Effect of annealing on the morphology evolution and densification of LiMn2O4 film from chitosan-containing solution

Dense LiMn₂O₄ films deposited on a Pt-coated silicon substrate were obtained by annealing the deposited Li–Mn–O-chitosan films under a two-stage heat-treatment procedure. It was demonstrated that the heat-treatment at 300 °C plays an important role in the subsequent densification of LiMn₂O₄ films. This is attributed to the formation and rearrangement of the nano-sized LiMn₂O₄ crystallites. The surface morphology of the calcined Li–Mn–O-chitosan films was highly related to the annealing temperature. Ridge-like bumps formed on the surface of the films after being heated at 200 °C for 1 h. With calcination at 400 °C or higher, the surface morphology turned into a wrinkle-like microstructure. This morphology transformation is ascribed to the flowing characteristics of the Li–Mn–O-chitosan films during heat-treatment and subsequent thermal decomposition of the precursor at higher temperatures. Moreover, the electrochemical tests showed that the 700 °C-annealed LiMn₂O₄ film possesses the highest discharge capacity of 56.3 μA h/(cm² μm) and best capacity retention of 90.7% after 50 charge/discharge cycles of all annealed films.     

Grain growth and precipitation in an annealed cold-rolled Ni50.2Ti49.8 alloy

In this paper we present a transmission electron microscopic study on the effect of annealing on the microstructure of a cold-rolled Ni_50.2Ti_49.8 ribbon. Transmission electron microscopy of the as-received sample shows the presence of alternating amorphous and crystalline bands. The crystalline bands have widths of the order of a few microns and contain amorphous nanopockets and B2 nanograins, the latter at around 20 nm diameter and preferentially oriented with their normal along the 111 direction and perpendicular to the strip surface. As-received samples were annealed for 30 min at different temperatures up to 800 °C. Crystallization starts in the amorphous bands at around 350 °C and finally ends up with the coarsening of the grains in the entire sample. Annealing of the samples at 450 °C entirely transforms the amorphous bands into crystalline bands. At 800 °C the grain size increases to 30–50 μm with a formation of a tweed kind of morphology inside the grains when observed at room temperature. Diffraction patterns from such grains reveal the presence of diffuse intensity around 1/3110^* indicating the formation of the R-phase. NiTi₂ precipitates form at 450 °C while annealing at 600 °C and higher yields Ni₃Ti₂ precipitates. For samples annealed at 500 °C for a longer time, Ni₄Ti₃ precipitates have been observed along with the austenite to martensite transformation in the grains.     

Effect of Y203 on microstructure and oxidation of γ-Ni＋γ′-Ni3Al coatings transformed from electrodeposited Ni-Al films at 1 000℃

The electrodeposited Y2O3-dispersed γ-Ni＋γ-Ni3Al coatings on Ni substrates were developed by the conversion of electrodeposited Ni-Al-Y2O3 films with dispersed AI microparticles in Ni matrix into Ni3Al by vacuum annealing at 800 ℃ for 3 h. For comparison, Y2O3-free γ-Ni＋γ＇-Ni3Al coatings with a similar AI content were also prepared by vacuum annealing the electrodeposited microparticle-dispersed composite coatings of Ni-AI under the same condition. SEM and TEM characterizations show that the electrodeposited Y2O3-dispersed γ＋γ＇ coatings exhibit finer grains, a more homogeneous distribution of γ＇, and a narrowed γ＇ phase spacing compared with the electrodeposited Y2O3-free γ-γ＇ coatings. The oxidation at 1 000 ~C shows that the addition of Y2O3 significantly improves the oxidation resistance of the electrodeposited γ＋γ＇coatings. The effect of Y2O3 particles on the microstructure and oxidation behavior of the electrodeposited γ＋y＇ coatings was discussed in detail.     

Preparation of neodymium sulphides by the reaction of Nd2(So4)3 with carbon disulphide

The reaction to synthetize neodymium sulphides from neodymium sulphate octahydrate in a stream of carbon disulphide gas was studied. The dehydration of the octahydrate in vacuum was finished at 300 °C. At 1050–1100 °C in air neodymium oxysulphide, Nd₂O₂SO₄, was formed. Neodymium oxysulphide, Nd₂O₂S, was formed upon heating with a reducing agent such as annealed carbon. The reaction of neodymium sulphate with carbon disulphide commenced at 500–600 °C, resulting in formation of the disulphide, NdS₂. The crystal structure of NdS₂ heated at 500 °C was, however, different from that of the sample heated at 600 °C. In the temperature range 800–900 °C -Nd₂S₃ was obtained as a single phase after heating for at least 3 h in high flow rates of gas mixtures of nitrogen and high concentrations of carbon disulphide. The sesquisulphide, γ-Nd₂S₃ (or Nd₃S₄), was formed at temperatures as high as 1100 °C. The reaction conditions for the compounds mentioned above are discussed together with the analysis of their crystal structures by X-ray powder diffractometry.     

Crystallization of magnesium niobate from mechanochemically derived amorphous phase

The effect of high-energy ball milling and subsequent annealing on the mixture of MgO and Nb₂O₅ has been investigated. X-ray diffraction (XRD) measurement indicates that an amorphous phase is produced after milling for 5 h, while traces of MgNb₂O₆ crystallized from the amorphous phase during prolonged milling. Significant crystallization of MgNb₂O₆ from the amorphous state is observed after annealing at 500 °C, while the reaction of the remaining MgO and Nb₂O₅ does not take place at this temperature. Single phase MgNb₂O₆ can be achieved for all the milled samples at 700 °C. No significant grain growth is observed when the milled powders were annealed at temperature below 900 °C. Almost fully dense MgNb₂O₆ ceramics are obtained after annealing at 1100 °C from the as-milled powders.     

Existence, structure and valence properties of the skutterudites CeyFe4−xCoxSb12

We report on sample preparation, annealing effects, electron microprobe analysis in the series Ce_yFe_4−xCo_xSb₁₂ which shows that a phase separation occurs for substituted samples (0<x<4) annealed at 650 and 550 °C. Single phase samples are obtained for either Ce_yFe₄Sb₁₂ or Ce_yCo₄Sb₁₂ samples annealed at 650 °C and for all compositions when annealed at 700 °C. The valence state of Ce in homogeneous samples has been studied using X-ray absorption spectroscopy (XAS). Ce ions are trivalent throughout the series and the XAS spectra does not show effect of the crystal field on the 5d-final state.     

Effect of vanadium doping on fabrication and property of Bi4Ti3O12 ceramics

Vanadium-doped bismuth titanate ceramics of composition Bi₄Ti_3−xV_xO_12+x/2 (BTV, x = 0.02, 0.03, 0.04, 0.06, 0.08) were prepared using the conventional solid-state reaction method. The sintering activity was significantly improved by the addition of even a small amount of vanadium. The effects of the incorporation of vanadium in the Bi₄Ti₃O₁₂ lattice on the microstructure, Raman characteristics, dielectric and ferroelectric properties of the samples were investigated.     

Two-phase intermetallic alloy Ni3(Al, Si):microstructure and mechanical properties

Yield stress in compression (0.2% flow stress) from ambient temperature up to 800 °C has been studied on Ni₃(Al, Si) alloy with the atomic composition Ni₇₈Al₁₁Si₁₁. When annealed at 1000 °C, the alloy has a pure L1₂ (γ′) ordered structure. After subsequent annealing at 750 °C, the disordered solid solution of Al and Si in Ni (face centred cubic, γ) precipitates in fine coherent particles. Calorimetry helps to describe the various phase transformations necessary to obtain the last microstucture. Solute addition of Si, which replaces Al atoms, increases the 0.2% flow stress of Ni₃Al in the fully γ′ microstructure. The γ precipitation shifts the peak stress towards higher temperatures and stresses.     

Microstructure and properties of CVD γ-Al2O3 coatings

This work deals with the microstructures and wear properties of chemical vapour deposited γ-Al₂O₃. The γ-Al₂O₃ coatings were deposited at 800 °C on TiN and Ti(C,N) pre-coated cemented carbide substrates. The microstructures developed in the γ-Al₂O₃ coatings and the influence of the nucleation surface on the growth of γ-Al₂O₃ were characterised using transmission electron microscopy, electron energy-loss spectroscopy and X-ray diffraction. The γ-Al₂O₃ coatings were fine-grained with a high density of {1 1 1} growth twins and contained some residual sulphur. γ-Al₂O₃ was found to grow epitaxially on the investigated substrates. The mechanical properties were evaluated in metal cutting and were compared with those of κ-Al₂O₃ coated tools. As compared with the κ-Al₂O₃ coatings, the γ-Al₂O₃ coatings exhibited slightly worse adhesion and tendency for edge chipping. However, the γ-Al₂O₃ coatings showed better crater wear resistance on the rake face than κ-Al₂O₃ coatings.     

Structural phase transformations of rare-earth modified transition alumina to corundum

The effect of rare-earth dopant on transformations of the γ→θ→ phases in fine alumina powders under vacuum was investigated by in situ neutron diffraction from 500 to 1300 °C. La-doped (1 mol%) Al₂O₃ powders (surface area 170 m²/g) were prepared by an impregnation technique. Below 800 °C both samples contain a dominant γ-phase. Above 1000 °C, transformation of the γ-phase to the intermediate θ-phase, and then completely to the -phase (corundum) was observed. Addition of 1 mol% of La in Al₂O₃ effectively shifts the -phase formation temperature from 1125 °C for pure alumina to 1250 °C, probably due to the larger size of La compared to Al ions, which hinders ionic diffusion in the processes of sintering and transformation. Consequently, doping La in alumina improves the surface-area and thermal stability at high temperatures, which is important for catalytic applications.     

Structural and electrical properties of SrBi2(Ta0.5Nb0.5)2O9 thin films

SrBi₂(Ta_0.5Nb_0.5)₂O₉ (SBTN) thin films were obtained by polymeric precursor method on Pt/Ti/SiO₂/Si(1 0 0) substrates. The film is dense and crack-free after annealing at 700 °C for 2 h in static air. Crystallinity and morphological characteristic were examined by X-ray diffraction (XRD), field emission scanning electron microscopy (FEG-SEM) and atomic force microscopy (AFM). The films displayed rounded grains with a superficial roughness of 3.5 nm. The dielectric permittivity was 122 with loss tangent of 0.040. The remanent polarization (P_r) and coercive field (E_c) were 5.1 μC/cm² and 96 kV/cm, respectively.     

Solid-phase equilibria in the Ti-rich part of the Ti---Al system

The solid-state-phase equilibria in the Ti-rich portion of the Ti---Al system (0–50%Al) have been investigated at temperatures between 800°C and 1415°C by electron probe microanalysis (EPMA) and by transmission electron microscopy (TEM) on diffusion couples as well as on annealed alloys. The TEM observations on the diffusion couples show that the phase field ₂, (ordered hexagonal DO₁₉) extends up to the β (bcc A2) phase field, leading to two peritectoid transformations, β + → ₂ at T = 1210 ± 10°C and β + ₂→ at T = 1160 ± 10°C (: hexagonal A3). The diffusion-couple experiments yield the tie lines of the observed phase equilibria. The present results confirm the existence of a eutectoid transition → ₂ + λ (λ: ordered fcc Ll₀) at about T = 1120 ± 10°C. An updated phase diagram based on these data is presented.     

Solid state reactions in highly dispersed praseodymium oxide–SiO2 system

This paper reports results of studies on the interaction of praseodymium oxide nanocrystals with an amorphous silica. Nano-sized (3–4 nm) amorphous precursor of praseodymium oxide synthesized using a microemulsion technique were supported onto a high surface SiO₂ or occluded into SiO₂ matrix. Solid state reactions occurring in these binary systems upon heat treatment in air, argon or hydrogen at 800–1100 °C were studied by TEM, XRD, FT-IR and UV–vis spectroscopy. It has been found that morphology of the sample as well as annealing atmosphere influence greatly the phase evolution. At temperatures above 900 °C, nanocrystalline praseodymium silicates of various morphology and crystal structure were obtained. In particular, a new polymorph of Pr₂Si₂O₇, isostructural with I-type Ln₂Si₂O₇ (Ln₆[Si₄O₁₃][SiO₄]₂) Ln = Ce, La, has been identified.     

Correlation between dielectric properties and strain in Pb0.5 Sr0.5TiO3 thin films prepared by using the sol–gel method

Pb_0.5Sr_0.5TiO₃ (PST) thin films were fabricated by the alkoxide-based sol–gel process using spin-coating method on Pt/Ti/SiO₂/Si substrate. The PST films annealed from 500 °C to 650 °C for 1 h show a perovskite phase and dense microstructure with a smooth surface. The grain size and dielectric constant of PST films increase with the increase in annealing temperature, which reduces the SiO₂ equivalent thickness of the PST film. The crystallinity or internal strain in the PST thin films analyzed from the diffraction-peak widths correlates well with the decrease in the dielectric losses. The dielectric constants and dielectric loss (%) of the PST films annealed at 650 °C (t_eq=0.89 nm) were 549 and 0.21%, respectively.     

Improved oxidation resistance of Ti with a thermal sprayed Ti3Al(O)–Al2O3 composite coating

A Ti₃Al(O)–Al₂O₃ in situ composite was explored as a coating system for Ti using thermal spray. Oxidation tests at 700–800 °C showed that this coating remarkably decreased the oxidation rate and increased the scale spallation resistance compared with Ti. The mechanisms for these improvements were then briefly discussed.     

Synthesis and characterization of molybdenum aluminide nanoparticles reinforced aluminium matrix composites

Aluminium matrix composites reinforced with molybdenum aluminide nanoparticles were synthesized by ball milling and reactive sintering of the mixture of aluminium and 10 wt% hydrated molybdenum oxide powders. Sintering the as milled powder in air below 750 °C produced MoAl₁₂ intermetallic compound nanoparticles, at 750 °C produced a mixture of MoAl₅ and MoAl₄ nanoparticles and at 800 °C under Argon atmosphere produced predominantly MoAl₄ intermetallic nano-particles in the Al matrix. The powder compacts sintered in air below 750 °C produced MoAl₁₂ whereas at 750 °C or above formed the Al matrix composite reinforced with the MoAl₅ nanoparticles. These nanoparticles become agglomerated to take up some irregular shaped flakes in the metal matrix. The reaction between Al and hydrated Mo oxide powders was found to be a favorable way to produce predominantly a particular Mo–Al intermetallic compound at a particular temperature. The Al₂O₃ particles formed as another reaction product, in all the above reactions, remain distributed in these composites. The composites thus formed were characterized by SEM-EDS, DTA, XRD and TEM analysis.     

In situ TEM observation of dislocation motion in thermally strained Al nanowires

Al thin films deposited epitaxially on (0001) -Al₂O₃ substrates, have been thinned cross-sectionally to form Al nanowires. The Al wires, consisting of two Σ3 twin variants, have been strained in situ by differential thermal expansion between the Al wires and the Al₂O₃ substrate during transmission electron microscopy heating. Dynamical observations show that maximum dislocation activity occurs in the first heating cycle up to 400°C, with decreasing activity during further cycles. The {111} Al || (0001) -Al₂O₃ interface acts as a source of dislocation half-loops. The motion of threading dislocations along the wires generates long trailing dislocation segments parallel to, and offset from, the {111} Al || (0001) -Al₂O₃ interface. Dislocation multiplication occurs by the reaction of half-loops and extended threading dislocation segments at the wire boundaries and substrate interface. The Σ3 twin grains bisecting the wires are observed to be stable during thermal cycling to 400°C, and their { } boundaries are weak pinning sites.     

Formation of Al–Y oxide during processing of γ-TiAl

While processing Y₂O₃ dispersed γ-TiAl, Y₂O₃ particles which dissolved during hot isostatic pressing (HIP’ing) were found to precipitate during the heat treatment in the form of a mixed Al–Y oxide. To understand the chemical reaction that occurs between Y₂O₃ and γ-TiAl during the heat treatment cycle, a powder mixture comprising of γ-TiAl and 10 wt.% Y₂O₃ was mechanically alloyed (MA’d) for 8 h and the milled powder was subjected to differential thermal analysis (DTA) at 1150 °C prior to analyzing it using X-ray diffraction technique. The present study clearly demonstrates that aluminum in the combined form either as γ-TiAl or Al₂O₃ reacts in a similar manner with Y₂O₃ when milled and heat treated at 1150 °C. In either case there is formation of Al₂Y₄O₉ (2Y₂O₃.Al₂O₃).     

Thermal Stability of WB2 and W-B-N Films Deposited by Magnetron Sputtering

The work is mainly to study the thermal stability including the phase stability, microstructure and tribo-mechanical properties of the AlB₂-type WB₂ and W-B-N (5.6 at.% N) films annealed in vacuum at various temperatures, which are deposited on Si and GY8 substrates by magnetron sputtering. For the WB₂ and W-B-N films deposited on Si wafers, as the annealing temperature increases from 700 to 1000 °C, a-WB (700 °C) and Mo₂B₅-type WB₂ (1000 °C) are successively observed in the AlB₂-type WB₂ films, which show many cracks at the temperature ≥?800 °C resulting in the performance failure; by contrast, only slight α-WB is observed at 1000 °C in the W-B-N films due to the stabilization effect of a-BN phase, and the hardness increases to 34.1 GPa first due to the improved crystallinity and then decreases to 31.5 GPa ascribed to the formation of α-WB. For the WB₂ and the W-B-N films deposited on WC-Co substrates, both the WB₂ and W-B-N films react with the YG8 (WC-Co) substrates leading to the formation of CoWB, CoW₂B₂ and CoW₃B₃ with the annealing temperature increasing to 900 °C; a large number of linear cracks occur on the surface of these two films annealed at ≥?800 °C leading to the film failure; after vacuum annealing at 700 °C, the friction performance of the W-B-N films is higher than that of the deposited W-B-N films, while the wear resistance of the WB₂ films shows a slight decrease compared with that of the deposited WB₂ films.     

Synthesis, crystal structure, oxygen stoichiometry, and electrical conductivity of La1−aCaaCr0.8Ti0.2O3−δ solid solutions

Series of perovskite-type compounds La_1−aCa_aCr_0.8Ti_0.2O_3−δ (a=0–1.0) were synthesized by the ceramic technique in air (final heating 1350 °C). The crystal structure of the compounds after cooling in air to room temperature was characterized as orthorhombic in space group Pbnm. Analysis of the lattice constants shows a noticeable decrease with increasing Ca content. All compounds prepared were stable in air and in a stream of Ar/1 Pa O₂ at 20–1400 °C, as also in Ar/5% H₂ (pH₂O/pH₂=0.01) at 850–1000 °C. Oxygen stoichiometry and electrical conductivity of the solid solutions with a=0.0–1.0 are investigated. Increasing Ca contents decrease the stability of the oxides in respect to the thermal dissociation of oxygen. All compounds are p-type semiconductors in the temperature range 20–1000 °C at oxygen partial pressures of 10⁻¹⁵ to 0.21×10⁵ Pa. A maximum conductivity of about 30 S/cm in air at 1000 °C is observed for the composition with a=0.6 corresponding to a ratio of Cr³⁺/Cr⁴⁺=1 at an oxygen stoichiometry near 3.0, and oxidation states of La, Ca, Ti, and O ions of 3+, 2+, 4+, and 2−, respectively.