Preparation of biomorphic porous calcium titanate and its application for preconcentration of nickel in water and food samples

Biomorphic porous nanocrystalline-calcium titanate (SPCTO) was successfully prepared using the sol–gel method and with sorghum straw as the template. Characterization was conducted through XRD, SEM and FTIR. The ability of SPCTO to adsorb nickel ion in water was assessed. Elution and regeneration conditions, as well as the thermodynamics and kinetics of nickel adsorption, were also investigated. The result showed that the sorbent by the sol–gel template method was porous and has a perovskite structure with an average particle diameter of 26 nm. The nickel ion could be quantitatively retained at a pH value range of 4–8, but the adsorbed nickel ion could be completely eluted using 2 mol L^? 1 HNO₃. The adsorption capacity of SPCTO for nickel was found to be 51.814 mg g^? 1 and the adsorption behavior followed a Langmuir adsorption isotherm and a pseudo-second-order kinetic model. The enthalpy change (ΔH) of the adsorption process was 33.520 kJ mol^? 1. At various temperatures, Gibbs free energy changes (ΔG) were negative, and entropy changes (ΔS) were positive. The activation energy (E_a) was 25.291 kJ mol^? 1 for the adsorption. These results demonstrate that the adsorption was an endothermic and spontaneous physical process. This same method has been successfully applied in the preconcentration and determination of nickel in water and food samples with good results.     

Site-specific Eu(III) binding affinities to a Datura innoxia biosorbent

The binding of Eu(III) to a biosorbent derived from cultured cells of the plant Datura innoxia, have been investigated through elucidation of apparent affinity constants associated with different chemical environments present on the cell wall. Adsorption isotherms for separate types of binding sites were generated using metal ion luminescence measurements. Application of regularized regression analysis to these isotherm data for four chemically distinguishable sites revealed the presence of sites exhibiting both low (mean log K_app = ?0.3 to 0.6) and higher (mean log K_app = 3.2–3.5) apparent affinities for pH conditions of 2.0, 4.0, and 5.0. Low affinity sites were observed for all pH conditions and attributed to non-specific binding of the metal ions to the negatively charged biomaterial. The pH-dependent higher affinity sites are ascribed to specific sites involving either an ion-exchange mechanism or formation of weak surface–metal ion complexes. These results differed significantly from a similar analysis of total metal binding isotherms that indicated mean log K_app values of ?0.5 to 0.25 (low affinity) and 5.6–6.0 (high affinity).     

Improvement of cycle stability at elevated temperature and high rate for LiNi0.5−xCuxMn1.5O4 cathode material after Cu substitution

A series of Cu-substituted LiNi_0.5−xCu_xMn_1.5O₄ (x = 0, 0.03, 0.05 and 0.08) spinels have been synthesized using a sol–gel method. The results demonstrate that when x = 0.05, the sample (LiNi_0.45Cu_0.05Mn_1.5O₄) exhibits the best electrochemical performance, achieving 124.5 mAh g⁻¹ and 115.0 mAh g⁻¹ at the discharge rates of 5 C and 20 C with the capacity retention of 97.7% and 95.7% after 150 cycles, respectively. Besides, the excellent cycle stability at 55 °C has been demonstrated to retain 96.8% of the maximum attainable discharge capacity (127.3 mAh g⁻¹) at the discharge rate of 5 C after 100 cycles. These data indicate that the LiNi_0.45Cu_0.05Mn_1.5O₄ cathode material has the real potential to be used for high power and high energy lithium ion battery in electric vehicle applications.     

Picosecond measurement of the nonlinear refractive index of new salts of carboxylate anions with chiral ammonium cations

The third order nonlinear optical properties of novel carboxylate anions with chiral amines and ammonium cations have been studied by a new alternative of the classical z-scan technique with picosecond laser pulses (pulse duration of 30 ps at 1064 nm wavelength). The materials do not present linear and nonlinear (two-photon) absorptions at the wavelength and the intensities used for the experiments. The non-resonant molecular second order hyperpolarizability γ obtained can reach 4.4 × 10⁻⁴⁸ SI. These values are two and three orders of magnitude larger than those CS₂ and of C₆H₆ respectively.     

Luminescent properties of Pb2MoO5 single crystals

Lanarkite type Pb₂MoO₅ single crystals were grown using low temperature gradient Czochralski technique and their optical and luminescent properties were studied. The luminescence band at 590–600 nm was observed under UV and X-ray excitations and ascribed to emission of self-trapped excitons. The band is thermally quenched at T > 15 K with the activation energy of process, E_act = 11 meV. The measurements of thermostimulated luminescence demonstrated the presence of shallow traps, which adversely influence the energy transfer to the emission centers.     

Impression creep behavior of a cast MRI153 magnesium alloy

Creep behavior of a cast MRI153 magnesium alloy was investigated using impression creep technique. The tests were carried out under constant punching stress in the range of 360–600 MPa at temperatures between 425 and 490 K. Microstructure of the alloy was composed of α(Mg) matrix phase besides Mg₁₇Al₁₂ and Al₂Ca intermetallic compounds. Stress exponent of minimum creep rate, n, was found to vary between 6.45 and 7. Calculation of the activation energy showed a slight decrease with increasing stress such that the creep activation energy of 115.2 kJ/mol under σ_imp/G = 0.030 decreased to 99.5 kJ/mol under σ_imp/G = 0.040. The obtained stress exponent and activation energy data suggested that the pipe diffusion dislocation climb controlled creep as the dominant mechanism during the creep test.     

Influence of Al2O3 on low-field spin-polarized tunneling magnetoresistance of (1 − x) La0.7Ca0.3MnO3 + x Al2O3 composites

In this study we report the effect of Al₂O₃ on the low field magnetoresistance (LFMR) of (1 ? x) La_0.7Ca_0.3MnO₃ + x Al₂O₃ composite synthesized through a solid-state reaction method combined with an energy milling method. Based upon a spin-polarized tunneling of conduction electrons at the grain boundaries, we have proposed a phenomenological model to explain the observed electrical transport behavior over the whole temperature range (5  300 K), especially the gradual drop of metal-insulator transition temperature (T_p = T_max) as a function of increasing Al₂O₃ content, while the ferromagnetic–paramagnetic transition temperature (T_C) remains almost constant (T_C = 250 K).     

Influence of Yttrium on optical,structural and photoluminescence properties of ZnO nanopowders by sol–gel method

Undoped and Yttrium doped ZnO nanopowders (Zn_1−xY_xO, 0 ⩽ x ⩽ 0.05) were prepared by sol–gel method and annealed at 500 °C for 4 h under air atmosphere. The prepared nanopowders were characterized by powder X-ray diffraction, energy dispersive X-ray spectra, UV–Visible spectrophotometer and Fourier transform infrared spectroscopy. The EDS analysis confirmed the presence of Y in the ZnO system. Both atomic and weight percentages were nearly equal to their nominal stoichiometry within the experimental error. XRD measurement revealed the prepared nanoparticles have different microstructures without changing a hexagonal wurtzite structure. The calculated average crystallite size decreased from 26.1 to 23.2 nm for x = 0–0.02 then reached 24.1 nm for x = 0.05. The change in lattice parameters was demonstrated by the crystal size, bond length, micro-strain and the quantum confinement effect. The observed blue shift of energy gap from 3.36 eV (Y = 0) to 3. 76 eV (Y = 0.05) (ΔE_g = 0.4 eV) revealed the substitution of Y³⁺ ions into ZnO lattice. The presence of functional groups and the chemical bonding are confirmed by FTIR spectra. The appreciable enhancement of PL intensity with slight blue shift in near band edge (NBE) emission from 396 to 387 nm and a red shift of green band (GB) emission from 513 to 527 nm with large reduction in intensity confirm the substitution of Y into the ZnO lattice. Y-doped ZnO is useful to tune the emission wavelength and hence is appreciable for the development of supersensitive UV detector.     

Synthesis and structure determination of new open-framework chromium carboxylate MIL-105 or CrIII(OH)·{O2C–C6(CH3)4–CO2}·nH2O

Two new three-dimensional chromium(III) dicarboxylate, MIL-105 or Cr^III(OH)·{O₂C-C₆(CH₃)₄-CO₂}·nH₂O, have been obtained under hydrothermal conditions, and their structures solved using X-ray powder diffraction data. Both solids are structural analogs of the known Cr benzenedicarboxylate compound (MIL-53). Both contain trans corner-sharing CrO₄(OH)₂ octahedral chains connected by tetramethylterephthalate di-anions. Each chain is linked by the ligands to four other chains to form a three-dimensional framework with an array of 1D pores channels. The pores of the high temperature form of the solid, MIL-105ht, are empty. However, MIL-105ht re-hydrates at room temperature to finally give MIL-105lt with pores channels filled with free water molecules (lt: low temperature form; ht: high temperature form). The thermal behaviour of the two solids has been investigated using TGA. Crystal data for MIL-105ht: monoclinic space group C2/c with a = 19.653(1) Å, b = 9.984(1) Å, c = 6.970(1) Å, β = 110.67(1)° and Z = 4. Crystal data for MIL-105lt: orthorhombic space group Pnam with a = 17.892(1) Å, b = 11.165(1) Å, c = 6.916(1) Å and Z = 4.     

Ionic conductivity of high-purity Gd-doped ceria solid solutions

The Ce_1−xGd_xO_2−δ (0.02 ≤ x ≤ 0.3) solid solutions with ∼30 ppm SiO₂ were prepared through the conventional mixed-oxide method from high-purity CeO₂ and Gd₂O₃ powders. The ionic conductivity (especially the grain boundary (GB) conduction) in this system was studied as a function of dopant content, over the temperature range of 250–750 °C in air, using an impedance spectroscopy. The GB impedance played an important role in the total conduction in the samples with low Gd content (usually x ≤ 0.1), but decreased sharply with increasing Gd content. Both the total and GB conductivities maximized at the composition x = 0.15, and this composition also had the lowest activation energies for the total and GB conduction. The maximum total conductivity at 700 °C, σ_t = 4.07 (Ω m)⁻¹ with the activation energy, E_t = 0.77 eV, was found for the composition x = 0.15.     

Development of an inconel self powered neutron detector for in-core reactor monitoring

The paper describes the development and testing of an Inconel600 (2 mm diameter×21 cm long) self-powered neutron detector for in-core neutron monitoring. The detector has 3.5 mm overall diameter and 22 cm length and is integrally coupled to a 12 m long mineral insulated cable. The performance of the detector was compared with cobalt and platinum detectors of similar dimensions. Gamma sensitivity measurements performed at the ⁶⁰Co irradiation facility in 14 MR/h gamma field showed values of −4.4×10⁻¹⁸ A/R/h/cm (−9.3×10⁻²⁴ A/γ/cm²-s/cm), −5.2×10⁻¹⁸ A/R/h/cm (−1.133×10⁻²³ A/γ/cm²-s/cm) and 34×10⁻¹⁸ A/R/h/cm (7.14×10⁻²³ A/γ/cm²-s/cm) for the Inconel, Co and Pt detectors, respectively. The detectors together with a miniature gamma ion chamber and fission chamber were tested in the in-core Apsara Swimming Pool type reactor. The ion chambers were used to estimate the neutron and gamma fields. With an effective neutron cross-section of 4b, the Inconel detector has a total sensitivity of 6×10⁻²³ A/nv/cm while the corresponding sensitivities for the platinum and cobalt detectors were 1.69×10⁻²² and 2.64×10⁻²² A/nv/cm. The linearity of the detector responses at power levels ranging from 100 to 200 kW was within ±5%. The response of the detectors to reactor scram showed that the prompt response of the Inconel detector was 0.95 while it was 0.7 and 0.95 for the platinum and cobalt self-powered detectors, respectively. The detector was also installed in the horizontal flux unit of 540 MW Pressurised Heavy Water Reactor (PHWR). The neutron flux at the detector location was calculated by Triveni code. The detector response was measured from 0.02% to 0.07% of full power and showed good correlation between power level and detector signals. Long-term tests and the dynamic response of the detector to shut down in PHWR are in progress.     

Mechanism of low energy S+ ion bombarded p-GaAs (100)

X-ray photoelectron spectroscopy (XPS) and low energy electron diffraction (LEED) have been used to characterize the chemical structure and site location of sulfur atom on p-GaAs (100) treated by bombardment of low energy S⁺ ions over the range from 10 to 100 eV. S⁺ ion bombardment resulted in the formation of Ga–S and As–S species on GaAs surface. It was found that the S⁺ ions with energy above 50 eV were more effective in formation of Ga–S species, which assisted the GaAs (100) surface in reconstruction into an ordered (1 × 1) structure upon annealing. After taking into account physical damage due to the process of ion bombardment, we found that 50 eV was the optimal ion energy to form Ga–S species in the sulfur passivation of GaAs (100). The subsequent annealing process removed both donor and acceptor states that were introduced during the ion bombardment of GaAs, and resulted in a sharp (1 × 1) LEED pattern.     

Kinetic energy release and mean life time of metastable ions produced from C3H3N

Metastable ions C₃H_nN⁺ (n = 1, 2 or 3) and C₂H₂⁺ produced by electron impact on the neutral C₃H₃N (acrylonitrile) undergo metastable decay reactions resulting in the fragment ions C₃H_mN⁺ (m = 1, 2) or C₂H₂⁺. We have monitored these reactions in a double focusing mass spectrometer of reversed B-E geometry. To identify the fragment ions and determine their kinetic energy release distribution (KERD), the mass-analyzed ion kinetic energy (MIKE) scan technique was utilized. For the above mentioned ions we obtained average KER values ranging from 9 up to 23 meV. Moreover, the fractions of decaying ions were measured. We have found the existence of two states of the metastable C₂H₂⁺ ion, one with a short life time of about 0.27 μs and the other one which is most likely a completely stable ion state.     

Synthesis and characterization of Bi2S3 nanorods by solvothermal method in polyol media

Bi₂S₃ nanorods were synthesized via a simple solvothermal process in polyol media through the reaction between Bi(NO₃)₃·5H₂O, urea and CS₂ at 150 °C for 15 h using diethylene glycol as solvent. The nanorods were characterized by XRD, TEM and SAED. The results showed that the products were well-crystallized orthorhombic phase with lattice parameters a = 11.15 Å, b = 11.3 Å and c = 3.984 Å, which are consistent with the value in standard JCPDS card No. 17-0320. DEG served as an excellent solvent and structure director. Besides, compared to water and EG as solvents, the DEG system can provide a mild and homogenous condition, which is favorable to anisotropic growth and increases the yield of high quality Bi₂S₃ nanorods. Based on the experimental results, the growth mechanism was discussed.     

Hopping conductivity of metal-dielectric nanocomposites produced by means of magnetron sputtering with the application of oxygen and argon ions

Testing of electrical properties of nanocomposites (Co_0,45Fe_0,45Zr_0,1)_x + (Al₂O₃)_1+x within the concentration range of 0.30 < x < 0.65, produced by means of magnetron sputtering of a target composed of stripes of metallic alloy and dielectric, has been carried out. It has been found that the studied materials contain metallic nanoparticles of a diameter ranging from 6 to 10 nm. Alternating current conduction at x < 0.50 is realized by hopping mechanism while at x > 0.50 metallic conductivity is observed.The obtained results have been analyzed using a model of hopping conductivity in the egime developed earlier. This analysis allowed to extract dependences of activation energy ΔE_τ and times τ in a hopping regime after isochronous (15 min) thermal annealings within the range from 293 K to 673 K.     

Structural and optical properties of BaTi2O5 thin films prepared by pulsed laser deposition at different substrate temperatures

BaTi₂O₅ thin films were prepared on MgO (1 0 0) substrates by pulsed laser deposition. The effect of substrate temperature (T_sub) on the structural and optical properties of the films, such as crystal phase, preferred orientation, crystallinity, surface morphology, optical transmittance and bandgap energy, was investigated. The preferred orientation of the films changed form (7 1 0) to (0 2 0) depending on T_sub, and the b-axis oriented BaTi₂O₅ thin film could be obtained at T_sub = 973–1023 K. The surface morphology of the films was different with changing T_sub, which showed a dense surface with an elongated granular texture at T_sub = 973–1023 K. The crystallinity and surface roughness increased at the elevated substrate temperatures. The as-deposited BaTi₂O₅ thin films were highly transparent with an optical transmittance of ～70%. The bandgap energy was found to decrease with increasing substrate temperature, from 3.76 eV for T_sub = 923 K to 3.56 eV for T_sub = 1023 K.     

Improvement of magnetic properties of nanostructured Ni79Fe16Mo5 alloyed powders by a suitable heat treatment

The supermalloy (Ni₇₉Fe₁₆Mo₅) nanostructured powder with average crystallite size of about 8 nm was prepared by high energy milling. The obtained powders were characterized by X-ray diffraction, scanning electron microscopy, differential scanning calorimetry and vibration sample magnetometer. The results showed that the coercivity and the saturation magnetization reach about 8 Oe and 75 emu/g at 96 h and become approximately 1 Oe and 85 emu/g after a suitable heat treatment, respectively. The magnetic measurements confirmed that the supermalloy soft magnetic nanostructure powder was produced by mechanical alloying followed by a post heat treatment. The results revealed that a small amount of Mo element remain in the system up to 96 h due to (i) high fusion temperature, T_f = 2893 K, (ii) high mechanical hardness, (iii) low solubility of Mo into Ni at low temperatures in mechanical alloying conditions.     

High piezoelectric response in the new coexistent phase boundary of 0.87BaTiO3–(0.13-x)BaZrO3–xCaTiO3

An investigation of the coexistent ferroelectric phase was carried out on the ternary system of 0.87BaTiO₃–(0.13-x)BaZrO₃–xCaTiO₃ [abbreviated as BT–BZ–xCT (where 0.00 ≤ x ≤ 0.13)]. Temperature-, frequency-dependent dielectric data, electric field-dependent strain and polarization as a function of composition are presented in order to understand the relationships of structure-properties and find the high piezoelectric response in this system. Results showed that ceramics in the composition range of 0.00 ≤ x < 0.04 were of a rhombohedral structure and transformed into a tetragonal structure at x > 0.06. The multiphase coexistence of the rhombohedral and tetragonal phase in this system was identified at x = 0.06. A large, virtually hysteresis-free electric field induced strain of 0.23% was achieved with the composition, x = 0.06, at 40 kV/cm on the boundary between rhombohedral and tetragonal phase. This relates to an extraordinarily high and normalized piezoelectric coefficient (S_max/E_max) of 1280 pm/V, which was reached at a low electric field applied at 10 kV/mm. These results indicated that a high piezoelectric response may stem primarily from the rhombohedral-tetragonal phase boundary, due to greater lattice softening and reduced energy barriers for polarized rotation.     

Yellow-emitting (Ca2Lu1−xCex)(ScMg)Si3O12 phosphor and its application for white LEDs

Luminescence properties of the yellow-emitting (Ca₂Lu_1?xCe_x)(ScMg)Si₃O₁₂ (CLSM:xCe³⁺ x = 0.01–0.15) phosphor are investigated for various Ce³⁺ concentrations. Different Ce³⁺ emission sites and energy transfers between them are observed, resulting in a red shift of the emission spectra from 530 to 575 nm with increasing x from 0.01 to 0.15. Combining with blue (460 nm) InGaN LEDs, CLSM:Ce³⁺ shows excellent performances for phosphor-converted white LEDs with higher color rendering index R_a of 87.4–87.9 and lower color temperature T_C of 5034–5814 K, especially for warm pcWLEDs with a high color rendering (R_a > 80) and a low color temperature (T_C < 4000 K). Thermal quenching behaviors depending on Ce³⁺ concentrations and temperatures are discussed.     

Toughening of denture base resin with short deformable fibers

Fracture resistance of polymer reinforced with short fibers consists of a sum of contributions from matrix and fiber fracture, fiber debonding and pull-out. The existing models for predicting dependence of fracture toughness on structural variables were derived for the commercially important fiber volume fractions, i.e., for v_f ? 0.1. In this contribution, modification of the existing model for the dependence of the critical strain energy release rate, G_IC, on the fiber type, length and aspect ratio, interfacial adhesion and volume fraction has been attempted to allow predictions at low v_f < 0.10. The predictions based on the modified model were compared with experimental data on fracture toughness of lightly x-linked PMMA used to manufacture base of removable dentures toughened with short randomly oriented deformable fibers. The composite toughness was measured under impact loading to simulate typical mode of fracture of removable dentures. The G_IC for composites containing short Kevlar 29, S2-glass and poly(vinyl alcohol) (PVOH) fibers were obtained using instrumented Charpy impact tests at room temperature and impact speed of 1.0 m/s. Theoretical prediction based on the proposed model and experimental results agreed reasonably well.