Magnetic properties and crystallization kinetics of Zn<Subscript>0.5</Subscript>Ni<Subscript>0.5</Subscript>Fe<Subscript>2</Subscript>O<Subscript>4</Subscript>

Precursor of nanocrystalline Zn0.5Ni0.5Fe2O4 was obtained by grinding mixture of ZnSO4·7H2O,NiSO4·6H2O,FeSO4·7H2O,and Na2CO3·10H2O under the condition of surfactant polyethylene glycol(PEG)-400 being present at room temperature,washing the mixture with water to remove soluble inorganic salts and drying it at 373 K.The spinel Zn0.5Ni0.5Fe2O4 was obtained via calcining precursor above 773 K.The precursor and its calcined products were characterized by differential scanning calorimetry(DSC) ,Fourier transform infrared(FT-IR) ,X-ray diffraction(XRD) ,and vibrating sample magnetometer(VSM) .The result showed that Zn0.5Ni0.5Fe2O4 obtained at 1073 K had a saturation magnetization of 74 A·m2·kg-1.Kinetics of the crystallization process of Zn0.5Ni0.5Fe2O4 was studied using DSC technique,and kinetic parameters were determined by Kissinger equation and Moynihan et al.equation.The value of the activation energy associated with the crystallization process of Zn0.5Ni0.5Fe2O4 is 220.89 kJ·mol-1.The average value of the Avrami exponent,n,is equal to 1.59±0.13,which suggests that crystallization process of Zn0.5Ni0.5Fe2O4 is the random nucleation and growth of nuclei reaction.     

Preparation and magnetic properties of Fe<Subscript>2</Subscript>O<Subscript>3</Subscript> microtubules prepared by sol-gel template method

Fe(OH)₃ precursor sol was prepared by a sol-gel method. The precursor sol was dipped onto the absorbent cotton, and gel was formed on the absorbent cotton template after the volatilization of moisture. Fe₂O₃ microtubules were synthesized after the process of self-propagation or calcination. The phase, morphology, and particle diameter of the samples were examined by X-ray diffraction (XRD) and scanning electron microscopy (SEM), and the magnetic properties of the samples were measured using a vibrating sample magnetometer (VSM). The external diameters of Fe₂O₃ microtubules ranged between 8 and 13 μm, and the wall thicknesses ranged between 0.5 and 2 μm. The type of the calcination method plays a significant role in developing the Fe₂O₃ phase and the variation in the magnetic properties in the sol-gel template complexing method. γ-Fe₂O₃ was synthesized by a self-propagation method. However, α-Fe₂O₃ was synthesized after calcination at 400°C for 2 h. The coercivity of the samples synthesized by calcination at 400°C for 2 h after self-propagation was found to increase significantly, thereby presenting hard magnetic properties.     

Fabrication and characterization of SmO_（0.7）F_（0.2）FeAs bulk with a transition temperature of 56.5 K

The superconductivity of iron-based superconductor SmO 0.7 F 0.2 FeAs was investigated. The SmO 0.7 F 0.2 FeAs sample was prepared by the two-step solid-state reaction method. The onset resistivity transition temperature is as high as 56.5 K. X-ray diffraction (XRD) results show that the lattice parameters a and c are 0.39261 and 0.84751 nm, respectively. Furthermore, the global J c was more than 2.3 × 10 5 A/cm 2 at T = 10 K and H = 9 T, which was calculated by the formula of J c = 20ΔM/[a(1-a/(3b))]. The upper critical fields, H c2 ≈ 256 T (T = 0 K), was determined according to the Werthamer-Helfand-Hohenberg formula, indicating that the SmO 0.7 F 0.2 FeAs was a superconductor with a very promising application.     

Fabrication and magnetic properties of NiFe<Subscript>2</Subscript>O<Subscript>4</Subscript> nanorods

NiFe₂O₄ nanorods have been successfully synthesized via thermal treatment of the rod-like precursor fabricated by Ni-doped α-FeOOH, which was enwrapped by the complex of citric acid and Ni²⁺. The morphology evolution during the calcination of the precursor nanorods was investigated with transmission electron microscopy (TEM), and the phase and the magnetic properties of samples were analyzed through X-ray diffraction (XRD) and vibrating sample magnetometer (VSM). The results indicated that the diameter of the NiFe₂O₄ nanorods obtained ranged between 30 and 50 nm, and the length ranged between 2 and 3 μm. As the calcination temperature was up to 600°C, the coercivity, saturation magnetization, and remanent magnetization of the samples were 36.1 kA·m⁻¹, 27.2 A·m²·kg⁻¹, and 5.3 A·m²·kg⁻¹, respectively. The NiFe₂O₄ nanorods prepared have higher shape anisotropy and superior magnetic properties than those with irregular shapes.     

Influence of CaF2 on the structure and dielectric properties of Ag（Nb0.8Ta0.2）O3 ceramics

Ag(Nb0.8Ta0.2)O3 ceramics were prepared by the traditional solid-state reaction method. The effect of CaF2 addition on the structure and di-electric properties of Ag(Nb0.8Ta0.2)O3 ceramics was investigated. The addition of CaF2 led the ceramics to a larger grain size and distortion of lattice. With the addition of 4.5 wt.% CaF2, the permittivity of the ceramics increased from 442 to 1028, the dielectric loss decreased sharply from 6.12 × 10-3 to 8.6 × 10-4, and the temperature coefficient of capacitance decreased from 1834 ppm/°C to-50 ppm/°C (at 1 MHz). These results indicated that the high permittivity was related with a large grain size, a low grain boundary density, and the weak Ta-O or Nb-O bond strength caused by the addition of CaF2.     

Solid reaction mechanism of CaHPO4·2H2O ＋ CaCO3 with and without yttria

The effect of yttria on the solid reaction mechanism of a CaHPO₄·2H₂O + CaCO₃ system at different temperatures was experimentally studied. The samples with and without yttria were subjected to thermogravimetric/differential scanning calorimetry measurement. The samples were heat treated at the temperatures corresponding to the peaks on the DSC spectra, and the resulted phase compositions were identified by X-ray diffraction. The transformation mechanism was deduced by comparing the phases obtained at different temperatures. The results show that the transformations at below 1073 K are not affected by yttria, but all those at above 1073 K are completely altered. The formation temperature of hydroxyapatite decreases by 134 K, and the decomposition temperature increases by 38 K. The polymorphous transformation of Ca₃(PO₄)₂ from β phase to α phase increases by 47 K. The thermodynamic properties of the transformations at above 1073 K are also modified by the addition of yttria; that is, the endothermal peaks are substituted by exothermal peaks.     

Fabrication and Properties of Plasma-Sprayed Al<Subscript>2</Subscript>O<Subscript>3</Subscript>/ZrO<Subscript>2</Subscript> Composite Coatings

Al₂O₃ /xZrO₂ (where x = 0, 3, 13, and 20 wt.%) composite coatings were deposited onto mild steel substrates by atmospheric plasma spraying of mixed α-Al₂O₃ and nano-sized monoclinic-ZrO₂ powders. Microstructural investigation showed that the coatings comprised well-separated Al₂O₃ and ZrO₂ lamellae, pores, and partially molten particles. The coating comprised mainly of metastable γ-Al₂O₃ and tetragonal-ZrO₂ with trace of original α-Al₂O₃ and monoclinic-ZrO₂ phases. The effect of ZrO₂ addition on the properties of coatings were investigated in terms of microhardness, fracture toughness, and wear behavior. It was found that ZrO₂ improved the fracture toughness, reduced friction coefficient, and wear rate of the coatings.     

Sol-gel preparation and characterization of Li1.3Al0.3Ti1.7（PO4）3 sintered with flux of LiBO2

Li_1.3Al_0.3Ti_1.7(PO₄)₃ pellets sintered with different mole fractions of LiBO₂ were prepared by sol-gel method. The structural identification, surface morphology, ionic conductivity, and activation energy of the pellets were studied by X-ray diffraction, scanning electron microscopy, and electrochemical impedance spectroscopy. The results show that all the Li_1.3Al_0.3Ti_1.7(PO₄)₃ pellets sintered with different mole fractions of LiBO₂ have similar X-ray diffraction patterns. The sintered pellet becomes denser and the boundary and corner of the particles become illegible with the increase of LiBO₂. Among the Li_1.3Al_0.3Ti_1.7(PO₃)₄ pellets sintered with different mole fractions of LiBO₂, the one sintered with 1 mol% LiBO₂ shows the highest ionic conductivity of 3.95×10⁻⁴ S.cm⁻¹ and the lowest activation energy of 0.2469 eV.     

Magnetic properties and crystallization kinetics of Zn_(0.5) Ni_(0.5) Fe_2O_4

Precursor of nanocrystalline Zn0.5Ni0.5Fe2O4 was obtained by grinding mixture of ZnSO4·7H2O,NiSO4·6H2O,FeSO4·7H2O,and Na2CO3·10H2O under the condition of surfactant polyethylene glycol(PEG)-400 being present at room temperature,washing the mixture with water to remove soluble inorganic salts and drying it at 373 K.The spinel Zn0.5Ni0.5Fe2O4 was obtained via calcining precursor above 773 K.The precursor and its calcined products were characterized by differential scanning calorimetry(DSC) ,Fourier transform ...     

Effect of heat treatment of titanium substrates on the properties of IrO<Subscript>2</Subscript>-Ta<Subscript>2</Subscript>O<Subscript>5</Subscript> coated anodes

The Ti substrates of IrO 2 -Ta 2 O 5 coated anodes were treated by solid-solution and aging, stress relieving annealing, and recrystallization annealing, and the coatings were prepared by thermal decomposition of a mixture of H 2 IrCl 6·6H 2 O dissolved in hydrochloric acid and TaCl 5 dissolved in alcohol. Scanning electron microscopy (SEM), cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), and accelerated life test (ALT) were employed to study the microstructure and electrochemical properties of the anodes. Compared with the anode without heat treatment, the anodes with heat treatment are of higher electrochemical activity and longer accelerated life; especially, the anode with recrystallization annealing treatment has the best electrochemical properties and the longest accelerated life.     

Structure and electric property comparison between Ge nanoclusters embedded in Al<Subscript>2</Subscript>O<Subscript>3</Subscript> and Al<Subscript>2</Subscript>O<Subscript>3</Subscript>/ZrO<Subscript>2</Subscript>

Metal-insulator-semiconductor (MIS) structures containing Ge nanocrystals embedded in both Al₂O₃ and ZrO₂/Al₂O₃ are fabricated by an ultra-high vacuum electron-beam evaporation method. Secondary ion mass spectroscopy (SIMS) results indicate that Ge embedded in Al₂O₃ diffuses towards the surface of the Al₂O₃ layer after annealing at 800°C in N₂ ambient for 30 min. Ge embedded in ZrO₂/Al₂O₃ is stable, thus inducing less leakage current. Capacitance voltage studies indicate that annealing can effectively passivate the negatively charged trapping centers. Memory effect of the Ge nanoclusters is verified by hysteresis in the C-V curves in the Al₂O₃/Ge+Al₂O₃/Al₂O₃ and ZrO₂/Ge+Al₂O₃/Al₂O₃ samples. This article is based on a presentation in “The 7th Korea-China Workshop On Advanced Materials” organized by the Korea-China Advanced Materials Cooperation Center and the China-Korea Advanced Materials Cooperation Center, held at Ramada Plaza Jeju Hotel, Jeju Island, Korea on August 24–27, 2003.     

Synthesis and characterization of Li<Subscript>1.3</Subscript>Al<Subscript>0.3</Subscript>Ti<Subscript>1.7</Subscript>(PO<Subscript>4</Subscript>)<Subscript>3</Subscript>-coated LiMn<Subscript>2</Subscript>O<Subscript>4</Subscript> by wet chemical route

Li_1.3Al_0.3Ti_1.7(PO₄)₃-coated LiMn₂O₄ was prepared by wet chemical route. The phase, surface morphology, and electrochemical properties of the prepared powders were characterized by X-ray diffraction, scanning electron micrograph, and galvanostatic charge-discharge experiments. Li_1.3Al_0.3Ti_1.7(PO₄)₃-coated LiMn₂O₄ has similar X-ray diffraction patterns as LiMn₂O₄. The corner and border of Li_1.3Al_0.3Ti_1.7(PO₄)₃-coated LiMn₂O₄ particles are not as clear as the uncoated one. The two powders show similar values of lithium-ion diffusion coefficient. When cycled at room temperature and 55°C for 40 times at the charge-discharge rate of 0.2C, Li_1.3Al_0.3Ti_1.7(PO₄)₃-coated LiMn₂O₄ shows the capacity retentions of 98.2% and 93.9%, respectively, which are considerably higher than the values of 85.4% and 79.1% for the uncoated one. Both the capacity retention differences between Li_1.3Al_0.3Ti_1.7(PO₄)₃-coated LiMn₂O₄ and LiMn₂O₄ cycling at room temperature and 55°C become larger with the increase of charge-discharge rate. When the charge-discharge rate reaches 2C, the capacity retention of LATP-coated LiMn₂O₄ becomes 8.4% higher than the uncoated LiMn₂O₄ for room temperature cycling, and it becomes 11.1% higher than the latter when cycled at 55°C.     

Kinetics of forward extraction of Ti（IV） from H_2SO_4 medium by P_（507） in kerosene using the single drop technique

The kinetics of forward extraction of Ti(IV) from H2SO4 medium by P507 in kerosene has been investigated using the single drop technique.In the low concentration region of Ti(IV),the rate of forward extraction at 298 K can be represented by F(kmol·m-2·s-1)=10-5.07 [TiO 2 + ][H+]-1 [NaHA 2 ](o)·Analysis of the rate expression reveals that the rate determining step is(TiO)(i)2+ +(HA 2)(i)-[TiO(HA2)](i)+.The values of Ea,H±,S±,and G±298 are calculated to be 22 kJ·mol-1,25 kJ·mol-1,-218 J·mol-1·K-1,and 25 kJ·mol-1,respectively.The experimental negative S± values indicate that the reaction step occurs via SN2 mechanism.     

Studies on Al<Subscript>2</Subscript>O<Subscript>3</Subscript>/ZrO<Subscript>2</Subscript>/Al<Subscript>2</Subscript>O<Subscript>3</Subscript> high K gate dielectrics applied in a fully depleted SOI MOSFET

Al₂O₃/ZrO₂/Al₂O₃ gate stacks were prepared on ultrathin SOI (Silicon on insulator) substrates by ultrahigh vacuum electron beam evaporation and post-annealed in N₂ at 450°C for 30 min. Three clear nanolaminate layered structure of Al₂O₃(2.1 nm)/ZrO₂(3.5 nm)/Al₂O₃(2.3 nm) was observed with a high-resolution cross-sectional transmission electron microscope (HR-XTEM). High frequency capacitance voltage (C-V) characteristics of a fully depleted (FD) SOI MOS capacitor at 1 and 5 MHz were studied. The minority carriers determine the high frequency C-V properties, which is opposite to the case of bulk MOS capacitors. The series resistance of the SOI substrate is found to be the determinant factor of the high frequency characteristics of FD SOI MOS capacitors. This article is based on a presentation in “The 7th Korea-China Workshop on Advanced Materials” organized by the Korea-China Advanced Materials Cooperation Center and the China-Korea Advanced Materials Cooperation Center, held at Ramada Plaza Jeju Hotel, Jeju Island, Korea on August 24≈27, 2003.     

Yttria-Stabilized Zirconia Thermal Barriers Sprayed Using N<Subscript>2</Subscript>-H<Subscript>2</Subscript> and Ar-H<Subscript>2</Subscript> Plasmas: Influence of Processing and Heat Treatment on Coating Properties

Thermal barrier coatings were produced using both Ar and N₂ as the primary plasma gas. Various aspects of the process and the coatings were investigated. It was found that higher in-flight particle temperatures could be produced using N₂, but particle velocities were lower. Deposition efficiencies could be increased by a factor of two by using N₂ as compared to Ar. Coatings having similar values of porosity, hardness, Young’s modulus, and thermal diffusivity could be produced using the two primary gases. The coatings exhibited similar changes (increased hardness, stiffness, and thermal diffusivity) when heat-treated at 1400 °C. However, the N₂-processed coatings tended to have lower values of Young’s modulus and thermal diffusivity following such treatment. The results point to the potential advantage, in terms of reduced powder consumption and increased production rate, of using N₂ as compared to Ar as the primary plasma gas for TBC deposition. This article is an invited paper selected from presentations at the 2007 International Thermal Spray Conference and has been expanded from the original presentation. It is simultaneously published in Global Coating Solutions, Proceedings of the 2007 International Thermal Spray Conference, Beijing, China, May 14-16, 2007, Basil R. Marple, Margaret M. Hyland, Yuk-Chiu Lau, Chang-Jiu Li, Rogerio S. Lima, and Ghislain Montavon, Ed., ASM International, Materials Park, OH, 2007.     

Up-Date of a Thermodynamic Database of the ZrO<Subscript>2</Subscript>-Gd<Subscript>2</Subscript>O<Subscript>3</Subscript>-Y<Subscript>2</Subscript>O<Subscript>3</Subscript>-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> System for TBC Applications

The thermodynamic database of the ZrO₂-Gd₂O₃-Y₂O₃-Al₂O₃ system is up-dated taking into account new data on lattice stabilities of ZrO₂, Gd₂O₃ and Y₂O₃ and heat capacity measurements for the monoclinic phase Gd₄Al₂O₉ and phase with garnet structure Gd₃Al₅O₁₂. New data for the heat capacities of Gd₂Zr₂O₇ (pyrochlore) and GdAlO₃ (perovskite) as well as on the enthalpy of formation of fluorite solid solutions (Zr_1−x Gd _x )O_2−x/2 were found to be in good agreement with calculated results. In comparison with the previous assessment, taking into account new experimental data resulted in a change of the melting character of the Gd₄Al₂O₉ phase from a peritectic one to a congruent one in the Gd₂O₃-Al₂O₃ system. Correspondently, in the ternary system ZrO₂-Gd₂O₃-Al₂O₃, the melting character of the three-phase assemblage Gd₂O₃ (B), Gd₄Al₂O₉ and GdAlO₃ changed from eutectic to transition type U. The T ₀-lines for T/M and F/T diffusionless transformations and driving force of partitioning to equilibrium assemblage T + F were calculated in the ZrO₂-Gd₂O₃-Y₂O₃ system.     

Phase Relations in the ZrO<Subscript>2</Subscript>-Nd<Subscript>2</Subscript>O<Subscript>3</Subscript>-Y<Subscript>2</Subscript>O<Subscript>3</Subscript> System: Experimental Study and Advanced Thermodynamic Modeling

Phase equilibria in the ZrO₂-Nd₂O₃-Y₂O₃ system at 1523-1873 K have been investigated by x-ray diffraction (XRD) and scanning electron microscopy combined with energy dispersive x-ray spectroscopy (SEM/EDX). Temperatures of phase transformations were determined by differential thermal analysis. Temperatures of invariant reactions in the ZrO₂-Nd₂O₃ system F = A + Pyr and H = F + A were determined as 1763 and 2118 K respectively and thermodynamic parameters of phases were re-assessed. Phase transformations in ternary systems were determined at 1732 K for composition ZrO₂-48.46Nd₂O₃-5.38Y₂O₃ (mol%) and at 1744 and 1881 K for composition ZrO₂-79.09Nd₂O₃-2.75Y₂O₃ (mol%). They were interpreted using XRD investigation before and after DTA as Pyr + B → F, Pyr → F and A → B, respectively. The solubility of the Y₂O₃ in pyrochlore phase was found to exceed 10 mol%. The thermodynamic parameters of the ZrO₂-Nd₂O₃-Y₂O₃ system were reassessed taking into account solubility of Y₂O₃ in the Nd₂Zr₂O₇ pyrochlore phase (Pyr). It is assumed that Y³⁺ substitutes Nd³⁺ and Zr⁴⁺ in their preferentially occupied sublattices. Ternary parameter was introduced into fluorite phase (F) for better reproducing of phase equilibria. Mixing parameters were reassessed for phase A (Nd₂O₃ based solution), monoclinic phase B and cubic phase C (Y₂O₃ based solution). The isothermal sections calculated for the ZrO₂-Nd₂O₃-Y₂O₃ system are in the reasonable agreement with experimental results.     

HVOF thermal spray deposited Y<Subscript>2</Subscript>O<Subscript>3</Subscript>-stabilized ZrO<Subscript>2</Subscript> coatings for thermal barrier applications

High velocity oxy-fuel (HVOF) thermal spray has been successfully used to deposit yttria-stabilized zirconia (YSZ) for thermal barrier coating (TBC) applications. Adherent coatings were obtained within a limited range of spray conditions using hydrogen as fuel gas. Spray parameters such as hydrogen-to-oxygen ratio, spray distance, and substrate cooling were investigated. Spray distance was found to have a pronounced effect on coating quality; adherent coatings were obtained for spray distances between 75 and 125 mm from the gun exit for the hydrogen-to-oxygen ratios explored. Compared to air plasma spray (APS) deposited YSZ coatings, the HVOF deposited coatings were more fully stabilized in the tetragonal phase, and of similar density, surface roughness, and cross-sectional microhardness. Notably, fracture surfaces of the HVOF coatings revealed a more homogeneous structure. Many theoretical models predict that it should not be possible to melt YSZ in an HVOF flame, and therefore it should not be possible to deposit viable YSZ coatings by this process. The experimental results in the present work clearly contradict those expectations. The present results can be explained by taking into account the effect of partial melting and sintering on particle cohesion, as follows. Combustion chamber pressures (P _o) of ∼3.9 bar (58.8 psi) realized during HVOF gun operation allows adiabatic flame temperature values that are above the zirconia melting temperature. Under these conditions, the Ranz-Marshall heat transfer model predicts HVOF sprayed particle surface temperatures T _p that are high enough for partial melting of small (∼10 μm) zirconia particles, T _p=(1.10−0.95)T _m. Further analysis shows that for larger particles (38 μm), adherent coatings are produced when the particle temperature, T _p=0.59−0.60 T _m, suggesting that sintering may have a role in zirconia particle deposition during HVOF spray. These results suggest two different bonding mechanisms for powders having a broad particle size distribution.     

Effect of Ga addition on the magnetic properties and microstructure of nanocrystalline Nd_（12.3）Fe_（81.7）B_（6.0） ribbons

Nd 12.3 Fe 81.7 x Ga x B 6.0 (x = 0-1.8) ribbons were prepared by melt spinning at 22 m/s and subsequent annealing treatment. The influences of Ga addition and annealing conditions on the magnetic properties and microstructure of the nanocrystalline alloys were systematically investigated. After being annealed at 620℃ for 20 min, the J r and H ci increased from 0.85 T and 582.6 kA/m for Ga-free sample to 0.97 T and 734.6 kA/m for the x = 0.9 sample, respectively. The (BH) max for the x = 0.9 sample increased by about 40% from 96.3 to 135.5 kJ/m 3 compared with that of the Ga-free one. The significant improvement of magnetic properties originated from the refinement of grains in the samples by introducing Ga, which led to a stronger exchange coupling between the neighboring grains in comparison with that in Ga-free samples. The microstructure and magnetic properties of the samples depended strongly on annealing parameters, while the sensitivity of micro-structure to annealing conditions could be significantly suppressed by the addition of Ga element.