Field emission enhancement of carbon nitride films by annealing with different durations

Magnetron sputtered carbon nitride films (CN_x) were annealed at 750 °C for periods from 30 to 120 min. Effects of annealing with different durations on the field emission of CN_x films were investigated and related to the variations of chemical bonding and surface morphology induced by annealing. The results show that annealing effectively enhances field emission ability of the CN_x films and that the threshold field was lowered from 13 to 5 V/μm. The measurements of Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM) indicated that annealing leads to a loss of N content and to formation of more graphite-like sp² C clusters in the films, and simultaneously the film surface becomes rougher after annealing, all of which is attributed to the increased film field emission. A large number of sp² C clusters with good conductivity enables tunneling in the film, making electron emission easier, and moreover, a rougher surface also improves the field enhancement factor of the films. However, continuing to increase annealing time eventually lowers the field emission of the films.     

Effects of high temperature treatment on microstructure and mechanical properties of laser-clad NiCrBSi/WC coatings on titanium alloy substrate

Laser-clad composite coatings on the Ti6Al4V substrate were heat-treated at 700, 800, and 900 °C for 1 h. The effects of post-heat treatment on the microstructure, microhardness, and fracture toughness of the coatings were investigated by scanning electron microscopy, X-ray diffractometry, energy dispersive spectroscopy, and optical microscopy. The wear resistance of the coatings was evaluated under dry reciprocating sliding friction at room temperature. The coatings mainly comprised some coarse gray blocky (W,Ti)C particles accompanied by the fine white WC particles, a large number of black TiC cellular/dendrites, and the matrix composed of NiTi and Ni₃Ti; some unknown rich Ni- and Ti-rich particles with sizes ranging from 10 nm to 50 nm were precipitated and uniformly distributed in the Ni₃Ti phase to form a thin granular layer after heat treatment at 700 °C. The granular layer spread from the edge toward the center of the Ni₃Ti phase with increasing temperature. A large number of fine equiaxed Cr₂₃C₆ particles with 0.2–0.5 μm sizes were observed around the edges of the NiTi supersaturated solid solution when the temperature was further increased to 900 °C. The microhardness and fracture toughness of the coatings were improved with increased temperature due to the dispersion-strengthening effect of the precipitates. Dominant wear mechanisms for all the coatings included abrasive and delamination wear. The post-heat treatment not only reduced wear volume and friction coefficient, but also decreased cracking susceptibility during sliding friction. Comparatively speaking, the heat-treated coating at 900 °C presented the most excellent wear resistance.     

Evaluation of microstructures and mechanical properties of diamond like carbon films deposited by filtered cathodic arc plasma

Diamond-like carbon (DLC) films were deposited by a cathodic arc plasma evaporation (CAPD) process, using a mechanical shield filter combined with a magnetic filter with enhanced arc structure at substrate-bias voltage ranging from − 50 to − 300 V. The film characteristics were investigated using Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM) and high-resolution transmission electron microscopy (HRTEM). The mechanical properties were investigated by using a nanoindentation tester, scratch test and ball on disc wear test. The Raman spectra of the films showed that the wavenumber ranging from 900 to 1800 cm^− 1 could be deconvoluted into 1140 cm^− 1, D band and G band. The bias caused a significant effect on the sp³ content which was increased with the decreasing of I_D/I_G ratio. The XPS spectra data of the films which were etched by H⁺ plasma indicated the sp³ content are higher than those of the as-deposited DLC films. This implied that there is a sp²-rich layer present on the surface of the as-deposited DLC films. The nanoindentation hardness increased as the maximum load increased. A 380 nm thick and well adhered DLC film was successfully deposited on WC-Co substrate above a Ti interlayer. The adhesion critical load of the DLC films was about 33 N. The results of the wear tests demonstrated that the friction coefficient of the DLC films was between 0.12 and 0.2.     

Photoluminescent properties of Eu3+ doped electrospun CeO2 nanofibers

In this study, CeO₂ nanofibers and that doped with Eu³⁺ were prepared via a facile electrospinning route and annealed at different temperatures ranging from 500 to 900 °C. Their structures were investigated using X-ray diffraction, scanning electron microscopy and transmission electron microscopy. Photoluminescence properties of the nanofibers were studied in detail. It was found that the nanofibers with Eu% concentration of 0.67 mol.% and annealed at 700 °C exhibited the highest intensities of the luminescence peaks between 550 and 650 nm.     

Experimental investigation and thermodynamic calculation of the phase equilibria in the Cu–Mo–Ni ternary system

The phase equilibria at 900 °C, 1000 °C, 1100 °C, 1200 °C and 1300 °C in the Cu–Mo–Ni system were experimentally determined by means of optical microscopy (OM), electron probe microanalyzer (EPMA) and X-ray diffraction (XRD) on the equilibrated alloys. The experimental results firstly found that the fcc-type miscibility gap exists at 900 °C, 1000 °C, 1100 °C and 1200 °C in the Cu–Mo–Ni system, and the solubility of Cu in the MoNi phase at 900 °C, 1000 °C, 1100 °C and 1200 °C are about 0.5 at.%, 1.5 at.%, 1.7 at.% and 4.0 at.%, respectively. The as-cast Cu₂₀Mo₂₀Ni₆₀ (at.%), Cu₂₀Mo₃₀Ni₅₀ (at.%), Cu₁₀Mo₆₀Ni₃₀ (at.%), Cu₇₀Mo₁₀Ni₆₀ (at.%), Cu₂₀Mo₆₀Ni₂₀ (at.%) and Cu₈₀Mo₁₀Ni₁₀ (at.%) alloys appear the separated macroscopic morphologies, which are caused by the liquid phase separation on cooling, while the as-cast Cu₁₀Mo₂₅Ni₆₅ (at.%), Cu₃₂Mo₅Ni₆₃ (at.%) and Cu_30.7Mo_6.3Ni₆₃ (at.%) alloys show the homogenous microscopic morphologies. On the basis of the experimental data investigated by the present and previous works, the phase equilibria in the Cu–Mo–Ni system were thermodynamically assessed by using CALPHAD (Calculation of Phase Diagrams) method, and a consistent set of the thermodynamic parameters leading to reasonable agreement between the calculated results and experimental data was obtained.     

Effects of strain amplitude and temperature on the damping capacity of an Fe-19Mn alloy with different microstructures

The influences of strain amplitude (10^?5–10^?4) and temperature (25 °C–500 °C) on the internal friction of a cold-drawn and solution treated Fe-19Mn alloy were investigated. The internal friction was measured using reversal torsion pendulum and multifunction internal friction equipment. The microstructure was observed using scanning electron microscopy. The phase transformation temperatures were determined using differential scanning calorimetry. The results indicated that the internal friction of the solution treated alloy was related to strain amplitude, which could be explained using the movement of Shockley partial dislocations (bowing out and breaking away). But the internal friction of the cold-drawn alloy was independent of strain amplitude because of high density dislocations formed by cold forming. Moreover, when the temperature was changed between 25 °C and 500 °C, the internal friction of the cold-drawn alloy increased slowly from 25 °C to 375 °C, and then increased quickly from 375 °C to 500 °C. However, for the solution treated alloy, there was an internal friction peak at about 210 °C in the heating process (from 25 °C to 500 °C), and there was another internal friction peak at about 150 °C in the cooling process. These peaks could be explained using the heat-assisted movement of dislocations.     

Preparation and electrochemical characterization of lithium cobalt oxide nanoparticles by modified sol–gel method

Uniformly distributed nanoparticles of LiCoO₂ have been synthesized through the simple sol–gel method in presence of neutral surfactant (Tween-80). The powders were characterized by X-ray diffractometry, transmission electron microscopy and electrochemical method including charge–discharge cycling performance. The powder calcined at a temperature of 900 °C for 5 h shows pure phase layered LiCoO₂. The results show that the particle size is reduced in presence of surfactant as compared to normal sol–gel method. Also, the sample prepared in presence of surfactant and calcined at 900 °C for 5 h shows the highest initial discharge capacity (106 mAh g^?1) with good cycling stability as compared to the sample prepared without surfactant which shows the specific discharge capacity of 50 mAh g^?1.     

Annealing effect on the microstructure and photoluminescence of ZnO thin films

Zinc oxide thin films have been obtained by pulsed laser ablation of a ZnO target in O₂ ambient at a pressure of 0.13 Pa using a pulsed Nd:YAG laser. ZnO thin films deposited on Si (1 1 1) substrates were treated at annealing temperatures from 400 °C up to 800 °C after deposition. The structural and optical properties of deposited thin films have been characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, photoluminescence spectra, resistivity and IR absorption spectra. The results show that the obtained thin films possess good single crystalline with hexagonal structure at annealing temperature 600 °C. Two emission peaks have been observed in photoluminescence spectra. As the post-annealing temperature increase, the UV emission peaks at 368 nm is improved and the intensity of blue emission at 462 nm decreases, which corresponds to the increasing of the optical quality of ZnO film and the decreasing of Zn interstitial defect, respectively. The best optical quality for ZnO thin films emerge at post-annealing temperature 600 °C in our experiment. The measurement of resistivity also proves the decrease of defects of ZnO films. The IR absorption spectra of sample show the typical Zn–O bond bending vibration absorption at wavenumber 418 cm⁻¹.     

Effect of substrate temperature on the properties of pyrolytically deposited nitrogen-doped zinc oxide thin films

The effect of substrate temperature (T_s) on the properties of pyrolytically deposited nitrogen (N) doped zinc oxide (ZnO) thin films was investigated. The T_s was varied from 300 °C to 500 °C, with a step of 50 °C. The positive sign of Hall coefficient confirmed the p-type conductivity in the films deposited at 450 °C and 500 °C. X-ray diffraction studies confirmed the ZnO structure with a dominant peak from (1 0 0) crystal plane, irrespective of the variation in T_s. The presence of N in the ZnO structure was evidenced through X-ray photoelectron spectroscopy (XPS) analysis. The obtained high N concentration reveals that the 450 °C is the optimal T_s. Atomic force microscope (AFM) analysis showed that the surface roughness was increased with the increasing T_s until 400 °C but then decreased. It is found that the transmittance of the deposited films is increased with the increasing T_s. The optical band gap calculated from the absorption edge showed that the films deposited with T_s of 300 °C and 350 °C possess higher values than those deposited at higher T_s.     

Solution combustion synthesis of LiMn2O4 fine powders for lithium ion batteries

In this work, fine powders of spinel-type LiMn₂O₄ as cathode materials for lithium ion batteries (LIBs) were produced by a facile solution combustion synthesis using glycine as fuel and metal nitrates as oxidizers. Single phase of LiMn₂O₄ products were successfully prepared by SCS with a subsequent calcination treatment at 600–1000 °C. The structure and morphology of the powders were studied in detail by X-ray diffraction, scanning electron microscopy and transmission electron microscopy. The electrochemical properties were characterized by galvanostatic charge–discharge cycling and cyclic voltammetry. The crystallinity, morphology, and size of the products were greatly influenced by the calcination temperature. The sample calcined at 900 °C had good crystallinity and particle sizes between 500 and 1000 nm. It showed the best performance with an initial discharge capacity of 115.6 mAh g⁻¹ and a capacity retention of 93% after 50 cycles at a 1 C rate. In comparison, the LiMn₂O₄ sample prepared by the solid-state reaction showed a lower capacity of around 80 mAh g⁻¹.     

Effects of post-annealing on the microstructure and mechanical properties of friction stir processed Al–Mg–TiO2 nanocomposites

Aluminum matrix nanocomposites were fabricated via friction stir processing of an Al–Mg alloy with pre-inserted TiO₂ nanoparticles at different volume fractions of 3%, 5% and 6%. The nanocomposites were annealed at 300–500 °C for 1–5 h in air to study the effect of annealing on the microstructural changes and mechanical properties. Microstructural studies by scanning and transmission electron microscopy showed that new phases were formed during friction stir processing due to chemical reactions at the interface of TiO₂ with the aluminum matrix alloy. Reactive annealing completed the solid-state reactions, which led to a significant improvement in the ductility of the nanocomposites (more than three times) without deteriorating their tensile strength and hardness. Evaluation of the grain structure revealed that the presence of TiO₂ nanoparticles refined the grains during friction stir processing while the in situ formed nanoparticles hindered the grain growth upon the post-annealing treatment. Abnormal grain growth was observed after a prolonged annealing at 500 °C. The highest strength and ductility were obtained for the nanocomposites annealed at 400 °C for 3 h.     

The tribological behavior of W–S–C films in pin-on-disk testing at elevated temperature

W–S–C films were deposited by magnetron sputtering in an Ar atmosphere with a Ti interlayer. A carbon target with several pellets of WS₂ incrusted in the zone of the preferential erosion was used. The number of pellets was changed to modify the carbon content in the films, which varied from 29 up to 70 at%. Doping W–S films with carbon led to a substantial increase of the hardness in the range 4–10 GPa; the maximum of hardness was obtained for coatings with the carbon content of 40 at%. X-ray diffraction (XRD) patterns showed that there was a loss of crystallinity with the increase of the carbon content in the film.The coatings were tested by pin-on-disk from room temperature (RT) up to 400 °C. At RT, the friction coefficient was in the range 0.2–0.30. At temperatures higher than 100 °C, the friction is below 0.05 for all compositions. The tribological behavior of the coatings with increasing temperatures depended on the films carbon content. For low-carbon content up to 40%, the wear rate was almost independent of the temperature up to 300 °C, while it increased dramatically in the case of the coatings with high-carbon content. In general, the limiting temperature for W–S–C coatings is 400 °C.     

Effects of rare-earth concentration and heat-treatment on the structural and luminescence properties of europium-doped zirconia sol–gel planar waveguides

Sol–gel zirconia films doped with Eu³⁺ concentrations ranging from 0.2% to 10%, were prepared by dip-coating a solution of the starting precursor, zirconium n-propoxide, ethanol, methanol, water, acetic acid and europium nitrate on glass and SiO₂/Si wafer substrates. The ZrO₂ sol thus synthesized remains stable for several months. Structural characterization of the zirconia films was performed using Waveguide Raman Spectroscopy. These films present an amorphous phase up to an annealing temperature of 400 °C. Above 400 °C the matrix evolves towards a metastable tetragonal phase. This transformation was found to depend on the concentration of Eu³⁺ ions. Indeed, while for samples doped with 0.2% Eu³⁺ this transformation occurs around 450 °C, in the case of 10% of Eu³⁺ ions, the transition is pushed off to 500 °C. The optical losses of these waveguides were found to be about 0.3 dB cm⁻¹ for samples annealed at 400 °C. The surfaces of the films were characterized using Atomic Force Microscopy and the roughness was measured. The Eu-doped films were investigated using Waveguide Photoluminescence Spectroscopy. The dynamical behaviour of the Eu³⁺ emissions indicated that concentration quenching effect is not observed even when the matrix is doped up to 10%.     

The effects of annealing temperature on characteristics of UBMS sputtered CNx films for protective coatings

The carbon nitride (CNx) films have been prepared by unbalanced magnetron sputtering (UBMS) at room temperature. The deposited CNx films have been post-annealed at temperatures ranging from 300 °C to 700 °C in increments of 200 °C using rapid thermal annealing (RTA) equipment in vacuum ambient. We investigated the effects of rapid thermal annealing on the structural, surface, and physical properties of CNx films for application of protective coatings. As the result, the increasing annealing temperature led to a decline in physical properties of CNx films such as hardness, elastic modulus, adhesion, frication coefficient, and surface roughness, however it is attributed to the improvement of the residual stress in the film. These results are related to the ordering of sp² bonded clustering and the increase of disordered graphite domain by the desorption of N contents in the films, Specially, high annealing temperature over 700 °C is attributed to the graphitization of film.     

Synthesis of TiO2 thin films using single molecular precursors by MOCVD method for dye-sensitized solar cells application and study on film growth mechanism

For dye-sensitized solar cells application, in this study, we have synthesized TiO₂ thin films at deposition temperature in the range of 300–750 °C by metalorganic chemical vapor deposition (MOCVD) method. Titanium(IV) isopropoxide, {TIP, Ti(OⁱPr)₄} and Bis(dimethylamido)titanium diisopropoxide, {BTDIP, (Me₂N)₂Ti(OⁱPr)₂} were used as single source precursors that contain Ti and O atoms in the same molecule, respectively. Crack-free, highly oriented TiO₂ polycrystalline thin films with anatase phase were deposited on Si(1 0 0) with TIP at temperature as low as 450 °C. XRD and TED data showed that below 500 °C, the TiO₂ thin films were dominantly grown in the [2 1 1] direction on Si(1 0 0), whereas with increasing the deposition temperature to 700 °C, the main film growth direction was changed to [2 0 0]. Above 700 °C, however, rutile phase TiO₂ thin films have only been obtained. In the case of BTDIP, on the other hand, only amorphous film was grown on Si(1 0 0) below 450 °C while a highly oriented anatase TiO₂ film in the [2 0 0] direction was obtained at 500 °C. With further increasing deposition temperatures over 600 °C, the main film growth direction shows a sequential change from rutile [1 0 1] to rutile [4 0 0], indicating a possibility of getting single crystalline TiO₂ film with rutile phase. This means that the precursor together with deposition temperature can be one of important parameters to influence film growth direction, crystallinity as well as crystal structure. To investigate the CVD mechanism of both precursors in detail, temperature dependence of growth rate was also carried out, and we then obtained different activation energy of deposition to be 77.9 and 55.4 kJ/mol for TIP and BTDIP, respectively. Also, we are tested some TiO₂ film synthesized with BTDIP precursor to apply dye-sensitized solar cell.     

Dependence of dynamic strain ageing on strain amplitudes during the low-cycle fatigue of TP347H austenitic stainless steel at 550 °C

Low-cycle fatigue (LCF) tests are carried out on TP347H stainless steel at a strain rate of 8 × 10⁻³ s⁻¹ with total strain amplitudes (Δε_t/2) of ±0.4% and ±1.0%, at room temperature (RT) and 550 °C. It is found that the stress responses and dislocation structures under cyclic loading strongly depend on the value of strain amplitude at 550 °C. Compared with those at the same strain amplitude at RT, the material shows a rapid strain softening, and finally attains a stabilized state at Δε_t/2 = ±0.4% and 550 °C, but the one presents an anomalous behavior, i.e., first a rapid hardening to the maximum stress, followed by a reducing softening at Δε_t/2 = ±1.0% and 550 °C. More cells resulting from dislocation cross-slip and planar structures due to dynamic strain ageing (DSA) restricting cross-slip develop at low strain amplitude of ±0.4% at the first cycle. However, there are more complicated dislocation structures, such as cells, elongated cells, walls/channels and planar structures at Δε_t/2 = ±1.0%. The observations of scanning electron microscopy (SEM) and transmission electron microscopy (TEM) exclude the effects of martensitic transformation, creep, oxidation, and precipitations on these stress responses and microstructure evolutions, which result from DSA appearing at 550 °C.     

Study of annealing time on sol–gel indium tin oxide films on glass

Indium and tin salt-based precursors maintaining In:Sn atomic ratio as 90:10 were utilized for the development of sol–gel dip coated indium tin oxide films (ITO) on SiO₂ coated (∼ 200 nm thickness) soda lime silica glass substrate. The gel films were initially cured in air at ∼ 450 °C to obtain oxide films of physical thickness ∼ 250 nm. These were then annealed in 95% Ar–5% H₂ atmosphere at ∼ 500 °C. The annealing time was varied from 0.5 h to 5 h. Variation of annealing time did not show any considerable change of transmittance in the visible region. Thermal emissivity (ε_d, 0.67–0.79) of the films were evaluated from their hemispherical spectral reflectance. These passed through a minima with increasing annealing time as the reflectivity of the films in the mid-IR passed through a maxima. The microstructure of the films revealed systematic growth of the ITO grains. XRD and XPS studies revealed the presence of both In and Sn metals in addition to the metal oxides. The energy dispersive X-ray (EDX) analysis showed little lowering of tin content in the films with increasing annealing time.     

Epitaxial growth of non-polar m-plane ZnO thin films by pulsed laser deposition

Non-polar ZnO thin films were deposited on m-plane sapphire substrates by pulsed laser deposition at various temperatures from 300 to 700 °C. The effects of growth temperature on surface morphology, structural, electrical, and optical properties of the films were investigated. All the films exhibited unique m-plane orientation indicated by X-ray diffraction and transmission electron microscopy. Based on the scanning electron microscopy and atomic force microscopy, the obtained films had smooth and highly anisotropic surface, and the root mean square roughness was less than 10 nm above 500 °C. The maximum electron mobility was ～18 cm²/V s, with resistivity of ～0.26 Ω cm for the film grown at 700 °C. Room temperature photoluminescence of the m-plane films was also investigated.     

Spray pyrolysis deposition of nanostructured zirconia thin films

Polycrystalline zirconia thin films were obtained on silica substrates by the spray pyrolysis technique using a water/isopropanol solution of a precursor containing zirconium in the form of an anionic oxalate complex. The as-deposited products were amorphous. Crystallization with formation of homogeneous dense nanostructured cubic zirconia thin films occurred after heat-treatment in air at temperatures T=500–700 °C. In the range 700–1000 °C both cubic and monoclinic zirconia was present in the films, the C-ZrO₂ content decreasing with temperature rise. Penetration of SiO₂ from the silica substrate was registered in the films by X-ray photoelectron spectroscopy (XPS). A severe attack of the substrate by zirconia resulting in formation of ZrSiO₄ was observed after annealing of the film at 1100 °C.     

Fabrication of HAp–8YSZ composite layer on Ti/TiO2 nanoporous substrate by EPD/MAO method

Zirconia/Hydroxyapatite composites containing 20–50 wt.% 8YSZ were prepared on Ti/TiO₂ substrates by electrophoretic deposition (EPD)/micro-arc oxidation (MAO) process. Titania, as an inner layer, was grown on the Ti plates using MAO treatment in order to form a strong join between substrate and HAp. These composites were produced by EPD in ethanol containing ZrO₂/HAp particles at 50, 100 and 150 V in 1 min. As-prepared samples were sintered at 900, 1100 and 1300 °C. HAp, β-TCP, CaZrO₃ phases were identified using X-ray diffractometry analysis (XRD). Scanning electron microscopy (SEM) utilized to study the surface morphology indicated a crack free microstructure at 1300 °C.