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1.
A novel method for liquid-liquid extraction, separation, preconcentration, and simultaneous trace determination of cerium(IV) and lanthanum(III) with N-phenyl-(1,2-methanofullerene C60)61-formohydroxamic acid (PMFFA) is reported. Lanthanum and cerium are extracted at pH 8.5 and 9.5, respectively in chloroform and recovered from monazite sands in the presence of thorium, uranium, and large number of cations and anions in high purity (99.98%). The extraction mechanism is investigated. The influence of PMFFA, pH, diverse ions, and temperature on the distribution constants of lanthanum and cerium was examined. The overall stability constants (log β2Ke) and extraction constants (Kex) for lanthanum(III) are 22.50 and 5.0 × 10-9, respectively and for cerium(IV) are 21.51 and 3.9 × 10-9, respectively. Lanthanum(III) gives a colourless complex with PMFFA which is extracted into chloroform having molar absorptivity 5.5 × 104 L mol-1 cm-1 at 395 nm, and Beer's law 0.12-2.52 µg mL-1, while cerium(IV) forms a red coloured complex, λmax 460 nm, molar absorptivity 1.5 × 104 L mol-1 cm-1, and Beer's law 0.46-9.26 µg mL-1. For trace determination the extracts were directly inserted into the plasma for inductively coupled plasma atomic emission spectrometry ICP-AES measurements of lanthanum and cerium which increases the sensitivity 60 folds and obey Beer's law in the range, 2.1-37.5 ng mL-1 for lanthanum and 9.2-186.4 ng mL-1 for cerium. The method is applied for the determination of lanthanum and cerium in real and standard samples, sea water, and environmental samples.  相似文献   

2.
A new reagent N-phenyl-(1,2 methanofullerene C60)61-formohydroxamic acid (PMFFA) is reported for extraction and trace determination of vanadium(V) in nutritional and biological substrates. The extraction mechanism of vanadium from 6 M HCl media is investigated. The influence of PMFFA, diverse ions, and temperature on the distribution constant of vanadium examined. The over all stability constant (log β2Ke) and extraction constant (Kex) are 20.89 ± 0.02 and 8.0 ± 0.02 × 10-15, respectively in chloroform. The thermodynamics parameters are calculated and kinetics of vanadium transport is discussed. The system obeys Beer's law in the range of 3.2-64.0 ng mL-1 of vanadium(V). The molar absorptivity is 7.96 × 105 L mol-1 cm-1, at 510 nm. The PMFFA-vanadium(V) complex chloroform extract in chloroform was directly inserted into plasma for ICP-AES measurement, which increases the sensitivity by 50 folds and obey Beer's law in the range of 50-1200 pg mL-1 of vanadium(V). The method is applied for determination vanadium in real standard samples, sea water, and environmental samples.  相似文献   

3.
ZnS-SiO2 targets have been directly soldered to copper backing plates at 180°C in air using an Sn56Bi4Ti(Ce, Ga) filler. The affinity of cerium to oxygen protects titanium from oxidation, allowing titanium to react with ZnS-SiO2 sputtering target. The shear strengths are 1.7, 8.7, and 1.3 MPa for ZnS-SiO2/ZnS-SiO2, copper/copper and ZnS-SiO2/copper joints, respectively. EPMA elemental mapping shows that aging test at 120° for 100 hours enhanced the segregation of titanium at the ZnS-SiO2/solder interfaces. The shear strength of ZnS-SiO2/copper joint after aging test is 1.3 MPa that shows no trace of degradation compared to the initial quality of the samples.  相似文献   

4.
The objective of the present study was to generate submicrometer calcium hydroxide aerosols and to investigate the effectiveness of such aerosols in sulfur capture. The effectiveness of SO2 removal by Ca(OH)2 aerosol has been investigated in an isothermal reactor. Ca(OH) 2 aerosol was generated by a novel fluidizer system in which submicrometer-sized powders were entrained in gases. SO2 was added to this aerosol to a concentration of 2000 ppm. The aerosol-SO2 mixture was heated to 550°C-750°C in an isothermal tube reactor. The SO2 removal efficiency, which varied from 20% to 70%, was determined to be a function of the aerosol concentration, reactor temperature and residence time. The fraction of aerosol reacted was not affected strongly by the aerosol concentration. The reaction kinetics were determined from the experimental data using a simple analytical model in which the rate is first order in both SO2 and calcium hydroxide aerosol concentrations.  相似文献   

5.
An effective method is developed for low temperature metal oxide deposition through thermal decomposition of metal diketonates in supercritical carbon dioxide (scCO2) solvent. The rates of Al(acac)3 (Aluminum acetyl acetonate) and Ga(acac)3 (Gallium acetyl acetonate) thermal decomposition in scCO2 to form conformal Al2O3 and Ga2O3 thin films on planar surfaces were investigated. The thermal decomposition reaction of Al(acac)3 and Ga(acac)3 was found to be initialized at  150 °C and 160 °C respectively in scCO2 solvent, compared to  250 °C and 360 °C in analogous vacuum-based processes. By measuring the temperature dependence of the growth rates of metal oxide thin films, the apparent activation energy for the thermal decomposition of Al(acac)3 in scCO2 is found to be 68 ± 6 kJ/mol, in comparison with 80–100 kJ/mol observed for the corresponding vacuum-based thermal decomposition reaction. The enhanced thermal decomposition rate in scCO2 is ascribed to the high density solvent which effectively reduces the energy of the polar transition states in the reaction pathway. Preliminary results of thin film deposition of other metal oxides including ZrOx, FeOx, Co2O3, Cr2O3, HfOx from thermal decomposition of metal diketonates or fluorinated diketonates in scCO2 are also presented.  相似文献   

6.
Sodium chloride aerosols were generated from a 1.0 percent solution and passed through a tubular furnace, then recondensed at 29°C in a cooling section in the presence of SO2. The dry particles ranged from 0.711 to 0.843 µm and the condensed droplets were in the 1.66 to 2.88 µm range. Final droplet size was varied by controlling the temperature of the nebulizer solution between 17 and 50°C. The SO2 concentration in the gas phase of the condensing cloud was varied between 0.5x10 - 3 and 2.5 xl0 - 3 atm.

Cloud droplets were separated from the gas stream in a point-to-plane electrostatic precipitator and the droplets analyzed colorimetrically for total sulfur content.

Concentrations of SO2 in the aqueous phase were about one order of magnitude greater than values obtained from equilibrium constants. The collection rate of SO2 at 29°C appeared to be first order in SO2 gas phase concentrations.

A model for this process was constructed, based on the hydrate formation in the gas-water interface[SO2]g + n[H2O]ℓ ⇋ [SO2 · n(H2O)]ℓ

The order of the hydrate n was estimated to be 4.0.  相似文献   

7.
A series of 0.2–0.6 μm thick SnOx films were deposited onto borosilicate and sodalime silica glass substrates by atmospheric plasma discharge chemical vapor deposition at 80 °C. SnOx films deposited from monobutyltin trichloride contained a large percentage of SnCl2:2H2O, and therefore were partially soluble in water. SnOx coatings deposited from tetrabutyltin were not soluble in water or organic solvents, had good adhesion even at growth rates as high as 2.3 nm/s, had high transparency of  90% and electrical resistivity of 107 Ω cm. As-grown tin oxide coatings were amorphous with a small concentration of SnO2, SnO and Sn crystalline phases as determined by grazing angle X-ray diffraction and X-ray photoelectron spectroscopy measurements. Upon annealing in air at 600 °C the resistivity of SnOx films decreased to 5–7 Ω cm. Furthermore, optical and X-ray measurements indicated that SnOx was converted into SnO2 (cassiterite) with a direct band gap of 3.66 eV. Annealing of as-grown SnOx films in vacuum at 340 °C led to formation of the p-type conductor SnO/SnOx. The indirect band gap of SnO was calculated from the optical spectra to be 0.3 eV.  相似文献   

8.
TiB2 is a material with very interesting properties with respect to erosion and corrosion resistance. Deposition on metallic substrates using TiCI4, BBr3 or BCI3 and H2 at temperatures around 900° C results in coronation of the substrate, which is most severe when using BBr3. Therefore, a TiN diffusion barrier is applied. Here we discuss the deposition of TiB2 using BCI3 on molybdenum and TiN and compare the results with those of the thermodynamically more favorable reaction with BBr3. Smooth TiB2 layers are formed when using BCI3, with faceting occurring above 900° C. The morphology seems to be independent of the BCI3/TiCl4 ratio in the gas phase for values between 0·5 and 4. With an excess of boron in the gas phase - BCI3/TiCl4 = 8, depletion occurs already at 800° C. An apparent activation energy of 210 KJ/mol has been determined for a stoichiometric gas phase with BCl3/TiCI4 = 2. When the supply of boron is limiting - BCl3/TiCl4 = 0·5, the activation energy is 120 KJ/mol.  相似文献   

9.
Atmospheric pressure chemical vapour deposition of tin monoselenide and tin diselenide films on glass substrate was achieved by reaction of diethyl selenide with tin tetrachloride at 350–650 °C. X-ray diffraction showed that all the films were crystalline and matched the reported pattern for SnSe and/or SnSe2. Wavelength dispersive analysis by X-rays show a variable Sn:Se ratio from 1:1 to 1:2 depending on conditions. The deposition temperature, flow rates and position on the substrate determined whether mixed SnSe–SnSe2, pure SnSe or pure SnSe2 thin films could be obtained. SnSe films were obtained at 650 °C with a SnCl4 to Et2Se ratio greater than 10. The SnSe films were silver–black in appearance and adhesive. SnSe2 films were obtained at 600–650 °C they had a black appearance and were composed of 10 to 80 μm sized adherent crystals. Films of SnSe only 100 nm thick showed complete absorbtion at 300–1100 nm.  相似文献   

10.
The current aqueous cleaning step in the surface preparation of aluminum nitride (AlN) prior to metallization causes performance and reliability issues for the substrates used for microelectronic packaging due to surface reactions. These issues limit the use of AlN and its replacing of BeO, an environmentally hazardous material currently used. The aim of this investigation was to determine the effects of different solutions on the surface of AlN substrates under varying conditions at times up to 2419.2 ks (28 days). Concentration of the solutions, temperature, and immersion time were varied for the AlN samples in the solutions. Both elevated temperatures (50°C and 90°C) and low temperatures (5°C) were investigated.

Four general types of behavior were observed: minor changes in average surface roughness and microstructure, linear change in average surface roughness and pitted grains, nonlinear change in average surface roughness and product formation on AlN surface, and miscellaneous change in average surface roughness with surface product formation.

The surface roughening kinetics were very complex due to changes in both the reaction product morphology and reaction mechanism with temperature, solvent, and pH for a specific solvent. Minor changes in average surface roughness and microstructure were observed for HCl pH = 5, H2 SO4 pH = 5, NaOH pH = 8, NaOH pH = 10, NaOH pH = 12, deionized water and Alfred tap water at 5°C, HCl pH = 3 and oleic acid at 50°C and citric acid and oleic acid at 90°C. Linear changes in average surface roughness and pitted grains were observed for HCl pH = 2 and H2SO4 pH = 3 at 50°C and HCl pH = 2, H2SO4 pH = 3, and deionized water at 90°C. Non-linear change in average surface roughness and product formation on AlN surface was observed for HCl pH = 5, NaOH pH = 8 and Alfred tap water at 50°C and HCl pH = 5 and H2SO4 pH = 2 at 90°C. Miscellaneous changes in average surface roughness with surface product formation were observed for H2SO4 pH = 2, H2SO4 pH = 5, NaOH pH = 10, NaOH pH = 12, citric acid, Micro-90 and deionized water at 50°C and HCl pH = 3, H2SO4 pH = 5, NaOH pH = 8, NaOH pH = 10, NaOH pH = 12, Micro-90 and Alfred tap water at 90°C.  相似文献   

11.
(100)-oriented 0.462Pb(Zn1/3Nb2/3)O3–0.308Pb(Mg1/3Nb2/3)O3–0.23PbTiO3 (PZN-PMN-PT) perovskite ferroelectric thin films were prepared on La0.7Sr0.3MnO3/LaAlO3 (LSMO/LAO) substrate via a chemical solution deposition route. The perovskite LSMO electrode was found to effectively suppress the pyrochlore phase while promote the growth of the perovskite phase in the PZN-PMN-PT film. The film annealed at 700 °C exhibited a high dielectric constant of 2130 at 1 kHz, a remnant polarization, 2Pr, of 29.8 μC/cm2, and a low leakage current density of 7.2 × 10− 7 A/cm2 at an applied field of 200 kV/cm. The ferroelectric polarization was fatigue-free at least up to 1010 cycles. Piezoelectric coefficient, d33, of 48 pm/V was also demonstrated. The results showed that much superior properties could be achieved with the PZN-PMN-PT thin films on the solution derived LSMO electrode than on Pt electrode by sputtering.  相似文献   

12.
The microwave dielectric properties and microstructures of Ba(Mg1/3Ta2/3)O3 (BMT) ceramics sintered at low temperatures with 2–3 wt.% NaF additives were investigated. BMT ceramics sintered at 1340 °C for 3–12 h showed dielectric constants (r) of 25.5–25.7, Qf values of 41 500–50 400 GHz and temperature coefficients of the resonator frequency (τf) of 10.9–21.4 ppm °C−1. The variation of sintering time almost had no effect on the dielectric constant. The Qf value increased and the τf decreased with increasing sintering time. The ordering degree of Mg2+ and Ta5+ at B-sites increased with increasing sintering time.  相似文献   

13.
随着全球核能的开发利用, 铀已成为土壤、地表水和地下水的常见污染物, 从含铀废水中去除铀(VI)已成为迫切需要。本工作以氟化钙、焦磷酸钙、氢氧化钙为反应原料合成氟磷灰石, 系统研究了其对铀(VI)的去除性能并采用不同测试手段对吸附铀(VI)前后的氟磷灰石进行表征, 揭示了其相关去除机理。结果表明: 在温度为308 K, pH=3, 固液比为0.12 g/L, 平衡时间为120 min, 初始铀浓度为100 mg/L的条件下, 氟磷灰石对铀(VI)的吸附容量可达655.17 mg/g, 其吸附过程符合准二级动力学和Langmuir等温吸附模型, 且为自发和吸热过程。氟磷灰石对铀(VI)的去除机理为表面矿化, 吸附铀(VI)的氟磷灰石表面产生了新相准钙铀云母[Ca(UO2)2(PO4)2·6H2O], 准钙铀云母在pH≥3水溶液中能保持较高稳定性。因此, 氟磷灰石可以作为一种有前景的矿化剂, 用于含铀废水的净化和固体化处理。  相似文献   

14.
Metal-organic chemical vapour deposition (MOCVD) of various phases in PrOx system has been studied in relation with deposition temperature (450–750 °C) and oxygen partial pressure (0.027–100 Pa or 0.2–750 mTorr). Depositions were carried out by pulsed liquid injection MOCVD using Pr(thd)3 (thd = 2,2,6,6-tetramethyl-3,5-heptanedionate) precursor dissolved in toluene or monoglyme. By varying deposition temperature and oxygen partial pressure amorphous films or various crystalline PrOx phases (Pr2O3, Pr7O12, Pr6O11) and their mixtures can be grown. The pure crystalline Pr2O3 phase grows only in a narrow range of partial oxygen pressure and temperature, while high oxygen pressure (40–100 Pa) always leads to the most stable Pr6O11 phase. The influence of annealing under vacuum at 750 °C on film phase composition was also studied. Near 90% step coverage conformity was achieved for PrOx films on structured silicon substrates with aspect ratio 1:10. In air degradation of Pr2O3 films with transformation to Pr(OH)3 was observed in contrast to Pr6O11 films.  相似文献   

15.
Electrochromic properties of nanocrystalline MoO3 thin films   总被引:1,自引:0,他引:1  
Electrochromic MoO3 thin films were prepared by a sol–gel spin-coating technique. The spin-coated films were initially amorphous; they were calcined, producing nanocrystalline MoO3 thin films. The effects of annealing temperatures ranging from 100 °C to 500 °C were investigated. The electrochemical and electrochromic properties of the films were measured by cyclic voltammetry and by in-situ optical transmittance techniques in 1 M LiClO4/propylene carbonate electrolyte. Experimental results showed that the transmittance of MoO3 thin films heat-treated at 350 °C varied from 80% to 35% at λ = 550 nm (ΔT =  45%) and from 86% to 21% at λ ≥ 700 nm (ΔT =  65%) after coloration. Films heat-treated at 350 °C exhibited the best electrochromic properties in the present study.  相似文献   

16.
Three methods were developed for the determination of aceclofenac in the presence of its degradation product, diclofenac. In the first method, third-derivative spectrophotometry (D3) is used. The D3 absorbance is measured at 283 nm where its hydrolytic degradation product diclofenac does not interfere. The suggested method shows a linear relationship in the range of 4-24 µg mL-1 with mean percentage accuracy of 100.05±0.88. This method determines the intact drug in the presence of up to 70% degradation product with mean percentage recovery of 100.42±0.94. The second method depends on ratio-spectra first-derivative (RSD1) spectrophotometry at 252 nm for aceclofenac and at 248 nm for determination of degradation product over concentration ranges of 4-32 µg mL-1 for both aceclofenac and diclofenac with mean percentage accuracy of 99.81±0.84 and 100.19±0.72 for pure drugs and 100.17±0.94 and 99.73±0.74 for laboratory-prepared mixtures, respectively. The third method depends on the quantitative evaluation of thin-layer chromatography of aceclofenac using chloroform:methanol: ammonia (48:11.5:0.5 v/v/v) as a mobile phase. Chromatograms were scanned at 274 and 283 nm for aceclofenac and diclofenac, respectively. The method determined aceclofenac and diclofenac in concentration ranges of 2-10 and 1-9 µg spot-1 with mean percentage accuracy of 100.20±1.03 and 100.14±0.98 for pure drugs and 99.77±0.74 and 100.07±0.78 for laboratory-prepared mixtures, respectively. This method retains its accuracy in the presence of up to 80% degradation product for the studied drug.

The suggested procedures were checked using laboratory-prepared mixtures and were successfully applied for the analysis of their pharmaceutical preparation. The validity of the proposed methods was further assessed by applying a standard addition technique. The obtained results agreed statistically with those obtained by the reported method.  相似文献   

17.
The deposition behavior of silicon in hot wire chemical vapor deposition was investigated, focusing on the generation of negatively charged species in the gas phase using a gas mixture of 20% SiH4 and 80% H2 at a 450 °C substrate temperature under a working pressure of 66.7 Pa. A negative current of 6–21 µA/cm2 was measured on the substrate at all processing conditions, and its absolute value increased with increasing wire temperature in the range of 1400 °C–1900 °C. The surface roughness of the films deposited on the silicon wafers increased with increasing wire temperature in the range of 1510 °C–1800 °C. The film growth rate on the positively biased substrates (+ 100 V, + 200 V) was higher than that on the neutral (0 V) and negatively biased substrates (− 100 V, − 200 V, − 300 V). These results indicate that the negatively charged species are generated in the gas phase and contribute to deposition. The surface roughness evolved during deposition was attributed to the electrostatic interaction between these negatively charged species and the negatively charged growing surface.  相似文献   

18.
Thin films of SrBi4Ti4O15 (SBTi), a prototype of the Bi-layered-ferroelectric oxide family, were obtained by a soft chemical method and crystallized in a domestic microwave oven. For comparison, films were also crystallized in a conventional method at 700 °C for 2 h. Structural and morphological characterization of the SBTi thin films were investigated by X-ray diffraction (XRD) and atomic force microscopy (AFM), respectively. Using platinum coated silicon substrates, the ferroelectric properties of the films were determined. Remanent polarization Pr and a coercive field Ec values of 5.1 μC/cm2 and 135 kV/cm for the film thermally treated in the microwave oven and 5.4 μC/cm2 and 85 kV/cm for the film thermally treated in conventional furnace were found. The films thermally treated in the conventional furnace exhibited excellent fatigue-free characteristics up to 1010 switching cycles indicating that SBTi thin films are a promising material for use in non-volatile memories.  相似文献   

19.
The effect of SiO2 addition on densification and grain-growth behavior of 8YSCZ/SiO2 composites was investigated using high purity 8 mol% yttria-stabilized cubic zirconia powders (8YSCZ) doped with 0, 1, 5, 10 wt% SiO2. The specimens were sintered at 1400°C for 1 hour. It was seen that the sintered density increased with SiO2 content up to 1 wt% and further increase in SiO2 content led to a decrease in density. The enhanced density with increasing SiO2 content up to 1 wt% could be mainly attributable to liquid phase sintering. For grain growth measurements, the specimens sintered at 1400°C were annealed at 1400, 1500, and 1600°C for 10, 50, and 100 hours. The experimental results showed that the grain growth in 8YSCZ/SiO2 composites occurred more slowly than that in undoped 8YSCZ. Also, the grain growth rate decreased with increasing SiO2 content. The grain growth exponent value and the activation energy for undoped 8YSCZ were found to be 2 and 289 kJ/mol, respectively. The addition of SiO2 raised the grain growth exponent value to 3, and activation energy for the grain growth process was increased from 289 to 420 kJ/mol for the addition of SiO2 from 0 to 10 wt%.  相似文献   

20.
Thermodynamic properties of fullerene hydride C60H36 in the ideal-gas and crystal states were studied by theoretical methods. Molecular structures and vibration frequencies were calculated for 9 isomers of C60H36 by the density functional theory (DFT) by use of a combination of the B3LYP functional with 6-31G* basis sets. Ideal-gas thermodynamic properties were calculated based on those parameters. Enthalpies of formation of C60H36 isomers in the ideal-gas state were derived from homodesmic reactions involving adamantane, cyclohexane, and C60 fullerene. Using the standard methods of statistical mechanics, heat capacity and derived thermodynamic properties of crystalline C60H36 were calculated at 340-1000 K that extended the range of experimental measurements. With a crystal-gas heat capacity difference, the experimental value of sublimation enthalpy was extrapolated to room temperature as ΔsubHmo (298.15 K)=(193±10) kJ · mol-1. Combining this value with the known experimental enthalpy of formation in the crystalline state, the ideal-gas enthalpy of formation of C60H36 at the synthesized sample isomer composition was obtained: Δf Hmo (298.15 K)=(1206±28) kJ · mol-1. Equilibrium constants and compositions were calculated for the reactions of hydrogenation of C60 fullerene in different states. It was shown that C60 can act as a hydrogen accumulator.  相似文献   

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