Growth kinetics of tin oxide nanocrystals in colloidal suspensions under hydrothermal conditions

Colloidal suspensions of tin oxide nanocrystals were synthesized at room temperature by the hydrolysis reaction of tin chloride (II), in an ethanolic solution. The coarsening kinetics of such nanocrystals was studied by submitting the as-prepared suspensions to hydrothermal treatments at temperatures of 100, 150 and 200 degrees C for periods between 60 and 12,000 min. Transmission electron microscopy (TEM) was used to characterize the samples (i.e. distribution of nanocrystal size, average particle radius and morphology). The results show that the usual Ostwald ripening coarsening mechanism does not fit well the experimental data, which is an indicative that this process is not significant for SnO2 nanocrystals, in the studied experimental conditions. The morphology evolution of the nanocrystals upon hydrothermal treatment indicates that growth by oriented attachment (OA) should be significant. A kinetic model that describes OA growth is successfully applied to fit the data. (c) 2006 Elsevier B.V. All rights reserved.

Sensitized thulium blue upconversion emission in Nd3+/Tm3+/Yb3+ triply doped lead and cadmium germanate glass excited around 800 nm

Bright blue upconversion emission by thulium ions in PbGeO3-PbF2-CdF2 glass triply doped with Nd3+-Tm3+-Yb3+ under diode laser excitation around 800 nm is reported. The results revealed that the Nd3+/Tm3+/Yb3+-codoped sample generated ten times more 475 nm blue upconversion fluorescence than the Yb3+-sensitized Tm3+-doped one, under the same excitation power. The upconversion process also showed a strong dependence upon the Yb3+ concentration. The results also indicated that the neodymium ions played a major role in the upconversion process by transfering the 800 nm excitation to thulium ions. The population of the Tm3+ ions (1)G(4) emitting level was accomplished through a multiion interaction involving ground-state absorption of pump photons around 800 nm by the Nd3+(I-4(9/2)-->H-2(9/2), F-4(5/2)) and Tm3+(H-3(6)-->F-3(4)) ions followed by energy-transfer processes involving the Nd3+-Yb3+(F-4(3/2), F-2(7/2)-->I-4(11/2), F-2(5/2)) and Yb3+-Tm3+(F-2(5/2), F-3(4)-->F-2(7/2), (1)G(4)) pairs. (C) 2003 American Institute of Physics.

Use of sugar cane bagasse as solid phase extractor for cadmium determination by FAAS

The present paper describes the use of sugar cane bagasse as solid phase extractor for cadmium determination after complexation of the analyte with ammonium diethyldithiophosphate (ADDP) and sorption of the Cd-DDP complexes on the solid support. The concomitants were separated using a flow injection analysis (FIA) system coupled to flame atomic absorption spectrometry (FAAS) for determination. The main parameters such as ADDP concentration, acid medium, flow rate, reaction coil length, and reaction time were investigated.The results obtained with HNO3 showed good accuracy and precision. The enhancement factor was 20.5 times for a 120-second preconcentration time, and the analytical frequency was 25 determinations per hour. The calibration curve was linear over the concentration range of 1-40 mu g L-1 Cd with a LOD of 0.697 mu g L-1 Cd and a relative standard deviation of 0.96% after 12 successive measurements of 30 mu g L-1 Cd.The proposed method was evaluated for the FIA-FAAS analysis of certified reference materials (tomato leaves, spinach leaves, and bovine liver) and Cd-spiked foods (shrimp, sardine, tuna, chicken liver and bovine liver). Good recoveries (80.0-97.1%) for the Cd-spiked samples and certified reference materials were obtained. The results of bagasse-packed minicolumns were compared with Si-C,8 packed minicolumns. The F-test was applied between Si-C-18/Bagasse minicolumns, Si-C-18/certified values, and bagasse/certified values. It was found that the results were in agreement with the certified values at a 95% confidence level.

Analyses of fatigue data in 4340 high strength steel after cadmium electroplating

Bending fatigue tests were carried out to clarify the effects of heat treatment parameters: temperature and time after cadmium electroplating on a high strength steel, to avoid hydrogen embrittlement. Temperatures heat of 190 degrees C, 230 degrees C, 250 degrees C and 300 degrees C at 3, 8 and 24 hours together with the base material electroplated, with and without heat treatment, resulted in 14 conditions studied with respect to fatigue behaviour. Statistical data analysis was performed to identify the best combination temperature/time regarding fatigue strength of the ABNT 4340 steel and the results obtained revealed that the fatigue strength depend on temperature/time conditions.

Simultaneous determination of zinc, copper, lead, and cadmium in fuel ethanol by anodic stripping voltammetry using a glassy carbon-mercury-film electrode

A new, versatile, and simple method for quantitative analysis of zinc, copper, lead, and cadmium in fuel ethanol by anodic stripping voltammetry is described. These metals can be quantified by direct dissolution of fuel ethanol in water and subsequent voltammetric measurement after the accumulation step. A maximum limit of 20% (v/v) ethanol in water solution was obtained for voltammetric measurements without loss of sensitivity for metal species. Chemical and operational optimum conditions were analyzed in this study; the values obtained were pH 2.9, a 4.7-mum thickness mercury film, a 1,000-rpm rotation frequency of the working electrode, and a 600-s pre-concentration time. Voltammetric measurements were obtained using linear scan (LSV), differential pulse (DPV), and square wave (SWV) modes and detection limits were in the range 10(-9)-10(-8) mol L-1 for these metal species. The proposed method was compared with a traditional analytical technique, flame atomic absorption spectrometry (FAAS), for quantification of these metal species in commercial fuel ethanol samples.

Simultaneous determination of cadmium and lead in wine by electrothermal atomic absorption spectrometry

A method has been developed for the direct simultaneous determination of Cd and Pb in white and red wine by electrothermal atomic absorption spectrometry (ET-AAS) using a transversely heated graphite tube atomizer (THGA) with longitudinal Zeeman-effect background correction. The thermal behavior of both analytes during pyrolysis and atomization stages were investigated in 0.028 mol l(-1) HNO3 and in 1 + 1 v/v diluted wine using mixtures of Pd(NO3)(2) + Mg(NO3)(2) and NH4H2PO4 + Mg(NO3)(2) as chemical modifiers. With 5 mug Pd + 3 mug Mg as the modifiers and a two-step pyrolysis (10 s at 400 degreesC and 10 s at 600 degreesC), the formation of carbonaceous residues inside the atomizer was avoided. For 20 mul of sample (wine + 0.056 mol l(-1) HNO3, 1 + 1, v/v) dispensed into the graphite tube, analytical curves in the 0.10-1.0 mug l(-1) Cd and 5.0-50 mug l(-1) Pb ranges were established. The characteristic mass was approximately 0.6 pg for Cd and 33 pg for Pb, and the lifetime of the tube was approximately 400 firings. The limits of detection (LOD) based on integrated absorbance (0.03 mug l(-1) for Cd, 0.8 mug l(-1) for Pb) exceeded the requirements of Brazilian Food Regulations (decree #55871 from Health Department), which establish the maximum permissible level for Cd at 200 mug l(-1) and for Pb at 500 mug l(-1). The relative standard deviations (n = 12) were typically < 8% for Cd and < 6% for Pb. The recoveries of Cd and Pb added to wine samples varied from 88 to 107% and 93 to 103%, respectively. The accuracy of the direct determination of Cd and Ph was checked for 10 table wines by comparing the results with those obtained for digested wine using single-element ET-AAS, which were in agreement at the 95% confidence level. (C) 2001 Elsevier B.V. B.V. All rights reserved.

Lead-cadmium oxyfluoride glasses and glass-ceramics

Glasses and glass-ceramics have been obtained in oxyfluoride systems involving lead and cadmium fluorides and one of the well-known glass former oxides SiO2, B2O3 and TeO2. Vitreous domains were established and a wide range of compositions including high heavy metal contents lead to stable glasses. Amorphous structures have been studied by short-range order spectroscopy techniques (Raman scattering and x-ray absorption) and molecular basic structures have been identified. Besides the usual oxides, the role of glass former could also be proposed for cadmium ions. Special attention has been paid for crystallization process. Cubic lead fluoride, cubic lead tellurite, tetragonal tellurium oxide and a solid solution of the type Pb1-xCdxF2 are obtained as crystallization products depending on the composition and temperature of heat treatments. Pb1-xCdxF2 solid solutions are well known superionic materials and obtaining this solid solution as a crystal phase could be very interesting for applications concerning ionic electrical conduction properties. The addition of rare earth ions led to the control of the crystallization process. In the presence of the nucleating ion only the cubic form beta-PbF2 was identified. Rare earth ions are present in the crystal phase and crystal-like spectroscopic properties were observed suggesting interesting applications for these perfectly transparent glass ceramics in photonics.

Red, green, and blue upconversion luminescence in ytterbium-sensitized praseodymium-doped lead-cadmium-germanate glass

Blue, green, red, and near-infrared upconversion luminescence in the wavelength region of 480-740 nm in Pr3+/Yb3+-codoped lead-cadmium-germanate glass under 980 nm diode laser excitation, is presented. Upconversion emission peaks around 485, 530, 610, 645, and 725 nm which were ascribed to the P-3(0)-H-3(J) (J = 4, 5, and 6), and P-3(0)-F-3(J) (J = 2, 3, and 4), transitions, respectively, were observed. The population of the praseodymium upper P-3(0) emitting level was accomplished through a combination of ground-state absorption of Yb3+ ions at the F-2(7/2), energy-transfer Yb3+(2F(5/2))-Pr3+(H-3(4)), and excited-state absorption of Pr3+ ions provoking the (1)G(4)-P-3(0) transition. The dependence of the upconversion luminescence upon the Yb3+-concentration and diode laser power, is also examined, in order to subsidize the proposed upconversion excitation mechanism. (C) 2004 Elsevier B,V. All rights reserved.

In situ UV-vis and EXAFS studies of ZnO quantum-sized nanocrystals and Zn-HDS formations from sol-gel route

We have pointed Out that. zinc-based particles obtained from zinc acetate sol-gel route is a mixture of quantum-sized ZnO nanoparticles, zinc acetate, and zinc hydroxide double salt (Zn-HDS). Aiming the knowledge of the mechanisms involved in the formation of ZnO and Zn-HDS phases, the thermohydrolysis of ethanolic zinc acetate solutions induced by lithium hydroxide ([LiOH]/[Zn2+] = 0.1) or water ([H2O]/[Zn2+] = 0.05) addition was investigated at different isothermal temperatures (40, 50, 60 and 70 degrees C) by in situ measurements of turbidity, UV-vis absorption spectra and extended X-ray absorption fine structures (EXAFS). Only the growth of ZnO nanoparticles was observed in sol prepared with LiOH, while a two-step process was observed in that prepared with water addition, leading the fast growth of Zn-HDS and the formation of ZnO nanoparticles at advanced stage. A mechanism of dissolution/reprecipitation governed by the water/ethanol proportion is proposed to account for relative amount of ZnO. (c) 2007 Elsevier Ltd. All rights reserved.

Environmental cadmium exposure and metabolic responses of the Nile tilapia, Oreochromis niloticus

The contamination of water by metal compounds is a worldwide environmental problem. This study was undertaken to evaluate the impact of short-term cadmium exposure on metabolic patterns of the freshwater fish Oreochromis niloticus. The fish were exposed to 320, 640, 1280 and 2560 mug/l sublethal concentrations of Cd++ (CdCl2) in water for 7 days. The specific activities of the enzymes phosphofructo kinase (PFK-E.C.2.7.1.11.), lactate dehydrogenase (LDH-E.C.1.1.1.27.) and creatine kinase (CK-E.C.2.7.3.2.) were decreased in white muscle after cadmium treatments, indicating decreases in the capacity of glycolysis in this tissue. Cadmium exposure induced increased glucose concentration in white muscle of fish. on the other hand, cadmium exposure at sublethal concentrations increased phosphofructo kinase and LDH in red muscle of fish. Cadmium significantly decreased total protein concentrations in liver and white muscle regardless of tissue glycogen levels. The data suggest that cadmium acts as a stressor, leading to metabolic alterations similar to those observed in starvation. (C) 2001 Elsevier B.V. Ltd. All rights reserved.

Upconversion luminescence in transparent glass ceramics containing beta-PbF2 nanocrystals doped with erbium

Frequency upconversion luminescence in erbium-doped PbGeO3-PbF2-CdF2-based transparent glass ceramics (TGC) under 980 nm infrared excitation is investigated. Upconversion emission signals around 410, 525, 550, 660, and 850 nm were generated and identified as due to the H-2(9/2) H-2(11/2), S-4(3/2), and F-4(9/2) transitions to the I-4(15/2) ground-state, and S-4(3/2)-I-4(13/2), respectively. The erbium ions excited-state emitting levels were populated via a combination of stepwise ground-state absorption (GSA), excited-state absorption (ESA), and cross-relaxation processes. The results also disclosed that both blue (410 nm) and red (660 nm) upconversion emission signals in the transparent glass ceramic sample presented twice as much intensity as compared to its vitreous counterpart. (C) 2003 Elsevier B.V. All rights reserved.

Differential/combined effect of water contamination with cadmium and nickel on tissues of rats

The contamination of water by metal compounds is a worldwide environmental problem. Concentrations of metals are widely related to biochemical values which are used in disease diagnosis due to environmental toxicity. The acute combined effects of cadmium and nickel on biochemical parameters were determined and compared with those of Cd2+ or Ni2+ alone in rats. Male adult rats were given drinking solutions of CdCl2 [Cd(II) cation, 100 mg/liter] or NiSO4 [Ni(II) cation, 100 mg/liter]. For the combined treatment, the animals (Ni+Cd) received both Ni(II)) cation (100 mg/liter) and Cd(II) cation (100 mg/liter). Nickel treatment induced increased alanine transaminase (ALT) activity and hepatotoxicity, but not renal injury. In contrast, cadmium exposure produced hepatic, renal and myocardial damage, characterized by increased creatinine, total and direct bilirubin concentrations and increased ALT and lactate dehydrogenase (LDH) activities. The combined effect Ni-Cd is less toxic than cadmium alone, suggesting antagonism between these toxicants. The toxicity of nickel and cadmium, alone and in combination, decreased Cu-Zn superoxide dismutase (SOD) activity and increased lipoperoxide formation. (C) 1998 Elsevier B.V. Ltd. All rights reserved.

Role of the oriented attachment mechanism in the phase transformation of oxide nanocrystals

Bottom-up methods to obtain nanocrystals usually result in metastable phases, even in processes carried out at room temperature or under soft annealing conditions. However, stable phases, often associated with anisotropic shapes, are obtained in only a few special cases. In this paper we report on the synthesis of two well-studied oxides-titanium and zirconium oxide-in the nanometric range, by a novel route based on the decomposition of peroxide complexes of the two metals under hydrothermal soft conditions, obtaining metastable and stable phases in both cases through transformation. High-resolution transmission electron microscopy analysis reveals the existence of typical defects relating to growth by the oriented attachment mechanism in the stable crystals. The results suggest that the mechanism is associated to the phase transformation of these structures.

An investigation of cadmium(II) and nickel(II) adsorption by chitin graft covolymer

Chitin hydrogels of poly(vinylpyrrolidone) (VP) were prepared by means of the hydrogen peroxide graft copolymerization process. The effect of the VP grafted chain on water diffusion through the biopolymer was studied. Fourier transform infrared spectra of the VP-g-Ch showed an increase in the intensities of the hydroxyl and carbonyl stretching bands indicating a reduction in the hydrogen bonding of chitin. An investigation was undertaken regarding the adsorption of nickel(II) and cadmium(II) ions from aqueous solutions by the VP grafted chitin and the effects of the grafting degree on the Cd2+ and Ni2+ sorption were studied. The Cd2+ and Ni2+ adsorption equilibrium data correlate well with the Freundlich equation. The results indicate that the Ch-g-VP graft copolymer under investigation is a potentially powerful chelating material that can be employed for Ni2+ and Cd2+ ion removal from wastewater effluents. (C) 2004 Wiley Periodicals, Inc.