Effect of the adsorbate (Bromacil) equilibrium concentration in water on its adsorption on powdered activated carbon. Part 2: Kinetic parameters

The application of several monosolute equilibrium models has previously shown that Bromacil adsorption on SA-UF (Norit) powdered activated carbon (PAC) is probably effective on two types of sites. High reactivity sites were found to be 10–20 less present in a carbon surface than lower reactivity sites, according to the q_m values calculated by isotherm models. The aims of this work were trying, primarily, to identify the kinetic-determinant stage of the sorption of Bromacil at a wide range of initial pesticide concentrations (5 to 500 μg L⁻¹ at pH 7.8), and secondly, to specify the rate constants and other useful design parameters for the application in water treatment. It was therefore not possible to specify a priori whether the diffusion or surface reaction is the key step. It shows that many of the tested models which describe the stage of distribution or the surface reaction are correctly applied. However, the diffusivity values (D and D₀) were found to be constant only constants for some specific experimental concentrations. The HSDM model of surface diffusion in pores was also applied but the values of the diffusion coefficient of surface (D_s) were widely scattered and reduce significantly with the initial concentration or the equilibrium concentration in Bromacil. The model of surface reaction of pseudo-second order fitted particularly well and led to constant values which are independent of the equilibrium concentration, except for the low concentrations where the constants become significantly more important. This last observation confirms perfectly the hypothesis based on two types of sites as concluded by the equilibrium data (part 1).     

The influence of Yb doping on the upconversion luminescence of Pr in aluminum oxide based powders prepared by combustion synthesis

The effect of ytterbium (Yb³⁺) doping on the upconversion (UC) emission of praseodymium (Pr³⁺) doped in aluminum oxide based powders prepared by combustion synthesis is reported for near-infrared excitation (λ = 980 nm). Our experimental results show that the crystalline structure and the UC emission changes with the Yb³⁺ concentration. The sample containing only Pr³⁺ (1.0 wt.%) did not show any UC signal and the UC emission profiles of the samples containing Pr³⁺ (1.0 wt.%) and Yb³⁺ (0.5, 2.0 wt.%) are quite different. The sample containing 0.5 wt.% of Yb³⁺ has five emission lines in the visible range associated to Pr³⁺ 4f–4f transitions, ³P₀ → ³H₄ (497 nm), ³P₀ → ³H₅ (525 and 550 nm), ³P₀ → ³H₆ (620 nm) and ³P₀ → ³F₂ (650 nm). We believe that the UC process has its origin in energy transfer from Yb³⁺ ions to Pr³⁺ ions in Pr_0.83Al_11.83O₁₉ phase. The sample containing 2.0 wt.% of Yb³⁺ has only one emission line in the visible range peaked at 507 nm which we believe has its origin in cooperative UC emission due to excited Yb³⁺ pairs in YbAlO₃ phase. The samples containing Yb³⁺ also present UC emission lines in the near-infrared which are assigned to intrinsic lattice defects.     

Thin films deposition with ECR planar plasma source

The results of film deposition of pure tungsten as well as intermetallic compound of NdFeB type on various substrates using planar ECR plasma source (with multipole magnetic field) developed in our laboratory are presented. The frequency of 2.45 GHz was generated within the magnetic system by two-slot antenna. The ions of ECR argon plasma are used for target sputtering. The main plasma parameters are density 10¹⁰ cm⁻³, T_e15 eV, ions energy 20 eV, ion current density 3.5 mA/cm² at the ultimate magnetron power. Under sputtering of Nd₈Fe₈₆B₆ target the amorphous films with high adherence and thickness of 5 μm were formed on the substrate. The deposition rate of tungsten films (target biasing 900 V) was 0.59 nm/s. The fine-grained films with high adhesion were obtained. They were tested against heat loads up to 100 J/cm² produced under irradiation of coatings with plasma streams.     

Microstructure and mechanical properties of nanocrystalline high strength Al–Mg–Si (AA6061) alloy by high energy ball milling and spark plasma sintering

In the present paper, the microstructure and mechanical properties of nanostructured Al–Mg–Si based AA6061 alloy obtained by high energy ball milling and spark plasma sintering were reported. Gas atomized microcrystalline powder of AA6061 alloy was ball milled under wet condition at room temperature to obtain nanocrystalline powder with grain size of 30 nm. The nanocrystalline powder was consolidated to fully dense compacts by spark plasma sintering (SPS) at 500 °C. The grain size after SPS consolidation was found to be 85 nm. The resultant SPS compacts exhibited microhardness of 190–200 HV_100 g, compressive strength of 800 MPa and strain to fracture of 15%.     

Superplastic flow in a nanostructured aluminum alloy produced using high-pressure torsion

Samples of a spray-cast Al-7034 alloy were processed by high-pressure torsion (HPT) at temperatures of 293 or 473 K using an imposed pressure of 4 GPa and torsional straining through five revolutions. Processing by HPT produced significant grain refinement with grain sizes of 60 and 85 nm at the edges of the disks for the two processing temperatures. In tensile testing at room temperature, the alloy processed by HPT exhibited higher strength and lower ductility than the unprocessed material. Good superplastic properties were achieved in tensile testing at elevated temperatures with a maximum elongation of 750% for the sample processed at 473 K and tested in tension at 703 K under an initial strain rate of 1.0 × 10⁻² s⁻¹. The measured superplastic elongations are lower than in samples prepared by equal-channel angular pressing because of the use of very thin disks in the HPT processing.     

Influence of additives on the impact toughness of Al–10.8% Si near-eutectic cast alloys

This article investigates the effects of melt treatment and addition of alloying elements on the impact toughness of as-cast and heat-treated Al–10.8% Si near-eutectic alloys. Increasingly precise impact behaviors are discussed in the context of differentiating between initiation and propagation energies, including the ductility index, which is the ratio of the propagation to initiation energies; total energy as a useful measure is also discussed. Details concerning the evaluation of tensile properties are reported in a separate article [Mohamed AMA, Samuel FH, Samuel AM, Doty HW. Influence of additives on the microstructure and tensile properties of near-eutectic Al–10.8%Si cast alloy. Mater Des, in press]. The concentration of elements in the alloys was changed to the following range: Fe 0.5–1 wt%, Mn 0.5–1 wt%, Cu 2.25–3.25 wt%, and Mg 0.3–0.5 wt%, while the impact toughness upon artificial aging in a temperature range of 155–240 °C for 5 h was also investigated. The results indicate that the morphology of fibrous Si in Sr-modified alloys enhances toughness because of its profound effect on crack initiation and crack propagation resistance. The combined addition of modifier and grain refiner leads to a 33% increase in the impact strength compared to the untreated alloy. In alloys containing high levels of iron, such as the RF2 (1% Fe, 1% Mn) and RF4 (1% Fe, 0.5% Mn) alloys, the addition of iron leads to an increased precipitation of sludge or β-Fe platelets, respectively; these particles also act as crack initiation sites and reduce the impact properties noticeably. In alloys already containing high levels of copper, such as the RC2 (3.25% Cu, 0.3% Mg) and RC5(0.3.25% Cu, 0.5% Mg) alloys, increasing the copper level lowers the impact properties significantly, in view of the fact that the fracture behavior is now predominantly influenced by the Al₂Cu phase rather than by the Si particles. The average crack propagation speed of impact-tested samples shows a good inverse relationship to impact energy. Crack propagation speed can thus provide a qualitative estimation of the impact energy expected for special alloy conditions.     

Effect of environment on fatigue crack growth in ultrafine grain Al–Mg

The fatigue crack growth rates, obtained in high vacuum and in ambient air, of ultrafine grain (UFG) Al–7.5Mg (grain size  250 nm) at various load ratios were compared to those of powder-metallurgy (P/M) Al–7Mg (grain size  2 μm) and ingot-metallurgy (I/M) Al–7Mg (grain size  100 μm). In both vacuum and ambient air, fatigue crack growth rates at all stress ratios decrease with increasing grain size. The fatigue crack growth threshold (ΔK_th) follows the reverse order, increasing with increasing grain size. These trends are interpreted in terms of fracture surface roughness effects that are correlated with grain size. In vacuum, the thresholds of all three materials exhibit no load ratio dependency at load ratios from 0.1 to 0.5. In air, the threshold of UFG Al–7.5Mg exhibits weak load ratio dependency, while P/M and I/M Al–7Mg exhibit modest load ratio dependency. The environmental effect on the fatigue crack growth rates is assessed by determining the difference in crack growth driving force (ΔK) between air and vacuum. It was found that the environmental contribution to the driving force of all three materials is similar, nearly independent of grain size.     

Dielectric and electrostrictive properties of PMNT near MPB

The dielectric constant (ε_r), dielectric loss (tan δ) and strain induced by electric field in lead magnesium niobate–lead titanate (PMN-PT/PMNT) solid solutions in the morphotropic phase boundary (MPB) region at different sintering temperatures have been studied. ε_r and tan δ increase, whereas Curie phase transition range decreases with the increase in sintering temperature. Strain levels in the range of 0.07–0.2% were obtained. A high saturated strain% 0.19, a high d₃₃ coefficient 320 pm/V and a low strain hysteresis% 3.5 in PMNT 68/32 composition sintered at 1200 °C indicate its suitability for actuator applications.     

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.     

Investigation of hot ductility in Al-killed boron steels

The influence of boron to nitrogen ratio, strain rate and cooling rate on hot ductility of aluminium-killed, low carbon, boron microalloyed steel was investigated. Hot tensile testing was performed on steel samples reheated in argon to 1300 °C, cooled at rates of 0.3, 1.2 and 3.0 °C s⁻¹ to temperatures in the range 750–1050 °C, and then strained to failure at initial strain rates of 1 × 10⁻⁴ or 1 × 10⁻³ s⁻¹. It was found that the steel with a B:N ratio of 0.19 showed deep hot ductility troughs for all tested conditions; the steel with a B:N ratio of 0.47 showed a deep ductility trough for a high cooling rate of 3.0 °C s⁻¹ and the steel with a near-stoichiometric B:N ratio of 0.75 showed no ductility troughs for the tested conditions. The ductility troughs extended from 900 °C (near the Ae₃ temperature) to 1000 or 1050 °C in the single-phase austenite region. The proposed mechanism of hot ductility improvement with increase in B:N ratio in these steels is that the B removes N from solution, thus reducing the strain-induced precipitation of AlN. Additionally, BN co-precipitates with sulphides, preventing precipitation of fine MnS, CuS and FeS, and forming large, complex precipitates that have no effect on hot ductility.     

Low-temperature fabrication of 0.65 PMN–0.35 PT by a mixed oxide method

Single-phase perovskite 0.65 PMN–0.35 PT was achieved at low temperature by a conventional mixed oxide method. It was prepared by ball-milling a mixture of PbO(orthorhombic), TiO₂, Nb₂O₅ and (MgCO₃)₄Mg(OH)₂·5H₂O instead of MgO and heat treatment at 800 °C for 2 h. The formation was studied by means of DSC, FT-IR, Coupled TG-Mass, XRD, and SEM. It proceeded via formation of PbO(tetragonal) and Pb₂Nb₂O₇(P₂N) intermediates to form perovskite phase. The pure perovskite PMN-PT powder was obtained in particle size of 0.5–0.8 μm, agglomerate-free, and pseudo-cube. The powder calcined at 600 °C was sintered to 97% T.D. at 900–1000 °C for 2 h and showed room temperature dielectric constant of 3200, loss of 1–2%, and specific resistance of 5 × 10¹¹ Ω cm.     

Dynamic recrystallization during high temperature deformation of magnesium

As a consequence of the high critical stresses required for the activation of non-basal slip systems, dynamic recrystallization plays a vital role in the deformation of magnesium, particularly at a deformation temperature of 200 °C, where a transition from brittle to ductile behavior is observed. Uniaxial compression tests were performed on an extruded commercial magnesium alloy AZ31 at different temperatures and strain rates to examine the influence of deformation conditions on the dynamic recrystallization (DRX) behavior and texture evolution. Furthermore, the role of the starting texture in the development of the final DRX grain size was investigated. The recrystallized grain size, measured at large strains (  −1.4) seemed to be more dependent on the deformation conditions than on the starting texture. In contrast to pure magnesium, AZ31 does not undergo grain growth at elevated deformation temperatures, i.e. 400 °C, even at a low strain rate of 10⁻⁴ s⁻¹. Certain deformation conditions gave rise to a desired fully recrystallized microstructure with an average grain size of 18 μm and an almost random crystallographic texture. For samples deformed at 200 °C/10⁻² s⁻¹, optical microscopy revealed DRX inside of deformation twins, which was further investigated by EBSD.     

Mechanical and thermal properties of AlN–BN–SiC ceramics

Mechanical and thermal properties were characterized for two AlN:BN:SiC composite ceramics produced from BN with different particle sizes. The ceramics were hot pressed at temperatures from 1950 to 2100 °C to 97% relative density. For both materials, the matrix (90:10 vol% SiC:AlN) had a grain size of 0.4 μm, and the BN grains (10 vol%) were crystallographically aligned. Microhardness values were between 20 and 22 GPa, while fracture toughness values were between 2.5 and 3.1 MPa m^1/2. Other properties were found to be dependent on testing direction. Elastic moduli were between 260 and 300 GPa and strengths were 630 MPa for small particle BN additions. Thermal conductivity was calculated to be between 25 and 37 W/m K at room temperature and 17 and 25 W/m K at 900 °C. The low values compared to traditional SiC ceramics were attributed to AlN–SiC solid solution formation and sub-micron matrix grain sizes.     

From iron(III) precursor to magnetite and vice versa

The syntheses of nanosize magnetite particles by wet-chemical oxidation of Fe²⁺ have been extensively investigated. In the present investigation the nanosize magnetite particles were synthesised without using the Fe(II) precursor. This was achieved by γ-irradiation of water-in-oil microemulsion containing only the Fe(III) precursor. The corresponding phase transformations were monitored. Microemulsions (pH  12.5) were γ-irradiated at a relatively high dose rate of 22 kGy/h. Upon 1 h of γ-irradiation the XRD pattern of the precipitate showed goethite and unidentified low-intensity peaks. Upon 6 h of γ-irradiation, reductive conditions were achieved and substoichiometric magnetite (Fe_2.71O₄) particles with insignificant amount of goethite particles found in the precipitate. Hydrated electrons , organic radicals and hydrogen gas as radiolytic products were responsible for the reductive dissolution of iron oxide in the microemulsion and the reduction Fe³⁺ → Fe²⁺. Upon 18 h of γ-irradiation the precipitate exhibited dual behaviour, it was a more oxidised product than the precipitate obtained after 6 h of γ-irradiation, but it contained magnetite particles in a more reduced form (Fe_2.93O₄). It was presumed that the reduction and oxidation processes existed as concurrent competitive processes in the microemulsion. After 18 h of γ-irradiation the pH of the medium shifted from the alkaline to the acidic range. The high dose rate of 22 kGy/h was directly responsible for this shift to the acidic range. At a slightly acidic pH a further reduction of Fe³⁺ → Fe²⁺ resulted in the formation of more stoichiometric magnetite particles, whereas the oxidation conditions in the acidic medium permitted the oxidation Fe²⁺ → Fe³⁺. The Fe³⁺ was much less soluble in the acidic medium and it hydrolysed and recrystallised as goethite. The γ-irradiation of the microemulsion for 25 h at a lower dose rate of 16 kGy/h produced pure substoichiometric nanosize magnetite particles of about 25 nm in size and with the stoichiometry of Fe_2.83O₄.     

Visualization of emitting sites on carbon fiber cathode by surface treatment in high-current vacuum discharge process

In this paper, a carbon fiber cathode, having robust, easily shaped, and epoxy-free properties, is constructed by squeeze casting technique that can overcome some disadvantages of conventional methods. Carbon fiber emitters on the cathode surface had a high distribution density, thus ensuring sufficient emission centers or emission uniformity. The fabricated cathode was tested in a diode powered by a 350 kV, 40 Ω, 400 ns high-voltage pulse generator. The turn-on electric field was estimated to be 50 kV/cm, and the field enhancement factor was (1.2–2.0) × 10³. It was found that the electron emission of carbon fiber cathode is initiated from the individual bright spots at a current density of up to 400 A/cm². Most notably, the X-ray images of electron beam on anode foil demonstrate the development of bright spots on the cathode surface. As a whole, this class of cathodes can endure high-current pulsed emission, and has a positive application prospect.     

A constitutive model for high strain rate deformation in FCC metals based on irreversible thermodynamics

The present work extends a recent model for plastic deformation of polycrystalline metals based on irreversible thermodynamics. A general dislocation evolution equation is derived for a wide range of strain rates. It is found that there is a transitional strain rate (10³ s⁻¹) over which the phonon drag effects play a dominant role in dislocation generation resulting in a significant raise in the dislocation density and flow stress. The model reduces to the classical Kocks–Mecking model at low strain rates.     

Superplastic behavior of a fine-grained ZK60 magnesium alloy processed by high-ratio differential speed rolling

Grain size of the ZK60 alloy was effectively reduced to 12 μm through high-ratio differential speed rolling (HRDSR) for a thickness reduction of 70% in a single pass. Due to the strengthening effects of grain boundaries and particles, the HRDSR processed ZK60 exhibited a high tensile strength of 340 MPa. Low temperature superplasticity was attained at 473–493 K at low strain rates (5 × 10⁻⁴ s⁻¹) and high strain rate superplasticity was attained at 523–553 K at high strain rates (10⁻² s⁻¹). The optimum superplastic temperature was found to be 553 K where a maximum tensile elongation of 1000% was obtained at 1 × 10⁻³ s⁻¹. The deformation behavior of the HRDSR processed ZK60 at elevated temperatures could be depicted by considering contribution of grain boundary sliding and slip creep to total plastic flow. Difference in superplastic deformation behavior between the HRDSR processed and equal channel angular press processed ZK60 alloys was examined and discussed.     

First-principles study of phase transition and structural properties of AlAs

We have investigated the phase transition and structural properties of AlAs in three crystallographic structures, i.e., B3 (zinc blende), B1 (rocksalt), and B8 (nickel arsenide), at high pressures using the full-potential linearized muffin-tin orbital (FP-LMTO) scheme within the generalized gradient approximation correction (GGA) in the frame of density functional theory (DFT). For B8 structure, it is found that the c/a ratios kept nearly constant (0.2% fluctuation) corresponding to V/V₀  0.7–1.05 (V is the primitive cell volume and V₀ is the experimental equilibrium volume of B3 structure), which is in full agreement with experiment, but the c/a ratios increase linearly with the values of V/V₀ decreasing corresponding to V/V₀  0.4–0.7. This indicates under low pressure the compression along c-axis and a-axis is the same, but the compression along c-axis is more difficult than along a-axis under higher pressure. Based on the condition of equal enthalpies AlAs is found to undergo a structural phase transition from B3 to B8 at 5.34 GPa, in agreement with the experimental value of 7 ± 5 GPa, and is speculated to undergo the B3–B1 transition at 6.24 GPa.     

Radioactivity contents in dicalcium phosphate and the potential radiological risk to human populations

Potentially harmful phosphate-based products derived from the wet acid digestion of phosphate rock represent one of the most serious problems facing the phosphate industry. This is particularly true for dicalcium phosphate (DCP), a food additive produced from either sulphuric acid or hydrochloric acid digestion of raw rock material. This study determined the natural occurring radionuclide concentrations of 12 DCP samples and 4 tricalcium phosphate (TCP) samples used for animal and human consumption, respectively. Metal concentrations (Al, Fe, Zn, Cd, Cr, As, Hg, Pb and Mg) were also determined. Samples were grouped into three different clusters (A, B, C) based on their radionuclide content. Whereas group A is characterized by high activities of ²³⁸U, ²³⁴U (10³ Bq kg⁻¹), ²¹⁰Pb (2 × 10³ Bq kg⁻¹) and ²¹⁰Po (800 Bq kg⁻¹); group B presents high activities of ²³⁸U, ²³⁴U and ²³⁰Th (10³ Bq kg⁻¹). Group C was characterized by very low activities of all radionuclides (<50 Bq kg⁻¹). Differences between the two groups of DCP samples for animal consumption (groups A and B) were related to the wet acid digestion method used, with group A samples produced from hydrochloric acid digestion, and group B samples produced using sulphuric acid. Group C includes more purified samples required for human consumption. High radionuclide concentrations in some DCP samples (reaching 2 × 10³ and 10³ Bq kg⁻¹ of ²¹⁰Pb and ²¹⁰Po, respectively) may be of concern due to direct or indirect radiological exposure via ingestion. Our experimental results based on ²¹⁰Pb and ²¹⁰Po within poultry consumed by humans, suggest that the maximum radiological doses are 11 ± 2 μSv y⁻¹. While these results suggest that human health risks are small, additional testing should be conducted.     

Electric field control photo-induced Hall currents in semiconductors

We generate spin-polarized carrier populations in GaAs and low temperature-grown GaAs (LT-GaAs) by circularly polarized optical beams and pull them by external electric fields to create spin-polarized currents. In the presence of the optically generated spin currents, anomalous Hall currents with an enhancement with increasing doping are observed and found to be almost steady in moderate electric fields up to 120 mV μm⁻¹, indicating that photo-induced spin orientation of electrons is preserved in these systems. However, a field 300 mV μm⁻¹ completely destroys the electron spin polarization due to an increase of the D’yakonov–Perel’ spin precession frequency of the hot electrons. This suggests that high field carrier transport conditions might not be suitable for spin-based technology with GaAs and LT-GaAs. It is also demonstrated that the presence of the excess arsenic sites in LT-GaAs might not affect the spin relaxation by Bir–Aronov–Pikus mechanism owing to a large number of electrons in n-doped materials.