n obtained from Matusita’s model are 442.01 kJ/mol and 1.7, respectively. The value of n reveals that bulk crystallization predominates slightly over surface crystallization during crystallization process. LAGP glass-ceramics after different heat treatments have the same crystalline phases determined as major phase LiGe2(PO4)3, with AlPO4 and GeO2 as their impurity phases.     

Effects of temperature and initial molar ratio of Na2O to Al2O3 on agglomeration of fine Al（OH）3 seed in synthetic Bayer solution

Fine Al（OH）3 crystals were aggregated from supersaturated aluminate solution in the batch reaction tanks. By means of laser particle size analyzer and scanning electron microscopy, the influences of temperature and initial molar ratio of Na2O to Al2O3 （aK） on agglomeration of fine seed in Bayer process were investigated. The results show that agglomeration is almost finished in 8 h, and seeds with size less than 2 μm are easily aggregated together, and almost disappear in 8 h under the optimal process conditions. In the aluminate solution with the same moderate initial aK, when the reaction temperature reaches 75 ℃, the secondary nucleation does not occur, and the effect of agglomeration is better. And at the same reaction temperature, when the initial aK is 1.62, the initial supersaturation of aluminate solution is moderate, the binders on the surfaces of the seed are enough to maintain the agglomeration process, and the agglomeration degree is better. From SEM images, agglomeration mainly occurs in the fine particles, the combinations among the fine particles are loose and the new formed coarse crystal shapes are irregular.     

Effect of cobalt loading on reducibility, dispersion and crystallite size of Co／Al2O3 Fischer-Tropsch catalyst

Co/Al2O3 Fischer-Tropsch synthesis catalysts with different cobalt loadings were prepared using incipient wetness impregnation method. The effects of cobalt loading on the properties of catalysts were studied by means of X-ray diffraction (XRD), temperature programmed reduction (TPR), hydrogen temperature programmed desorption (H2-TPD) and O2 titration. Co-support compound formation can be detected in catalyst system by XRD.For the Co/Al2O3 catalysts with low cobalt loading, CoAl2O3 phase appears visibly. Two different reduction regions can be presented for Co/Al2O3 catalysts, which belong to Co3 O4 crystallites (reduction at 320 ““C) and cobalt oxidealumina interaction species (reduction at above 400℃). Increasing Co loading results in the increase of Co3 O4 crystallite size. The reduced Co/Al2O3 catalysts have two adsorption sites, and cobalt loading greatly influences the adsorption behavior. With the increase of cobalt loading, the amount of low temperature adsorption is increased, the amount of high temperature adsorption is decreased, and the percentage reduction and cobalt crystallite size are increased.     

Structural Properties and Energy Analysis of ZrxCu90-xAl10Ternary Metallic Glasses

Classical molecular dynamics(MD) were conducted to study the structure and energy distribution of Zr_xCu_90-xAl₁₀(x=20, 30, 40, 50, 60, 70) ternary alloys. When the Zr composition is 30%, the glass transition temperature reaches the maximum value and the Zr₃₀Cu₆₀Al₁₀ owns high glass forming ability(GFA). Analysis of the short-range structure shows that there are more low-energy Zr-centered polyhedron with high coordination number(CN...     

Synthesis of γ-Al2O3 nanoparticles by chemical precipitation method

Highly pure active γ-Al₂O₃ nanoparticles were synthesized from aluminum nitrate and ammonium carbonate with a little surfactant by chemical precipitation method. The factors affecting the synthesis process were studied. The properties of γ-Al₂O₃ nanoparticles were characterized by DTA, XRD, BET, TEM, laser granularity analysis and impurity content analysis. The results show that the amorphous precursor Al(OH)₃ sols are produced by using 0.1 mol/L Al(NO₃)₃ · 9H₂O and 0.16 mol/L (NH₄)₂CO₃ · H₂O reaction solutions, according to the volume ratio 1.33, adding 0.024% (volume fraction) surfactant PEG600, and reacting at 40 °C, 1 000 r/min stirring rate for 15 min. Then, after stabilizing for 24 h, the precursors were extracted and filtrated by vacuum, washed thoroughly with deionized water and dehydrated ethanol, dried in vacuum at 80°C for 8 h, final calcined at 800 °C for 1 h in the air, and high purity active γ-Al₂O₃ nanoparticles can be prepared with cubic in crystal system, O _H ⁷ -FD3M in space group, about 9 nm in crystal grain size, about 20 nm in particle size and uniform size distribution, 131. 35 m²/g in BET specific surface area, 7 – 11 nm in pore diameter, and not lower than 99.93% in purity. Foundation item: Project(03JJY3015) supported by the Natural Science Foundation of Hunan Province     

Coordination properties and structural units distribution of Q^iT in calcium aluminosilicate melts from MD simulation

The distribution of AI(j) and the structural units distribution of Q^iT in calcium aluminosilicate melts were studied by means of molecular dynamics simulation. The results show that provided there exists lower-field strength cation relative to Al^3 , such as alkaline and alkaline earth metals, AI will be four-coordinated but not six-coordinated. Meanwhile, if there exist a large number of higher-field strength cations such as Si^4 and little lower-field strength cation, six-coordinated aluminum will be formed. The relation of structural units distribution of Q^iT with chemical composition shift was also extracted, showing that as Ca^2 exists, the distributions of Q^Si, QAl or QT have the similar changing trend with the variation of component. Because of high-temperature effect, the Al-tetrahedral units in melts are greatly active and unstable and there exist dynamic transforming equilibria of Al(3)←→AI(4) and Al(5)←→Al(4). The three-coordinated oxygen and charge-compensated bridging oxygen are proposed to explain phenomena of the negative charge redundancy of AIO4 and location of network modifier with charge-compensated function in aluminosilicate melts.     

A Modified Co-precipitation Method to Prepare Cu/ZnO/Al<Subscript>2</Subscript>O<Subscript>3</Subscript> Catalyst and Its Application in Low Temperature Water-gas Shift (LT-WGS) Reaction

A modified co-precipitation method for the production of Cu/ZnO/Al₂O₃ complex was studied. The modification was that part of Al was introduced by adding Al³⁺ into Cu²⁺/Zn²⁺ solution, and the rest of Al was added after co-precipitation step in the form of pseudo-boehmite. The prepared samples were characterized by different techniques such as X-ray diffraction, N₂ adsorption, H₂-N₂O titration, temperature programmed reduction and scanning electron microscopy. X-ray diffraction characterizations revealed that Al³⁺ can be doped in aurichalcite lattice, and the maximum doping amount of Al³⁺ was 5.0% of total Cu and Zn atoms. The Cu/ZnO/Al₂O₃ sample produced by the modified method, in which co-precipitated Al³⁺ was 2.5% of total Cu and Zn atoms showed much better activity and stability in water-gas shift reaction than commercial sample. The high Cu surface area (26.1 m²/g) obtained by decompositon of doped aurichalcite is believed to be responsible for the activity enhancement. The stability was enhanced mainly because of the support effect of γ-Al₂O₃, which was decomposed from pseudo-boehmite in the calcination step.     

Preparation and electrical properties of BaPbO3 thin film

BaPbO3 thin films were deposited on Al2O3 substrates by sol-gel spin-coating and rapid thermal annealing. The microstructure and phase of BaPbO3 thin films were determined by X-ray diffractometry, scanning electrons microscopy and energy dispersive X-ray spectrometry. The influence of annealing temperature and annealing time on sheet resistance of the thin films was investigated. The results show that heat treatment, including annealing temperature and time, causes notable change in molar ratio of Pb to Ba, resulting in the variations of sheet resistance. The variation of electrical properties demonstrates that the surface state of the film changes from two-dimensional behavior to three-dimensional behavior with the increase of film thickness. Crack-free BaPbO3 thin films with grain size of 90 nm can be obtained by a rapid thermal annealing at 700 ℃ for 10 min. And the BaPbO3 films with a thickness of 2.5 μm has a sheet resistance of 35 Ω·-1.     

Adsorption of Pb^2＋ on macroporous weak acid adsorbent resin from aqueous solutions： Batch and column studies

The adsorption properties of a novel macroporous weak acid resin (D152) for Pb²⁺ were investigated with chemical methods. The optimal adsorption condition of D152 resin for Pb²⁺ is at pH 6.00 in HAc-NaAc medium. The statically saturated adsorption capacity is 527 mg/g at 298 K. Pb²⁺ adsorbed on D152 resin can be eluted with 0.05 mol/L HCl quantitatively. The adsorption rate constants determined under various temperatures are k _{288 K}=2.22×10⁻⁵ s^t-1, k _{298 K}=2.51×10⁻⁵ s⁻¹, and k _{308 K}= 2.95×10⁻⁵ s⁻¹, respectively. The apparent activation energy, E _a is 10.5 kJ/mol, and the adsorption parameters of thermodynamics are ΔH ^Θ=13.3 kJ/mol, ΔS ^Θ=119 J/(mol·K), and ΔG ^Θ 298 K =−22.2 kJ/mol, respectively. The adsorption behavior of D152 resin for Pb²⁺ follows Langmuir model. Foundation item: Project(2008F70059) supported by the Scientific and Technological Research Planning of Zhejiang Province, China     

The mechanism study on annealing embrittlement of Al_(88)Ce_2Ni_9Fe_1 metallic glass

The mechanism of annealing embrittlement of Al88Ce2Ni9Fe1 metallic glass is studied by using SAXS. For this alloy the activation energy for embrittlement, Eb=(160±10) kJ·mol-1 is obtained It approaches the value of the activation energy for crystallization, Ec= (170± 10} kJ·mol-1 . The significant change in SAXS intensity is observed as the sample transformed from the ductile to the brittle state. About 0. 1 volume fraction of Al crystalline particle and 60 m2/cm3 of specific inner surface between crystalline and amorphous phase appear as the sam ple transformed from the ductile to the brittle state. The annealing embrittlement is caused by crystallization of this alloy.     

Decoioration and mineralization of yeast wastewater by using Ce-Fe/Al2O3 as heterogeneous photo-Fenton catalyst

Decoloration and mineralization of yeast wastewater were investigated by using Ce-Fe/Al2O3 as a heterogeneous photo-Fenton catalyst in fluidized bed reactor in order to solve the problem of yeast wastewater discharge. The experimental results were assessed in terms of total organic carbon（TOC） reduction. The operational and reaction conditions affecting the efficiencies of TOC removal such as initial pH value, H2O2 concentration, catalyst loading and UV power were studied. The results show that TOC is reduced from 347.6 mg/L to 10.8 mg/L, color is changed from 500 units to 0 under the conditions as follows： initial pH value 6. 0, H2O2 concentration of 1. 000 g/L, catalyst loading of 5 g/L, reaction duration of 120 rain and reaction temperature of 30 ℃. The irradiated Ce-Fe/Al2O3 catalyst was complexed with 1,10-phenanthroline and then it was subjected to Fourier transform infrared spectroscopy and diffuse reflectance spectroscopy to confirm the formation of Fe（Ⅱ） in the solid state. Heterogeneous photo-Fenton reaction proves to be effective for the treatment of yeast wastewater.