Low-energy EDX – A novel approach to study stress corrosion cracking in SUS304 stainless steel via scanning electron microscopy

Intergranular stress corrosion cracking (IGSCC) in type SUS304 stainless steels, tested under pressurized water reactor (PWR) primary water conditions, has been characterized with unprecedented spatial resolution using scanning electron microscopy (SEM) and novel low-energy (∼3 kV) energy dispersive X-ray spectroscopy (EDX). An advancement of the large area silicon drift detector (SDD) has enhanced its sensitivity for X-rays in the low-energy part of the atomic spectrum. Therefore, it was possible to operate the SEM at lower accelerating voltages in order to reduce the interaction volume of the beam with the material and achieve higher spatial resolution and better signal-to-noise ratio. In addition to studying the oxide chemistry at the surface of intergranular stress corrosion cracks, the technique has proven capable of resolving Ni enrichment ahead of some crack tips. Active cracks could be distinguished from inactive ones due to the presence of oxides in the open crack and Ni-rich regions ahead of the crack tip. Furthermore, it has been established that SCC features can be better resolved with low-energy (3 kV) than high-energy (12 kV) EDX. The low effort in sample preparation, execution and data analysis makes SEM the ideal tool for initial characterization and selection of the most important SCC features such as dominant cracks and interesting crack tips, later to be studied by transmission electron microscopy (TEM) and atom probe tomography (APT).     

Application of indium tin oxide (ITO) thin film as a low emissivity film on Ni-based alloy at high temperature

Indium tin oxide (ITO) films as the low emissivity coatings of Ni-based alloy at high temperature were studies. ITO films were deposited on the polished surface of alloy K424 by direct current magnetron sputtering. These ITO-coated samples were heat-treated in air at 600–900 °C for 150 h to explore the effect of high temperature environment on the emissivity. The samples were analyzed by X-ray diffraction (XRD), SEM and EDS. The results show that the surface of sample is integrity after heat processing at 700 °C and below it. A small amount of fine crack is observed on the surface of sample heated at 800 °C and Ti oxide appears. There are lots of fine cracks on the sample annealed at 900 °C and a large number of various oxides are detected. The average infrared emissivities at 3–5 μm and 8–14 μm wavebands were tested by an infrared emissivity measurement instrument. The results show the emissivity of the sample after annealed at 600 and 700 °C is still kept at a low value as the sample before annealed. The ITO film can be used as a low emissivity coating of super alloy K424 up to 700 °C.     

Performance and application of a high energy monochromated Cu Kα1 X-ray source for the electron spectroscopy of materials

A Cu Kα₁ sealed tube X-ray source (hν = 8047.8 eV) and LiF(2 2 0) Johansson geometry monochromator crystal have been interfaced to a Scienta ESCA300 spectrometer for high energy XPS studies of materials, in particular for the measurement of Auger parameters associated with deep core levels in metallic alloys. The detailed arrangement of the source, monochromator and spectrometer combination is described, and factors affecting the overall intensity and resolution are discussed. The optimisation and characterisation of the system are also described. Several examples of Cu Kα₁ excited survey spectra (Cr, Fe, stainless steel), deep core level spectra (Cr 1s, Fe 1s) and Auger spectra (Cr KLL, Cr LMM, Fe KLL) are presented, which illustrate the capability of the system. Auger vacancy satellites are identified in the Cr LMM spectrum. For a series of Cr–Si alloys measurements are reported of the change in the Cr Auger parameter on going from metal to alloy.     

Segregation of lead in oxide film of high-purity aluminum containing 100 ppm lead

Surface segregation in high-purity Al–100 ppm Pb foil annealed for 4 h at 540 °C was studied mainly by transmission electron microscopy (TEM) observations. TEM–EDX demonstrated that almost of the lead element segregated not to aluminum surface but predominantly to the oxide amorphous film formed just above aluminum surface. The enrichment of lead in the oxide film was about 30 000 fold.     

Galvanostatically deposited Fe: MnO2 electrodes for supercapacitor application

The present investigation describes the addition of iron (Fe) in order to improve the supercapacitive properties of MnO₂ electrodes using galvanostatic mode. These amorphous worm like Fe: MnO₂ electrodes are characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), energy dispersive X-ray analysis (EDAX), Fourier transform infrared spectroscopy (FTIR) and wettability test. The supercapacitive properties of MnO₂ and Fe: MnO₂ electrodes are investigated using cyclic voltammetry, chronopotentiometry and impedance techniques. It is seen that the supercapacitance increases with increase in Fe doping concentration and achieved a maximum of 173 F g^?1 at 2 at% Fe doping. The maximum supercapacitance obtained is 218 F g^?1 for 2 at% Fe: MnO₂ electrode. This hydrous binary oxide exhibited ideal capacitive behavior with high reversibility and high pulse charge–discharge property between ?0.1 and +0.9 V/SCE in 1 M Na₂SO₄ electrolyte indicating a promising electrode material for electrochemical supercapacitors.     

Magnetic phase transitions in the Nd(Mn0.9Me0.1)O3 (Me=Al, Fe, Cr, Zn) perovskites

It is shown that perovskite NdMnO₃ is a weak ferromagnet with an anomalous magnetization behavior due to Nd sublattice contribution. Ferromagnetic component drastically increases whereas T_N slightly decreases when a part of manganese ions is replaced with Cr, Al, Fe, Zn. It is suggested that the Mn³⁺–O–Mn³⁺ superexchange interaction changes a sign in the microdomains enriched with Me=Cr, Al, Fe, Zn ions due to removing static Jahn–Teller distortions. All these substituted perovskites show a sharp drop of the magnetization as temperature decreases. A large temperature hysteresis indicates first-order phase transition. Below this transition neodymium magnetic moments orient opposite to a moment of manganese magnetic sublattice. It is supposed that this phase transition results from a change of the ground state of Nd ions.     

Determining the work function of a carbon-cone cold-field emitter by in situ electron holography

Cold-field emission properties of carbon cone nanotips (CCnTs) have been studied in situ in the transmission electron microscope (TEM). The current as a function of voltage, i(V), was measured and analyzed using the Fowler–Nordheim (F–N) equation. Off-axis electron holography was employed to map the electric field around the tip at the nanometer scale, and combined with finite element modeling, a quantitative value of the electric field has been obtained. For a tip-anode separation distance of 680 nm (measured with TEM) and a field emission onset voltage of 80 V, the local electric field was 2.55 V/nm. With this knowledge together with recorded i(V) curves, a work function of 4.8 ± 0.3 eV for the CCnT was extracted using the F–N equation.     

Cadmium sulfide quantum dots stabilized by castor oil and ricinoleic acid

Castor oil and ricinoleic acid (an isolate of castor oil) are environmentally friendly bio-based organic surfactants that have been used as capping agents to prepare nearly spherical cadmium sulfide quantum dots (QDs) at 230, 250 and 280 °C. The prepared quantum dots were characterized by Ultra violet–visible (UV–vis), Photoluminescence (PL), Transmission Electron Microscopy (TEM), High Resolution Transmission Electron Microscopy (HRTEM) and X-ray diffraction (XRD) giving an overall CdS QDs average size of 5.14±0.39 nm. The broad XRD pattern and crystal lattice fringes in the HRTEM images showed a hexagonal phase composition of the CdS QDs. The calculated/estimated average size of the prepared castor oil capped CdS QDs for various techniques were 4.64 nm (TEM), 4.65 nm (EMA), 5.35 nm (UV–vis) and 6.46 nm (XRD). For ricinoleic acid capped CdS QDs, the average sizes were 5.56 nm (TEM), 4.78 nm (EMA), 5.52 nm (UV–vis) and 8.21 nm (XRD). Optical properties of CdS QDs showed a change of band gap energy from its bulk band gap of 2.42–2.82 eV due to quantum size confinement effect for temperature range of 230–280 °C. Similarly, a blue shift was observed in the photoluminescence spectra. Scanning electron microscope (SEM) observations show that the as-synthesized CdS QDs structures are spherical in shape. Fourier transform infra-red (FTIR) studies confirms the formation of castor oil and ricinoleic acid capped CdS QDs.     

Understanding of redox behavior of Ni–YSZ cermets

The oxidation of Ni–YSZ cermet as well the reduction of re-oxidized Ni–YSZ cermet was investigated by using temperature-programmed oxidation (TPO), temperature-programmed reduction (TPR) and scanning electron microscope (SEM). The scanning electron microscope (SEM) photographs and temperature-programmed reduction (TPR) profiles indicated that the sintering of smaller nickel oxide crystallites to larger aggregates occurred concurrently with the formation of smaller nickel oxide crystallites from the oxidation of nickel at 800 °C, and the sintering of smaller nickel oxide crystallites at 600 °C was slower than that at 800 °C. The SEM results showed that each Ni particle was separated into a lot of smaller NiO particles during oxidation. The TPO profiles showed that two kinds of nickel particles exist in the anode reduced at 800 and 600 °C, one with high activity towards oxidation for the nickel crystallites directly from reduction, and another one with low activity towards oxidation for the sintered nickel particles. The Ni–YSZ anodes reduced at higher temperature showed higher re-oxidation temperature than the one reduced at lower temperature because of the accelerated passivating and sintering of the smaller nickel particles at higher temperature. The re-oxidation profiles were almost unchanged during redox cycling at 600 °C, whereas the re-oxidation peak temperature decreased during redox cycling at 800 °C, indicating that the primary nickel grains split to smaller ones upon cyclic reduction at higher temperature.     

Fe alloying effect on the performance of the Ni anode in hydrogen fuel

Composite materials of YSZ (yttria-stabilized zirconia) with various Ni–Fe alloys were synthesized and evaluated as the solid oxide fuel cell (SOFC) anode using a 200-µm thick YSZ electrolyte as support and YSZ +La_0.8Sr_0.2MnO₃ (LSM) as cathode. The single cell with the YSZ + Ni_0.75Fe_0.25 anode exhibited the highest performance among all the investigated cells, e.g. a peak power density of 403, 337, 218 and 112 mW/cm² was achieved with H₂ fuel at 900, 850, 800 and 750 °C, respectively. The composite anode with the Ni_0.75Fe_0.25 alloy also had the lowest polarization resistance of 0.55 Ω·cm² at 800 °C among all the alloy compositions, indicating that this specific alloy offered a better anode composition than pure Ni. The possible mechanism for the improved performance of Ni with the Fe alloying addition towards H₂ oxidation was discussed.     

Characterization of Laves phase in Crofer 22 H stainless steel

This study investigated the effect of annealing temperature on the precipitation behavior of Crofer^® 22 H at 600 °C, 700 °C, and 800 °C. The grain size distribution, precipitate phase identification, and microstructure were analyzed using electron backscatter diffraction (EBSD) and energy dispersive X-ray spectroscopy (EDS). The morphology of Laves phase (Fe,Cr,Si)₂(Nb,W) precipitates having the Cr₂Nb structure changed from strip-like to needle-shaped as the annealing temperature was increased. The precipitates of the Laves phase also shifted from the grain boundaries to the grain interiors when the temperature was increased. However, the average grain size (150 μm) of the ferritic matrix did not significantly change at 600 °C, 700 °C, and 800 °C for 10 h.     

Effect of alloying contents and processing factors on the microstructure and homogenization of Si alloyed Cr–Mo sintered steels

Fe–Si alloys are of significant commercial and academic interests, due to the large diversity of their physical properties. In practice, alloy powders are unsuitable because of their hardness, poor compactibility and resulting excessive tool wear. Therefore the powder mixture route is suitable as alloying technique. The properties of the Fe–Si sintered materials depend strongly on the influence of the element Si and content of it, which influence mainly the compactibility and the sintering behaviour as well as sintering parameters such as the optimum temperature. In this study, Cr–Mo prealloyed steel powders with different Si contents were prepared by powder mixture route. Mixed powders compacted under pressing pressure of 600 MPa, and then sintered at 1120 and 1250 °C. It was found out that in Si alloyed Cr–Mo steels sintered at higher temperatures such as 1250 °C, an intermediate liquid phase appeared and caused extreme shrinkage and distortion, but strongly accelerated sintering and had a beneficial effect also on homogenization.     

Surface modification of Ni and Co metal nanowires through MeV high energy ion irradiation

Nickel (Ni) and cobalt (Co) metal nanowires were fabricated by using an electrochemical deposition method based on an anodic alumina oxide (Al₂O₃) nanoporous template. The electrolyte consisted of NiSO₄ · 6H₂O and H₃BO₃ in distilled water for the fabrication of Ni nanowires, and of CoSO₄ · 7H₂O with H₃BO₃ in distilled water for the fabrication of the Co ones. From SEM and TEM images, the diameter and length of both the Ni and Co nanowires were measured to be ∼ 200 nm and 5–10 μm, respectively. We observed the oxidation layers in nanometer scale on the surface of the Ni and Co nanowires through HR–TEM images. The 3 MeV Cl²⁺ ions were irradiated onto the Ni and Co nanowires with a dose of 1 × 10¹⁵ ions/cm². The surface morphologies of the pristine and the 3 MeV Cl²⁺ ion-irradiated Ni and Co nanowires were compared by means of SEM, AFM, and HR–TEM experiments. The atomic concentrations of the pristine and the 3 MeV Cl²⁺ ion-irradiated Ni and Co nanowires were investigated through XPS experiments. From the results of the HR–TEM and XPS experiments, we observed that the oxidation layers on the surface of the Ni and Co nanowires were reduced through 3 MeV Cl²⁺ ion irradiation.     

CO2-enhanced dehydrogenation of ethane over sonochemically synthesized Cr/clinoptilolite-ZrO2 nanocatalyst: Effects of ultrasound irradiation and ZrO2 loading on catalytic activity and stability

CO₂-enhanced oxidative dehydrogenation of ethane was investigated over sonochemically synthesized Cr/clinoptilolite-ZrO₂ nanocatalyst with the aim of assessing the effect of composite support and ultrasonic irradiation on the nanocatalyst reactivity and stability. To this aim, ZrO₂ promoted clinoptilolite supports varying in zirconia content (0, 25, 50 wt%) were synthesized by hydrothermally precipitation method and impregnated with chromium nitrate under ultrasound irradiation. The samples were characterized by XRD, FESEM, EDX, TEM, ICP, BET, FTIR, TPR-H₂ and TPD-NH₃ techniques. The characterization results indicated that ultrasound irradiation could not only reduce the formation of Cr₂O₃ and decrease submicron particle size of chromium oxide to nanometer scale, but also promote the distribution of metallic particles and strengthen the chromium-support interaction. As a result, utilizing ultrasound irradiation in the synthesis of Cr/Clinoptilolite helped to maintain a high and stable catalytic activity. These features were more prominent in the presence of zirconia. It was found that the metal oxide nanoparticles with about 4–8 nm are dispersed uniformly on the surface of composite support containing 25 wt% ZrO₂ (CLT-Z25). Moreover, the addition of ZrO₂ resulted in the formation of new strong acid sites and a significant modification in the reducibility of chromium species, which alongside homogenous and small Cr nanoparticles account for the superior catalytic performance of ZrO₂ containing samples. However, excessive loading of ZrO₂ (50 wt%) severely covered the surface of clinoptilolite, afforded the aggregations of metallic particles and thereupon, weakened the contact between clinoptilolite and ZrO₂, which together with more acid strength seriously resulted in the deactivation of catalyst. In spite of superior initial activity of ZrO₂-rich sample among the catalysts tested, ultrasonic synthesized Cr/CLT-Z25 nanocatalyst showed the best catalytic performance after 5 h-catalytic reaction.     

Electronic core levels of hydroxyls at the surface of chromia related to their XPS O 1s signature: A DFT + U study

The Cr 2p and O 1s binding energy (BE) levels have been calculated by first principles methods for different models of hydroxylated (0001)-Cr₂O₃ surfaces. Several surface terminations have been considered. The calculations allow us to reproduce the O 1s shifts between O in oxide and OH groups. It is found that two main effects account for the OH binding energy shifts. On the one hand, the increased covalency of the O–H bond with respect to the Cr–O bond, lowers the electronic O (1s and 2p) energy, and in consequence the BE of the core levels (O 1s) are higher. On the other hand, the lower the OH coordination number, the higher the valence and core levels energy, and the lower the BE. Consequently, mono-coordinated hydroxyls have a binding energy near that of O^2? in the oxide (ΔBE_OH–O = ? 0.2–0.0 eV). Two-fold coordinated hydroxyls have a slightly higher BE (ΔBE_OH–O = + 0.3 eV). Three-fold coordinated OH groups have a higher binding energy (ΔBE_OH–O = + 0.6?0.7 eV), corresponding to that experimentally measured for OH groups. Finally, water adsorbed above OH groups exhibits a still higher BE (ΔBE_HOH–O = + 0.9–1.0 eV). The ΔBE are slightly under-estimated under the initial state approximation, and overestimated under the final state (Z + 1) approximation.     

Band-gap engineering of ZnSe quantum dots via a non-TOP green synthesis by use of organometallic selenium compound

Single-step green synthesis of ZnSe quantum dots (QDs) from 1,2,3-selenadiazole and zinc acetate resulted in formation of high-quality mono-disperse ZnSe with engineered band-gap. The present method is a non-TOP green route where oleic acid is used as a surfactant. The size quantization effect can be monitored by UV–visible spectroscopy which shows in the range 370–387 nm (3.20–3.35 eV), a blue shift of about 70–90 nm with respect bulk ZnSe. Photoluminescence measurement revealed band-gap emission at ∼390 nm (3.18 eV, Stokes shift of <10 nm with FWHM <30 nm). Broadened XRD pattern indicated formation of cubic ZnSe and the estimation of particle size from the line broadening at 〈1 1 1〉 matched well the TEM analysis.     

High coercivity and superparamagnetic behavior of nanocrystalline iron particles in alumina matrix

Single-domain nanoscale magnetic iron particles have been embedded uniformly in an amorphous matrix of alumina using a pulsed laser deposition technique. Structural characterization by transmission electron microscopy (TEM) reveals the presence of a crystalline iron and an amorphous alumina phase. Fine particle magnetism have been investigated by carrying out field and temperature dependence of magnetization measurements using superconducting quantum interference device magnetometer. The particle size of Fe in Al₂O₃ matrices prepared by changing the deposition time of Fe, have been found to be 9, 7 and 5 nm from TEM studies. At 10 K, the coercivities of these samples are found be 450, 350 and 150 Oe, respectively. At 300 K, the coercivity of Fe–Al₂O₃ sample decreases from 100 to 50 Oe as the particle size decreases from 9 to 7 nm and finally the sample turns superparamagnetic when the Fe particle size becomes around 5 nm. Based on the calculated value of blocking temperature, T_B, (481 K), magnetic anisotropy K (4.8×10⁵ erg/cm³) for Fe, and the Boltzmann constant k_B (1.38×10⁻¹⁶ erg/K) from T_B=KV/25k_B, the mean radius of Fe particles is found to be 9.3 nm. in one of the samples. This is in good agreement with the particle size measured using TEM studies.     

XRD and XPS characterisation of transition metal silicide thin films

Binary transition metal silicides based on the systems Ti–Si, Fe–Si, Ni–Si and Cr–Si were fabricated on Si wafers by means of ion-beam co-sputter deposition and subsequent annealing. The crystalline structures of the phases formed were identified from the characteristic patterns acquired by means of X-ray diffraction (XRD) measurements. The phase formation sequences were described by means of the Pretorius' effective heat of formation (EHF) model. For the Ti–Si, Fe–Si and Ni–Si systems, single phase thin films of TiSi₂, β-FeSi₂ and NiSi₂ were generated as the model predicts, while a mixture of CrSi + CrSi₂ phases was obtained for the Cr–Si system. The surface chemical condition of individual specimens was analysed by using X-ray photoelectron spectroscopy (XPS). The chemical shifts of transition metal 2p_3/2 peaks from their metallic to silicide states were depicted by means of the Auger parameters and the Wagner plots. The positive chemical shift of 2.0 eV for Ni 2p_3/2 peak of NiSi₂ is mainly governed by the initial-state effects. For the other silicide specimens, the initial-state and final-state effects may oppose one another with similar impact. Consequently, smaller binding energy shifts of both negative and positive character are noted; a positive binding energy shift of 0.3 eV for the Fe 2p_3/2 level was shown for β-FeSi₂ and negative binding energy shifts of 0.1 and 0.3 eV were determined for CrSi + CrSi₂ and TiSi₂, respectively.     

Synthesis of carbon nanotubes via Fe-catalyzed pyrolysis of phenolic resin

Carbon nanotubes (CNTs) with 40–100 nm in diameter and tens of micrometers in length were prepared via catalytic pyrolysis of phenol resin in Ar at 673–1273 K using ferric nitrate as a catalyst precursor. Structure and morphology of pyrolyzed resin were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and Raman spectroscopy. Ferric nitrate was transformed to Fe₃O₄ at 673 K, and to metallic Fe and Fe_xC carbide at 873–1273 K. The optimal weight ratio of Fe catalyst to phenol resin for growing CNTs was 1.00 wt%, and the optimal temperature was 1073 K. In addition, use of a high pressure increased the yield of CNTs. Density functional theory (DFT) calculations suggest that Fe catalysts facilitate the CNTs growth by increasing the bond length and weakening the bond strength in C₂H₄ via donating electrons to the C atoms in it.     

Effect of thin aluminum interlayer on growth and microstructure of carbon nanotubes

The aluminum (Al) interlayer with various thicknesses ranging from 0.75 to 6 nm was deposited on silicon (Si) substrates prior to the deposition of ultra-thin iron (Fe) catalyst for the growth of carbon nanotubes. In this paper we report the effect of ultra-thin Al interlayer on the growth of multiwalled carbon nanotubes (MWCNTs). The SEM was used to examine the microstructures of nanotubes. We observed as the Al interlayer thickness increases the height of nanotube decreases. Raman spectra of MWCNT showed typical D and G peaks at ∼1345 cm⁻¹ and ∼1575 cm⁻¹, respectively. The XPS revealed the presence of Al and Fe on the top of CNT surface which were further supported by TEM. The high resolution TEM results also revealed bamboo like CNTs with diameter ∼10–40 nm.