Influence of bond defects on coiling of graphite

The effect of annealing at 1400 °C in argon on the bond structure of graphite ball milled for 100 h at 400 rpm in polar (water) and in non-polar (n-dodecane) liquids was investigated primarily by near-edge X-ray absorption fine structure spectroscopy (NEXAFS) and transmission electron microscopy (TEM). Carbon K-edge NEXAFS allows the distortion of bonds in the hexagonal lattice to be investigated. It is shown that in-plane sp² bonds are strained and distorted after ball milling because sp³ bonds are introduced. Not surprisingly, annealing of the milled product restores sp² bonds but at the same time, coiling and formation of tube-like structures takes place. It is well established that graphite is not formed on annealing, and hence the results shown here demonstrate that the loss of sp³ carbons on annealing must proceed via a different mechanism by which they are formed by milling.     

Structural analysis of Sm doped nanocrystalline Mg–Cd ferrites prepared by oxalate co-precipitation method

The structural properties of polycrystalline Sm³⁺ doped Mg_1 − xCd_x Fe₂O₄ (x = 0.0, 0.2, 0.4, 0.6, 0.8, 1.0) have been investigated by oxalate co-precipitation method from high purity sulphates. The samples were sintered at 1050 °C for a duration of 5 h. The X-ray diffraction measurements confirmed the formation of a cubic spinel structure. The different parameters like lattice constant, X-ray density, physical density, porosity, crystallite size, site radii and bond length on tetrahedral and octahedral sites have been calculated. The lattice constant increases with an increase in Cd²⁺ content and shows non linear behavior. The crystallite size was calculated using Scherrer formula and varies from 28.69 to 32.05 nm. Physical densities were obtained by Archimedes principle. The surface morphology studied by scanning electron microscope shows that the grain size of the samples increases with an increase in Cd²⁺ content. The IR spectra show two strong absorption bands around 5.87 × 10⁴ m^− 1 and 4.27 × 10⁴ m^− 1 on the tetrahedral and octahedral sites respectively. IR spectra also show that Sm³⁺ occupies the octahedral B-site.     

Single step synthesis of nanocrystalline ZnO via wet-milling

In this work, we describe the effect of milling speed on the formation, crystallite size, and lattice parameter of nanocrystalline ZnO in a single step process that is based on wet-milling of metallic Zn in distilled water. The samples were characterized by XRD, TEM, and FTIR spectra. The analyses reveal that although the 150 rpm milled sample exhibits imprints of Zn (OH)₂, 200, 250, 300, and 350 rpm milled samples possess the standard hexagonal ZnO wurtzite structure. The crystallite size and lattice parameters of the samples were calculated from the XRD patterns by applying the Maud refinement procedure. According to the results, average crystallite size of the ZnO nanocrystals is in the range of 27.3-31.4 nm depending on the milling speed.     

Effect of oxygen pressure of SiOx buffer layer on the electrical properties of GZO film deposited on PET substrate

The present work was made to investigate the effect of oxygen pressure of SiO_x layer on the electrical properties of Ga-doped ZnO (GZO) films deposited on poly-ethylene telephthalate (PET) substrate by utilizing the pulsed-laser deposition at ambient temperature. For this purpose, the SiO_x buffer layers were deposited at various oxygen pressures ranging from 13.3 to 46.7 Pa. With increasing oxygen pressure during the deposition of SiO_x layer as a buffer, the electrical resistivity of GZO/SiO_x/PET films gradually decreased from 7.6 × 10^− 3 to 6.8 × 10^− 4 Ω·cm, due to the enhanced mobility of GZO films. It was mainly due to the grain size of GZO films related to the roughened surface of the SiO_x buffer layers. In addition, the average optical transmittance of GZO/SiO_x/PET films in a visible regime was estimated to be ~ 90% comparable to that of GZO deposited onto a glass substrate.     

Coercivity and superparamagnetic evolution of high energy ball milled (HEBM) bulk CoFe2O4 material

Ball milling (BM) of bulk CoFe₂O₄ powder material carried out in order to study its structural stability and attendant property changes with respect to coercivity enhancements and superparamagnetic behaviors, showed that drastic crystallite size reduction occurred within the first 1 h of ball milling. Crystallite size dropped from 74 nm for the as-received material to a value of 11.6 nm for 600 min of ball milling. Combined X-ray diffraction (XRD) and scanning electron microscopy (SEM) analyses confirmed crystallite size reduction with corresponding increase in interparticle agglomeration/pores with increasing milling time. The maximum coercivity of 0.46 T and the crystallite size of 15.6 nm were recorded with 20 min, while peak residual strain of 0.0066 mm/mm was for 180 min of BM. Material with peak coercivity value did not have peak residual strain, or minimum crystallite size, thereby suggesting that other structural defects contributed to coercivity enhancement. The saturation magnetization (M_s) value decreased continuously with increasing milling time, while remanence magnetization (M_r) and coercivity decreased with increasing BM time, after an initial increase. Mössbauer spectroscopy (MS) measurements confirmed both particle size distribution and decomposition/disordering of the material together with superparamagnetism as BM time increased. The degree of inversion ranged from 41% to 71.7% at different milled states from Mössbauer spectroscopy. The internal magnetic fields of the Fe sites associated with the tetrahedral and octahedral sites were 507.4 kOe and 492 kOe respectively in the unmilled state, while 484 kOe and 468.5 kOe in the 600 min milled state correspondingly.     

Compressive and wear behaviors of bulk nanostructured Al2024 alloy

Compressive and wear properties of bulk nanostructured Al2024 alloy prepared by mechanical milling and hot pressing methods were investigated. Al2024 powders were subjected to high-energy milling for 30 h to produce nanostructured alloy. As-milled powders were compacted at 500 °C under 250 MPa in a uniaxial die. Consolidated sample had an average hardness and relative density values of 207.6 HV and 98%, respectively. Uniaxial compression tests at strain rates in the range of 1.67 × 10⁻⁴–1.67 × 10⁻² s⁻¹ were performed using an Instron-type machine. The wear behavior of nanostructured sample was investigated using a pin-on-disk technique under an applied load of 20 N. The compression and wear experiments were also executed on samples of commercial coarse-grained Al2024-O (annealed) and Al2024-T6 (artificially-aged) alloys, for comparison. The structure of consolidated Al2024 was characterized by X-ray diffraction (XRD). The yield strength and compressive strength of nanostructured Al2024 reached a value of 698 MPa and 712 MPa at strain rate of 1.67 × 10⁻⁴ s⁻¹, respectively, which was considerably higher than those for coarse-grained Al2024-O and Al2024-T6 counterparts. Worn surfaces and the wear debris were analyzed by scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS) and XRD. Nanostructured Al2024 revealed a low friction coefficient of 0.3 and a wear rate of 12 × 10⁻³ mg/m, which are significantly lower than those obtained for Al2024-O and Al2024-T6 alloys. This enhanced wear resistance was mainly caused by nanocrystalline structure with high hardness value. The dominating wear mechanism of nanostructured Al2024 appeared to be delamination mechanism.     

Growth, thermal and spectroscopic characteristics of LiNd(WO4)2 crystal

Crystal growth, thermal and optical characteristics of LiNd(WO₄)₂ crystal have been investigated. The LiNd(WO₄)₂ crystal up to Ø15 × 32 mm³ has been grown by Czochralski technique. The hardness is about 5.0 Mohs’ scale. The specific heat at 50 °C is 0.42 J g⁻¹ K⁻¹. The thermal expansion coefficient for c- and a- axes is 1.107 × 10⁻⁵ and 2.104 × 10⁻⁵ K⁻¹, respectively. The absorption and fluorescence spectra and the fluorescence decay curve of LiNd(WO₄)₂ crystal were measured at room temperature. Some spectroscopic parameters such as the intensity parameters, the spontaneous transition probabilities, the fluorescence branching ratios, the radiative lifetimes and emission cross sections were estimated.     

Anisotropic thermal expansion of stoichiometric lithium niobate crystals grown along the normal direction of facets

In this paper, a stoichiometric lithium niobate (SLN) crystal with the size up to 20 × 20 × 18 mm³ was grown along the normal direction of the (0 1 2) facet from the 16 mol% K₂O fluxed melt by the top-seeded solution growth method. The anisotropic thermal expansion of the SLN crystal and congruent lithium niobate (CLN) crystal was measured along different directions by using a Shimadzu thermomechanical analyzer. As compared with CLN, the SLN crystal exhibited slightly larger thermal expansion along the Z-axis and slightly smaller expansion along the X-axis. Both the SLN and CLN crystals showed strong anisotropy in the thermal expansion. The thermal expansion coefficient of SLN along the X-axis (16.7 × 10⁻⁶ °C⁻¹ at 300 °C) is much larger than that along the Z-axis (2.5 × 10⁻⁶ °C⁻¹ at 300 °C). Based on the experimental data and polynomial fitting results, we calculated the thermal expansion coefficients for different directions. In the case of growing the SLN crystal along the normal direction of (0 1 2) facet, we studied the radial anisotropic thermal expansion and discussed the cracking problem of the crystal according to its actual growth morphology. It is found that the cracks of SLN can be suppressed by growing the crystal along the W-axis due to its reduced radial anisotropy in the thermal expansion.     

Growth and optical characterizations of (Ba0.32Sr0.68)5Nb4O15 crystal

(Ba_0.32Sr_0.68)₅Nb₄O₁₅ crystal with sizes of Ø 17 × 35 mm was grown successfully by Czochralski technique method. The thermal anisotropy was discussed. The principal coefficients of thermal expansion along (100), (010), (001) directions were precisely measured to be 1.308 × 10^− 5, 1.288 × 10^− 5, 1.478 × 10^− 5 K^− 1, respectively. Its optical transparency range has been measured and found to span from 323 to 5500 nm. The bands present in the IR spectra were identified and assigned to the corresponding vibration modes of NbO₆ anions.     

Crystallite size reduction of Cr doped Al2O3 materials via optimized high-energy ball milling method

α-Al₂O₃ based compounds have large crystals and it is very difficult to reduce the crystallite size because they are very stable and hard. One way of reducing the crystallite size of the materials is by using high-energy ball milling method. Pure and single-phase micron-sized α-Al_2−xCr_xO₃ (x = 0.1, 0.2, 0.3) materials were successfully obtained via self-propagating combustion method. These materials were then subjected to a simple milling process from their microcrystalline powders. Comparisons between the micron-sized and milled samples in terms of their phase, structure, morphology and crystallite size were discussed. The XRD results reveal that all the milled samples were pure with no impurity or other phases present. Structural parameters are extracted via the Rietveld method, revealing that the cell constant, a, of the milled samples is higher than that of the micron-sized materials by 0.09 % to 0.11 %, resulting in a 0.28 % to 0.39 % increase in cell volume. FESEM results show a gradual decrease in crystallite size with increased milling time. Notably, the method successfully reduces the crystallite size without changing the phase of the materials and preserving the stoichiometry of the Al_2−xCr_xO₃ materials which may offer improved properties in various applications.     

Electrochemical determination of cadmium(II) at platinum electrode modified with kaolin by square wave voltammetry

In this work, determination of cadmium(II) using square wave voltammetry (SWV) was described. The method is based on accumulation of these metal ions on kaolin platinum electrode (K/Pt). The K/Pt performance was optimized with respect to the surface modification and operating conditions. The optimized conditions were obtained in pH of 5.0 and accumulation time of 25 min. Under the optimal conditions, the relationship between the peak current versus concentration was linear over the range of 9 × 10⁻⁸ to 8.3 × 10⁻⁶ mol L⁻¹. The detection limit (DL, 3σ) was 5.4 × 10⁻⁹ mol L⁻¹. The analytical methodology was successfully applied to monitor the Cd(II) content in natural water. Interferences were also evaluated.     

Surface and grain-boundary energies as well as surface mass transport in polycrystalline CeO2

The multiphase equilibration technique for the determination of the equilibrium angles that develop at the interphase boundaries of a solid–liquid–vapor system, has been used to calculate the surface and interfacial energies in polycrystalline CeO₂ and CeO₂/Cu system in argon atmosphere at the temperature range 1473–1773 K. Linear temperature functions were obtained by extrapolation, for the surface energy γ_sv (J/m²) = 2.465–0.563 × 10⁻³ T and the grain-boundary energy γ_ss (J/m²) = 1.687–0.391 × 10⁻³ T of the ceramic, as well as for the interfacial energy γ_sl (J/m²) = 2.623–1.389 × 10⁻³(T −1356 K) of the CeO₂/Cu system. Grain-boundary grooving studied on polished surfaces of CeO₂ annealed in argon atmosphere at the same temperature range has shown that surface diffusion was the dominant mechanism for the mass transport. The surface diffusion coefficient can be expressed according to the equation D_s (m²/s) = 3.82 × 10⁻⁴ exp(−308,250/RT).     

Determination of cadmium at ultra-trace levels by CPE–molecular fluorescence combined methodology

A highly sensitive micelle-mediated extraction methodology for the preconcentration and determination of trace levels of cadmium by molecular fluorescence has been developed. Metal was complexed with o-phenanthroline (o-phen) and eosin (eo) at pH 7.6 in buffer Tris medium and quantitatively extracted into a small volume of surfactant-rich phase of PONPE 7.5 after centrifugating. The chemical variables affecting cloud point extraction (CPE) were evaluated and optimized. The RSD for six replicates of cadmium determinations at 0.84 μg L⁻¹ level was 1.17%. The linearity range using the preconcentration system was between 2.79 × 10⁻³ μg L⁻¹ and 2.81 μg L⁻¹ with a correlation coefficient of 0.99. Under the optimal conditions, it obtained a LOD of 8.38 × 10⁻⁴ μg L⁻¹ and LOQ of 2.79 × 10⁻³ μg L⁻¹. The method presented good sensitivity and selectivity and was applied to the determination of trace amounts of cadmium in commercially bottled mineral water, tap water and water well samples with satisfactory results. The proposed method is an innovative application of CPE-luminescence to metal analysis comparable in sensitivity and accuracy with atomic spectroscopies.     

Biosensor enhanced by glucose oxidase biomimetic membrane containing the platinum and silica nanoparticles

In this paper, glucose biosensor is fabricated with immobilization of glucose oxidase (GOx) in platinum and silica sol. The glucose biosensor combined with Pt and SiO₂ nanoparticles could make full use of the properties of nanoparticles. A set of experimental results indicates that the current response for the enzyme electrode containing platinum and silica nanoparticles increases from 0.32 µA cm^− 2 to 33 µA cm^− 2 in the solution of 10 mM β-D-glucose. The linear range is 3 × 10^− 5 to 3.8 × 10^− 3 M with a detection limit of 2 × 10^− 5 M at 3σ. The effects of the various volume ratios of Pt and SiO₂ sols with respect to the current response and the stability of the enzyme electrodes are studied.     

Plastic deformation behavior in dual-phase Ni–31Al intermetallics at elevated temperature

Plastic deformation behavior of dual-phase Ni–31Al intermetallics at elevated temperature was examined. It was found that the alloy exhibited good plasticity under an initial strain rate of 1.25 × 10⁻⁴ s⁻¹ to 8 × 10⁻³ s⁻¹ in a temperature range of 950–1075 °C. A maximum elongation of 281.3% was obtained under an initial strain rate of 5 × 10⁻⁴ s⁻¹ at 1000 °C. The strain rate sensitivity, m value was correlated with temperature and initial strain rate, being in the range of 0.241–0.346. During plastic deformation, both the two phases Ni₃Al and NiAl in dual-phase Ni–31Al could co-deform without any void formation or debonding, the initial coarse microstructure became much finer after plastic deformation. Dislocation played an important role during the plastic deformation in dual-phase Ni–31Al alloy, the deformation mechanism in dual-phase Ni–31Al could be explained by continuous dynamic recovery and recrystallization.     

Novel oxidative electrophilic coupling reactions of phenoxazine derivatives with MBTH and their applications to spectrophotometric determination of residual chlorine in drinking water and environmental water samples

Novel, sensitive and rapid spectrophotometric methods, using phenoxazine (PNZ), 2-chlorophe-noxazine (CPN) and 2-trifluoromethylphenoxazine (TPN) as chromogenic reagents for the determination of residual chlorine are proposed. The methods are based on the reduction of chlorine by an electrophilic coupling reagent, 3-methyl-2-benzothiazoline hydrazono hydrochloride hydrate (MBTH) in mild hydrochloric acid medium and subsequent coupling with PNZ, CPN or TPN. The blue color formed in the reaction showed maximum absorbance at 680–690 nm and obeyed Beer's law over the range 0.1–2.2 μg ml⁻¹. The molar absorptivity values with PNZ, CPN and TPN were 2.80 × 10⁴, 2.67 × 10⁴ and 1.91 × 10⁴ l mol⁻¹ cm⁻¹ and Sandell's sensitivity values were 0.028, 0.027 and 0.028 μg cm⁻² respectively. The proposed methods were successfully applied in the determination of residual chlorine in drinking water and environmental water samples. The performance of proposed methods was evaluated in terms of Student's t-test and variance ratio F-test which indicated the significance of proposed methods over the standard spectrophotometric method.     

Electrochemical behaviour of Cu24Zn5Al alloy in alkaline medium in the presence of chloride ions and benzotriazole

This paper deals with electrochemical behaviour of Cu24Zn5Al alloy in a sodium tetraborate solution (borax), in the presence of chloride ions and benzotriazole. It was found that during anodic polarization of the investigated alloy, in a sodium tetraborate solution, at lower potentials, copper (I)-oxide formed on the alloy surface. The voltammograms show peak potential shifts corresponding to the formation of Cu₂O towards more positive values with longer immersion time. It was found that chloride ions had an activating effect in a sodium tetraborate solution containing various concentrations of chloride ions (0.001, 0.005, 0.010, 0.050 and 0.100 mol dm⁻³ Cl⁻). It was observed that Cu24Zn5Al alloy corroded more intensely in more concentrated solutions and with longer exposure to Cl⁻. Investigations of the effect of inhibitor concentrations (8.4 × 10⁻⁶, 8.4 × 10⁻⁵, 8.4 × 10⁻⁴ and 8.4 × 10⁻³ mol dm⁻³ BTA in 0.1 mol dm⁻³ borax solution) showed that BTA had a good protective effect. The inhibiting effect of BTA was also confirmed with various times of immersion of this alloy in a 1.7 × 10⁻² mol dm⁻³ solution of this inhibitor.     

Study on preparation and mechanical property of nanocrystalline NiAl intermetallic

Nanocrystalline NiAl materials were fabricated using mechanical alloying and hot-pressing sintering technique. The crystal structural and microstructure of milled powders during mechanical alloying, and the microstructure and mechanical properties of bulk NiAl intermetallic were characterized. The results show that B2 ordered nanocrystalline NiAl powders were successfully synthesized by solid-state diffusion via the gradual exothermic reaction mechanism during mechanical alloying. Scanning electron microscope image confirmed that the powder particles were flat and flake shape in the early stage of milling, but changed to a spherical shape with the crystallite size about 30 nm after the milling. After sintering, the crystal structure of nanocrystalline NiAl intermetallic was assigned to B2 order NiAl phase with the average crystallite size about 100 nm. The nanocrystalline NiAl intermetallic exhibited prominent room temperature compressive properties, such as the true ultimate compressive strength and the fracture strain were 2143 MPa and 32.2%, respectively. The appearances of vein-like patterns on the fracture surface of NiAl intermetallic materials indicated that the fracture mechanism could be characterized as ductile fracture. It can be concluded that higher sintering density and nanocrystalline of NiAl intermetallic were benefited for the improvement of mechanical properties.     

Deformability enhancement in ultra-fine grained, Ar-contained W compacts by TiC additions up to 1.1%

Nano-sized Ar bubbles give negative influence on the fracture resistance and occurrence of superplasticity in ultra-fine grained (UFG) W–TiC compacts. In order to enhance deformability in UFG, Ar-contained W–TiC compacts, effects of TiC addition on the high-temperature deformation behavior were examined. W–TiC compacts with TiC additions of 0, 0.25, 0.5, 0.8 and 1.1 wt% were fabricated by mechanical alloying in a purified Ar atmosphere and hot isostatic pressing. Tensile tests were conducted at 1673–1973 K (0.45–0.54 T_m, T_m: melting point of W) at initial strain rates from 5 × 10⁻⁵ to 5 × 10⁻³ s⁻¹. It is found that as TiC addition increases, the elongation to fracture significantly increases, e.g., from 3 to 7% for W–0 and 0.25TiC/Ar to above 160% for W–1.1TiC/Ar when tested at 1873 and 1973 K at 5 × 10⁻⁴ s⁻¹. The flow stress takes a peak at 0.25%TiC and decreases to a nearly constant level at 0.5–1.1%TiC. The ranges of the strain rate sensitivity of flow stress, m, and the activation energy for deformation, Q, with TiC additions are 0.17–0.30 and 310–600 kJ/mol, respectively. The observed effects of the TiC additions on the tensile properties are discussed.     

Amorphisation and phase transformations in mechanically alloyed Ti–Al powders: electron microscopy investigation

Abstract

The microstructural evolution during mechanical alloying of Ti and Al powders has been investigated by X-ray diffraction, scanning electron microscopy (SEM)–energy dispersive spectroscopy, and transmission electron microscopy (TEM). Observations by SEM showed a progressive change of the powders' morphology as a function of milling time. Observations by TEM, performed on a sample milled for 20 h, revealed the simultaneous occurrence of amorphous zones and nanocrystalline domains. The observed amorphous phase is not the final milling product. After 34 h of milling it was possible to identify by TEM fcc (a=0·41 nm) nanocrystalline zones, with a mean size of about 10 nm. By irradiating the powder milled for 20 h with high density electron beams, a sudden in situ crystallisation took place. The crystallite (fcc with a=0·41 nm) size was between 0·1 and 0·5 μm.

MST/1281