Synthesis and characterization of nanolamellar tungsten and molybdenum disulfides

Tungsten and molybdenum disulfides were produced in direct self-sustained combustion in argon between elementary sulfur and metal (W, Mo) nanopowders prepared by electrical explosion of wires. The results of XRD analysis show that the main phases of the synthesized nanopowders are hexagonal WS₂ and MoS₂. According to SEM and TEM observations, they are agglomerated nanolamellar particles of thickness 40–150 nm and width 100–3000 nm.     

Microstructural characterisation of vacuum sintered T42 powder metallurgy high-speed steel after heat treatments

High-speed steel powders (T42 grade) have been uniaxially cold-pressed and vacuum sintered to full density. Subsequently, the material was heat treated following an austenitising + quenching + multitempering route or alternatively austenitising + isothermal annealing. The isothermal annealing route was designed in order to attain a hardness value of ～50 Rockwell C (HRC) (adequate for structural applications) while the multitempering parameters were selected to obtain this value and also the maximum hardening of the material (～66 HRC). Microstructural characterisation has been carried out by scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The microstructure consists of a ferrous (martensitic or ferritic) matrix with a distribution of second phase particles corresponding to nanometric and submicrometric secondary carbides precipitated during heat treatment together with primary carbides. The identification of those secondary precipitates (mainly M₃C, M₆C and M₂₃C₆ carbides) has allowed understanding the microstructural evolution of T42 high-speed steel under different processing conditions.     

Effect of heat treatment on morphology and thermal decomposition kinetics of multiwalled carbon nanotubes

High temperature treatment in inert atmosphere proved to be an effective way to improve high temperature stability of MWNTs in ambient condition. TEM analysis of heat-treated MWNTs confirmed successful removal of impurities and formation of ordered graphene layers and internal bamboo structure. TG–DTG curves indicated that decomposition range and rate of as-received MWNTs were narrow and notably higher, respectively, than heat-treated MWNTs mainly due to presence of impurities like metal nanoparticles in the former. Non-isothermal kinetic analysis revealed that the rate determining mechanism for as-received MWNTs was random nucleation and growth of active species. However, for heat-treated MWNTs, rate controlling mechanism was chemical reaction. Higher activation energies (～203 kJ mol^?1 and 280 kJ mol^?1) and reaction orders (3 and 4) of MWNTs heat-treated at 1200 °C and 1800 °C in inert, respectively, indicated delayed thermal decomposition than as-received MWNTs (E_a ≈ 178 kJ mol^?1; n = 1) even in oxidative atmosphere.     

Studies on the structural,electrical and magnetic properties of LaCrO3, LaCr0.5Cu0.5O3 and LaCr0.5Fe0.5O3 by sol–gel method

The structural, electrical and magnetic properties of LaCr_0.5M_0.5O₃ (M = Cr³⁺, Cu²⁺ and Fe³⁺) synthesized by a sol–gel technique were studied. The X-ray diffraction pattern shows the structure to be orthorhombic and the size of the particles is around 100 nm as seen from the TEM images. The effects of Cu²⁺ and Fe³⁺ on the electrical properties of LaCrO₃ were studied using impedance spectroscopy at room temperature (RT). The properties of LaCr_0.5Cu_0.5O₃ were studied over a wide range of temperature from RT to 533 K. A maximum conductivity of 1.7 × 10^?3 S cm^?1 was observed for LaCr_0.5Cu_0.5O₃ at a measured temperature of 533 K. The impedance spectra indicate a negative temperature coefficient of resistance (NTCR) and also imply the conduction is through bulk of the material. The magnetic studies performed using a SQUID magnetometer interpret the antiferromagnetically ordered LaCrO₃ to behave ferromagnetically on the addition of Cu²⁺ and Fe³⁺, and the magnetization was found to be enhanced in the LaCr_0.5Fe_0.5O₃.     

Mixture of fuels approach for the solution combustion synthesis of LaAlO3 nanopowders

A modified solution combustion approach was used in the preparation of nanosize LaAlO₃ (～23.6 nm) using mixture of citric acid and oxalic acid as fuels with corresponding metal nitrates. The synthesized and calcined powders were characterized by Fourier transform infra red spectrometry (FTIR), Differential thermal analysis-Thermogravimetry analysis (DTA–TGA), X-ray diffractometry (XRD) and Transmission electron microscopy (TEM). The FTIR spectra show the lower frequency bands at 656 and 442 cm^?1corresponds to metal–oxygen bonds (possible La–O and Al–O stretching frequencies) vibrations for the perovskite structure compound. DTA confirms the formation temperature of LaAlO₃ varies between 830–835 °C. XRD results show that mixture of fuels ratio is influential on the crystallite size of the resultant powders. The average particle size of LaAlO₃-1 as determined from TEM was about 41 nm, whereas for LaAlO₃-2 and LaAlO₃-3 samples, particles are seriously aggregated.     

Laser-tungsten inert gas hybrid welding of dissimilar metals AZ31B Mg alloys to Zn coated steel

Laser-tungsten inert gas (TIG) hybrid welding has been developed for joining Mg alloys to Zn coated steel in a lap joint configuration. The joint could not be produced in laser or arc welding only, while acceptable joints without obvious defects were obtained with a relatively wide processing window in the hybrid process. Two reaction layers were observed to form at the interface and were identified as Mg–Zn eutectic structure (α-Mg + MgZn) and Fe₃Al phase by TEM analysis. In some cases, Al₆Mn phase also formed adjacent to the Fe–Al reaction layer. The tensile-shear strength attained the maximum value of 68 MPa, representing 52.3% joint efficiency relative to Mg base metal. The element Al from AZ31B Mg alloys diffused to the liquid/solid interface and then reacted with the elements from steel, such as Fe and Mn, contributing to the metallurgical bonding at the interface. The weak bonding between Mg–Zn reaction layer and newly formed Fe–Al layer resulted in the interfacial failure.     

Microstructure,mechanical and corrosion properties of friction stir welded high nitrogen nickel-free austenitic stainless steel

Friction stir welding (FSW) was applied to a 2.4 mm thick high nitrogen nickel-free austenitic stainless steel plate using tungsten–rhenium (W–Re) tool. The high-quality weld was successfully produced at a tool rotational speed of 400 rpm and a traveling speed of 100 mm/min. The microstructure, mechanical and corrosion properties of the weld were studied. The nitrogen content of the weld was almost identical to that of base metal (BM). FSW refined grains in the stir zone (SZ) through dynamic recrystallization and led to increase in hardness and tensile strength within the SZ, while the ductility was slightly decreased. The failure of tensile specimens occurred in the BM. TEM results revealed precipitates of Cr₂₃C₆ of size ~ 1 μm in the SZ, although their content was small. The precipitation of Cr₂₃C₆ and increase in δ-ferrite in the SZ led to small decrease in both pitting and intergranular corrosion resistance.     

Characterization of M(H2PO4)2·2H2O (M = Mn,Co, Ni) and their in situ thermal decomposition by magnetic measurements

It has been established that M(H₂PO₄)₂·2H₂O (M = Mn, Co, Ni) are paramagnetics between 173 and 353 K with weak antiferromagnetic exchange interaction between the metal ions. In situ magnetic measurements during the thermal decomposition of the salts show that the oxidation state and the octahedral coordination of M²⁺ are preserved. From the data obtained it could be supposed that in M(H₂PO₄)₂·2H₂O (M = Co, Ni) this process is topotactic with no long-range diffusion transport. In Mn(H₂PO₄)₂·2H₂O, the formation of the large variety of intermediate products probably requires more drastic rearrangement and diffusion of the manganese ions during the complex transformations, which reflect on both the value and the sign of the θ constants. M₂P₄O₁₂ (M = Mn, Co, Ni), which are the final decomposition products of the corresponding dihydrogen phosphates are paramagnetics in the temperature range of 295–573 K with antiferomagnetic interactions between the metal ions. The lattice parameters of Ni(H₂PO₄)₂·2H₂O have been calculated. It crystallizes in the monoclinic system with a = 7.228(1) Å; b = 9.778(1) Å; c = 5.306(1) Å; β = 94.50(1)°, SG P2₁/n with Z = 2.     

Magnetic properties and transmission electron microscopy studies of Ni nanoparticles encapsulated in carbon nanocages and carbon nanotubes

Three types of carbon nanomaterials, including bamboo-shaped carbon nanotubes with Ni encapsulated and hollow and Ni catalytic particles filled carbon nanocages, have been prepared by methane catalytic decomposition at a relatively low temperature. Transmission electron microscopy observations showed that fascinating fullerene-like Ni–C (graphitic) core–shell nanostructures predominated. Detailed examination of high-resolution transmission electron microscopy showed that the walls of bamboo-shaped carbon nanotubes with quasi-cone catalytic particles encapsulated consisted of oblique graphene planes with respect to the tube axis. The Ni particles encapsulated in the carbon nanocages were larger than that encapsulated in carbon nanotubes, but the diameters of the cores of hollow carbon nanocages were less than that of Ni particles encapsulated in carbon nanotubes, suggesting that the sizes of catalyst particles played an important role during carbon nanomaterial growth. The magnetic properties of the carbon nanomaterials were measured, which showed relatively large coercive force (H_c = 138.4 O_e) and good ferromagnetism (M_r/M_s = 0.325).     

Fabrication of CuO/Fe2O3 hollow hybrid microspheres

CuO/Fe₂O₃ hollow hybrid spheres with the size of 3–5 μm were successfully synthesized by a convenient hydrothermal method, using FeSO₄·7H₂O and CuSO₄·5H₂O as the starting materials and urea as the homogeneous precipitant. The samples were characterized by XRD, TEM, ED, SEM, EDX, IR and XPS measurements. XRD and XPS analyses indicated that the nanostructured materials consisted of CuO and α-Fe₂O₃. TEM and SEM measurements showed that the morphology of binary metal oxide was in the shape of hollow sphere. Careful observation from SEM measurements could find that CuO/Fe₂O₃ hollow microsphere shell was composed of uniform and dense metal oxide nanorods with about 20–40 nm in diameter and 100–200 nm in length. Moreover, the influence of calcination temperature on the thermal stability of the hollow structures was investigated. It showed that the hollow structure was stable after being calcined at 300 °C for 2 h. The formation mechanism of the CuO/Fe₂O₃ hollow spheres under hydrothermal condition was discussed.     

Microstructure and mechanical behaviors of electron beam welded NiTi shape memory alloys

The vacuum electron beam welding (EBW) technique was employed to weld Ni_50.8Ti_49.2 shape memory alloy sheets, and the microstructure, transformation behaviors and mechanical behaviors of the welding joints were investigated systematically. The microstructure observation showed that the weld seam was composed of coarse columnar crystals at the center and relatively fine columnar crystals near the fusion line. The abnormal high intensity of B2_2 0 0 peak in XRD patterns and preferred orientation in EBSD indicated that the grains in the weld seam have grown preferentially along the 〈1 0 0〉 crystal orientation. Differential scanning calorimetry (DSC) curves exhibited an increase of the martensite start temperature (M_s) of the weld seam, which led to the mixed microstructure of martensite and austenite at room temperature. As a result, the ultimate tensile strength of the welding joint was 85% as high as that of the base metal at room temperature, while it could reach 93% at 223 K when both the weld seam and the base metal were in pure martensitic state.     

Effect of 10Ce-TZP/Al2O3 nanocomposite particle amount and sintering temperature on the microstructure and mechanical properties of Al/(10Ce-TZP/Al2O3) nanocomposites

A zirconia/alumina nanocomposite stabilized with cerium oxide (Ce-TZP/Al₂O₃ nanocomposite) can be a good substitute as reinforcement in metal matrix composites. In the present study, the effect of the amount of 10Ce-TZP/Al₂O₃ particles on the microstructure and properties of Al/(10Ce-TZP/Al₂O₃) nanocomposites was investigated. For this purpose, aluminum powders with average size of 30 μm were ball-milled with 10Ce-TZP/Al₂O₃ nanocomposite powders (synthesized by aqueous combustion) in varying amounts of 1, 3, 5, 7, and 10 wt.%. Cylindrical-shape samples were prepared by pressing the powders at 600 MPa for 60 min while heating at 400–450 °C. The specimens were then characterized by scanning and transmission electron microscopy (SEM and TEM) in addition to different physical and mechanical testing methods in order to establish the optimal processing conditions. The highest compression strength was obtained in the composite with 7 wt.% (10Ce-TZP/Al₂O₃) sintered at 450 °C.     

The effects of Ta on the stress rupture properties and microstructural stability of a novel Ni-base superalloy for land-based high temperature applications

A novel polycrystalline Ni-base superalloy was developed for land-based high temperature applications, such as isothermal forging dies and industrial gas turbines. The alloy possessed surprisingly high stress rupture life of 52 h at 1100 °C/118 MPa which is comparable to the first generation single crystal (SC) superalloy and exhibited good microstructural stability. The effects of Ta addition on the phase change, stress rupture properties and microstructural stability of the alloy were investigated. The results indicated that Ta is a γ′-former and promotes the formation of eutectic γ′. The alloys with ∼7 vol.% eutectic γ′ possess higher stress rupture life at 1100 °C/118 MPa than the alloys with higher ∼20 vol.% eutectic. However, ∼20 vol.% excessive eutectic phases will enhance the stress rupture life at intermediate temperature of 760 °C for 686 MPa but weaken high temperature stress rupture properties. The (Al + Ta) content over 14.4 at.% led to the formation of large amounts of eutectic γ′ and exceeded the solubility of W and Mo in the residue liquid pool, which then promoted the precipitation of primary α-(W,Mo) and M₆C phases. Tantalum was also found as a strong MC carbides forming element. The order of ability to form monocarbide decreased from NbC to TaC to TiC. 6Al–0Ta (wt.%) alloys possessed good microstructural stability with no harmful topologically close-packed (TCP) phases being observed after thermal exposure at 850 °C/3000 h, 900 °C/1000 h. Only trace amounts of secondary plate-like M₆C carbides appeared in Ta-free and 5Al–4Ta (wt.%) alloys at 1100 °C/100–500 h. However, excessive Ta addition will destabilize the alloy and large amounts of secondary plate-like M₆C carbides precipitated after thermal exposure at 1100 °C. The transmission electron microscopy (TEM) and selected area electron diffraction (SAED) results showed the existence of the plate-like M₆C carbides.     

Crystal structure,oxygen permeability and stability of Ba0.5Sr0.5Co0.8Fe0.1M0.1O3−δ (M = Fe,Cr, Mn,Zr) oxygen-permeable membranes

Oxygen-permeable ceramic membrane materials of the Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3−δ (BSCFO) and partially Fe-substituted Ba_0.5Sr_0.5Co_0.8Fe_0.1M_0.1O_3−δ (M = Cr, Mn, Zr) were synthesized by solid-state reaction method. These materials possess purely cubic perovskite structure with the exception of Ba_0.5Sr_0.5Co_0.8Fe_0.1M_0.1O_3−δ (M = Mn, Zr), in which minor impurities exist. Oxygen permeability across these dense membrane disks were measured under an air/He oxygen partial pressure gradient in the temperature range of 973–1123 K. The results demonstrated that the oxygen permeation fluxes of the Ba_0.5Sr_0.5Co_0.8Fe_0.1M_0.1O_3−δ (M = Fe, Cr, Mn, Zr) membranes increased in the following order: Fe (BSCFO) > Cr > Zr > Mn. The corresponding activation energies for oxygen permeation of Ba_0.5Sr_0.5Co_0.8Fe_0.1M_0.1O_3−δ (M = Fe, Cr, Zr) membranes were calculated to be similar (53 ± 4 kJ/mol), which was remarkably lower than that (99 ± 3 kJ/mol) of Ba_0.5Sr_0.5Co_0.8Fe_0.1M_0.1O_3−δ (M = Mn) membrane. In addition, good oxygen permeation stability of the Ba_0.5Sr_0.5Co_0.8Fe_0.1M_0.1O_3−δ (M = Cr) membrane was achieved at the temperature lower than 1123 K. The X-ray diffraction (XRD) and differential thermal analysis (DTA) experiments showed that the structural stability of BSCFO could be significantly improved when Fe ions in the BSCFO material were partially substituted by Cr, Mn or Zr ions.     

Sol–gel derived Cr(III) and Cu(II)/γ-Al2O3 doped solids: Effect of the dopant precursor nature on the structural,textural and morphological properties

Powders of xerogel γ-Al₂O₃ doped with various concentrations of Cr³⁺ and Cu²⁺ (M/M + Al molar fraction = 0.75–10%) were prepared via a sol–gel method. Cr³⁺ and Cu²⁺ precursors (acetylacetonate, nitrate or chloride) were added to 0.12 M 2-propanol solution of aluminum tri-sec-butoxide (ASB) and hydrolysis was performed using a H₂O/ASB molar ratio of 4.7. The effect of the dopant precursor on structural, textural and morphological properties was studied. Employing acac precursors resulted in unique properties after calcination at 500 °C including high surface areas, as high as 455 m²/g, homogeneous mesopores, 3–12 nm, and amorphous powders (5–10 nm particles in diameter). On the other hand, the acac precursor enhanced the resistance to sintering mainly at higher metal loads (10%) and elevated temperature (800 °C). Nevertheless, the solids issued from nitrate and chloride precursors exhibited lower surface areas at high metal loads, and lower resistance to sintering.     

Synthesis of submicron B4C by mechanochemical method

Synthesis of boron carbides by the reduction of boron oxides with carbon and magnesium in mechanical alloying process using a planetary ball mill has been studied. XRD, EPMA and TEM have been used to characterize the product and the results showed submicron B₄C particles were obtained at the mass ratio of ball to load about 5 : 1 and the mass ratio of B₂O₃ : C : Mg about 10 : 1 : 11.     

Sugar response of boronic acid-substituted azobenzene dye-modified polymer

We synthesized a boronic acid-appended azobenzene dye (BA) and attached it to poly(ethyleneimine) (polyBA) for studying its sugar response. The addition of d-glucose induced a significant change in the UV–visible absorption spectra of the polyBA solution. The binding constants for d-glucose (K_glu) and d-fructose (K_fru) were calculated to be 54 M^? 1 and 110 M^? 1, respectively. The selectivity for d-glucose was higher in polyBA as compared with that of monomeric BA (K_glu = 1.2 M^? 1, K_fru = 17 M^? 1). We also fabricated multilayered films composed of polyBA and polyanions {poly(vinyl sulfate) (PVS), carboxymethylcellulose (CMC)} using a layer-by-layer deposition technique. In (PVS/polyBA)₁₀ films, the affinity for d-glucose was relatively low (K_glu = 1.7 M^? 1, K_fru = 28 M^? 1). In contrast, (CMC/polyBA)₅ films showed a high affinity for d-glucose (K_glu = 18 M^? 1, K_fru = 42 M^? 1). The loosely packed structure of the (CMC/polyBA)₅ film and the suitable chemical structures of CMC probably led to a high affinity for d-glucose.     

Low temperature synthesis of nanocrystalline calcium aluminate compounds with surfactant-assisted precipitation method

Nanocrystalline calcium aluminates with different CaO:Al₂O₃ and surfactant/metal ion molar ratios were prepared by wet chemical synthesis method using Poly (ethylene glycol)-block-poly(propylene glycol)-block poly(ethylene glycol) (PEG–PPG–PEG, MW:5800) as surfactant. X-ray diffraction (XRD) and N₂ adsorption–desorption results showed that the increase in CaO:Al₂O₃ ratio decreased the specific surface area and increased the particle sizes of prepared samples while the surfactant/metal ion molar ratios were kept constant. These analyses also declared that for the sample with CaO:Al₂O₃ = 1:2 (CA2) addition of polymeric surfactant increased the specific surface area and decreased the crystallite size. Scanning electron microscopy (SEM) results confirmed that size of particles for CaO:Al₂O₃ = 1:6 (CA6) sample are smaller than CA2. Transmission electron microscopy (TEM) revealed no particular particle shape for the CA2 sample but it showed the high degree of crystallinity and single phase for the prepared sample at 1100 °C.     

Preparation,characterization and photocatalytic properties of terbium orthoferrite nanopowder

Perovskite-type terbium orthoferrite (TbFeO₃) nanopowder was synthesized through a polyacrylamide gel route. The as-synthesized particles were characterized by XRD, TEM, BET surface area, UV–visible absorption spectroscopy, and XPS. It is shown that the particles are uniformly and regularly shaped like spheres with an average size of ～50 nm, and have a BET specific surface area of 15.4 m² g^?1. The optical energy bandgap of the nanosized TbFeO₃ is obtained to be 1.98 eV. The photocatalytic activity of the TbFeO₃ particles was evaluated by the photodegradation of various organic dyes including methyl orange (MO), rhodamine B (RhB), methylene blue (MB), acid fuchsine (AF), and congo red (CR). It is demonstrated that the product exhibits a pronounced photocatalytic degradation of the dyes under visible-light irradiation. The photocatalytic efficiency is observed to depend on the dye type, and under the present experimental conditions it follows the sequence: CR > AF > MB > RhB > MO.     

Synthesis of aluminium nanoparticles by arc plasma spray under atmospheric pressure

The present study addresses the feasibility to synthesize aluminium nanoparticles (NPs) from micron-sized aluminium powder with the use of a customized atmospheric plasma spraying (APS) technique. Using APS, nanoparticle synthesis can be achieved via rapid melting and vaporization of the initial micrometric particles and their subsequent re-nucleation. A custom mantle system was designed and developed with the aid of relevant simplified CFD simulations. The mantle provided the necessary inert environment (argon), at ambient pressure, in order to avoid any oxidation of the metal during plasma spraying while promoted rapid quenching of the gasified metal. The particles formed were collected with the aid of a quartz filter downstream of the plasma flame and the production rate achieved was 2 g min^?1. Ex situ post-characterization of the particles via X-ray diffraction, specific surface area measurement (BET), transmission electron microscopy (TEM) coupled with energy dispersive spectrometry (EDS) and thermogravimetric analysis (TGA) under air revealed that the powders obtained primarily comprised of monocrystalline metallic aluminium nanoparticles of almost spherical shape. The NPs possessed a 2–5 nm oxide coating layer. By regulating the conditions inside the mantle, a variety of different size distributions were obtained.