Amperometric detection of hydrazine by cyclic voltammetry and flow injection analysis using ruthenium modified glassy carbon electrodes

Glassy carbon electrodes modified with (5-amino-1,10-phenanthroline)bis(bipyridine)ruthium(II) chloride hydrate, [(bpy)₂Ru(5-phenNH₂)]Cl₂·H₂O, are shown to oxidize hydrazine with excellent sensitivity. The presence of an amine group on the ruthenium complex facilitates electropolymerization onto the electrode surface. Using cyclic voltammetry, a large catalytic current is observed upon oxidation of hydrazine in phosphate buffer (pH 5.0), compared to the current obtained from the ruthenium-modified electrode with no hydrazine present. The sensitivity of cyclic voltammetry is sufficient for obtaining a linear calibration curve for hydrazine over the range of 10⁻⁵ to 10⁻² M. Hydrodynamic amperometry was used to determine the working potential for flow injection analysis. The limit of detection for hydrazine was determined to be 8.5 μM using FIA. The thickness of these films was shown to increase linearly with the number of electropolymerization cycles, in the range of 1000-2500 nm for 5-20 cycles, respectively, using Rutherford backscattering spectrometry (RBS). RBS analysis also suggests that the film is multilayered with the outermost layers containing a high ruthenium concentration, followed by layers where the concentration of ruthenium decreases linearly and approaches zero at the electrode surface.     

Physicochemical characterization of biological glass coatings

Metallic implants are widely used in orthopaedic surgery but metal release has been reported by several authors. High metallic ion concentration in surrounding tissues may play a major role in therapeutic failure. We have investigated in vivo and in vitro two biological glasses (BVA and BVH) used as coatings of metal implants. Physicochemical characterization was made by several complementary methods, particularly particle induced x‐ray emission (PIXE) and energy‐dispersive x‐ray spectroscopy (EDXS) associated with electronic microscopy. Analyses clearly show the differences of behaviour between both glasses. The BVA glass is bioactive, i.e. it develops a direct chemical bond between prosthesis and bone by the formation of a calcium phosphate layer at its surface. These structural and compositional modifications are caused by hydrolysis of the glass. After its dissolution BVA glass is replaced by bone, which ensures better integration of the implant in the bone site. The BVH glass is not bioactive and is used as a cement to isolate the metal implant from the biological environment, but the coating disaggregates with implantation time and glass grains migrate through the bony lacuna network. Copyright © 2003 John Wiley & Sons, Ltd.     

Multivariate comparison of concentration profiles in materials analysis

Hierarchical cluster analysis (HCA) and principal components analysis (PCA) were applied to find groups between similar depth-profiles in thin-layers investigated by Rutherford backscattering spectrometry (RBS).HCA yields in one run an objective hierarchy of similarity for several profiles. Among the similarity coefficients examined the linear measure, the Euclidean distance and the exponential measure respond with different sensitivity to overall shifts in direction of the concentration axis, whereas the correlation measure relates to parallelism of the profiles.For agglomerative HCA with Euclidean distance, a lowest significant linkage level has been defined by use of Fisher'sF-test. For divisive HCA based also on Euclidean distance, the maximum of a separating function marks the most separating cluster step. The outcomes of both proposals agree for the data set investigated.PCA is useful for verifying the results of HCA and yields additional information about the data structure. In the actual example quite different positions of features (concentrations at definite depths) in the space of the two first principal components hint at peculiarities during the metallurgical coating process.     

Ultrashallow depth profiling using SIMS and ion scattering spectroscopy

The accuracy of ultrashallow depth profiling was studied by secondary ion mass spectrometry (SIMS) and high‐resolution Rutherford backscattering spectroscopy (HRBS) to obtain reliable depth profiles of ultrathin gate dielectrics and ultrashallow dopant profiles, and to provide important information for the modeling and process control of advanced complimentary metal‐oxide semiconductor (CMOS) design. An ultrathin Si₃N₄/SiO₂ stacked layer (2.5 nm) and ultrashallow arsenic implantation distributions (3 keV, 1 × 10¹⁵ cm^?2) were used to explore the accuracy of near‐surface depth profiles measured by low‐energy O₂⁺ and Cs⁺ bombardment (0.25 and 0.5 keV) at oblique incidence. The SIMS depth profiles were compared with those by HRBS. Comparison between HRBS and SIMS nitrogen profiles in the stacked layer suggested that SIMS depth profiling with O₂⁺ at low energy (0.25 keV) and an impact angle of 78° provides accurate profiles. For the As⁺‐implanted Si, the HRBS depth profiles clearly showed redistribution in the near‐surface region. In contrast, those by the conventional SIMS measurement using Cs⁺ primary ions at oblique incidence were distorted at depths less than 5 nm. The distortion resulted from a long transient caused by the native oxide. To reduce the transient behavior and to obtain more accurate depth profiles in the near‐surface region, the use of O₂⁺ primary ions was found to be effective, and 0.25 keV O₂⁺ at normal incidence provided a more reliable result than Cs⁺ in the near‐surface region. Copyright © 2007 John Wiley & Sons, Ltd.     

铜铟镓硒太阳能电池多层膜的结构分析

对于溅射后硒化和共蒸发等方法制备的铜铟镓硒（CIGS）太阳能电池薄膜,利用多种分析方法研究了CIGS多层膜的复杂结构等．研究表明：卢瑟福背散射（RBS）在分析CIGS多层膜方面具有其独特优势和可靠的结果;溅射后硒化方法制备的CIGS薄膜中,Ga和In在CIGS薄膜中呈梯度分布,这种Ga表层少而内层多的不均匀分布与Mo层没有必然关系;RBS和俄歇电子能谱分析（AES）均显示CIGS太阳能电池器件多层膜界面处存在扩散,尤其是CdS与CIGS,Mo与CIGS的界面处;X射线荧光（XRF）结果表明,电池效率最高的CIGS层中In,Ga比例为In：Ga=0．7：0.3;X射线衍射（XRD）结果显示：退火后的CIGS／Mo薄膜结晶品质得到了优化．     

Synchrotron radiation photoelectron spectroscopy and near-edge X-ray absorption fine structure study on oxidative etching of diamond-like carbon films by hyperthermal atomic oxygen

Surface structural changes of a hydrogenated diamond-like carbon (DLC) film exposed to a hyperthermal atomic oxygen beam were investigated by Rutherford backscattering spectroscopy (RBS), synchrotron radiation photoelectron spectroscopy (SR-PES), and near-edge X-ray absorption fine structure (NEXAFS). It was confirmed that the DLC surface was oxidized and etched by high-energy collisions of atomic oxygen. RBS and real-time mass-loss data showed a linear relationship between etching and atomic oxygen fluence. SR-PES data suggested that the oxide layer was restricted to the topmost surface of the DLC film. NEXAFS data were interpreted to mean that the sp² structure at the DLC surface was selectively etched by collisions with hyperthermal atomic oxygen, and an sp³-rich region remained at the topmost DLC surface. The formation of an sp³-rich layer at the DLC surface led to surface roughening and a reduced erosion yield relative to the pristine DLC surface.     

Simulation of high fluence fast neutron damage with heavy ion bombardment

316 stainless steel has been irradiated with 5 MeV Cu ions to a fluence of 2 × 10¹⁶ ions/cm² at 500°C. Transmission electron microscopy of this sample reveals that 6 × 10¹⁵ voids/cm² of average diameter equal to 180 Å were produced. A method for correlating the fluence of ions with equivalent neutron fluences is described. This method predicts that the Cu bombardment in this study should produce a microstructure similar to that found in steel irradiated with 2–5 × 11²² neutrons/cm². A comparison of the ion produced voids with those found after previous neutron irradiation experiments confirms this prediction.     

Investigation of energetic ion-induced mixing in Bi/Ge system

The present study is carried out for the investigation of energetic ion beam mixing in the Bi/Ge system, induced by electronic excitation. The system Ge/Bi/C was deposited on Si substrate at room temperature in the high vacuum deposition system and irradiated using Au ions of 120?MeV at the fluences 1?×?10¹³, 5?×?10¹³ and 1?×?10¹⁴?ions/cm². The top layer of carbon was deposited as the protecting layer to avoid oxidation. The swift heavy ions (SHI)-induced interface mixing was studied by Rutherford backscattering spectroscopy (RBS) for depth profiles and compositions, grazing incidence X-ray diffraction (GIXRD) for phase identification and atomic force microscopy (AFM) for surface roughness. We have calculated the mixing rate, mixing efficiency and inter-diffusion coefficient for the Bi/Ge system. We observed that the thickness of the mixed region increased with increasing fluence. In the GIXRD pattern, no new crystalline phase formation was observed after irradiation, the mixed region may be in an amorphous form. The mixing effect is explained in the framework of the thermal spike model.     

Uranium association with corroding carbon steel surfaces

We investigated the association of uranium with clean and corroded surfaces of 1010 carbon steel. Studying steel contaminated by uranium species will have an important effect on the development of methods used to clean radioactively contaminated metal waste. X‐ray photoelectron spectroscopy, synchrotron infrared microspectroscopy and laboratory‐based Fourier transform infrared analysis of steel surfaces exposed to uranyl nitrate showed the presence of crystallized hydrated uranyl oxides, uranyl hydroxides, iron oxyhydroxides and iron oxides. In general, heavily corroded areas physically shield the uranium species, which tended to associate spatially with hydroxyl groups and lepidocrocite. Lightly corroded areas contained uranium species with stronger axial U–O bonding. Infrared spectroscopy, Rutherford backscattering spectroscopy and energy‐dispersive spectroscopy mapping analysis revealed that the uranium species are well distributed within the upper micron of the thick corrosion layer and associated more with areas of high hydroxide content. Parameters such as the concentration of uranyl nitrate solution used to expose the carbon steel coupons, the method of contamination (dipped or sprayed with dilute uranyl nitrate solution) and the degree of corrosion (accelerated corrosion before and/or after contamination) played significant roles in the distribution and nature of the uranyl hydroxide/iron oxyhydroxide corrosion products found on the surface of all coupons. These factors must be considered in the development and optimization of decontamination processes for metal waste. Copyright © 2003 John Wiley & Sons, Ltd.     

Effect of ion velocity on SHI-induced mixing in Ti/Bi system

Energetic ion beams are proving to be versatile tools for modification and depth profiling of materials. The energy and ion species are the deciding factor in the ion-beam-induced materials modification. Among the various parameters such as electronic energy loss, fluence and heat of mixing, velocity of the ions used for irradiation plays an important role in mixing at the interface. The present study is carried out to find the effect of the velocity of swift heavy ions on interface mixing of a Ti/Bi bilayer system. Ti/Bi/C was deposited on Si substrate at room temperature by an electron gun in a high-vacuum deposition system. Carbon layer is deposited on top to avoid oxidation of the samples. Eighty mega electron volts Au ions and 100?MeV Ag ions with same value of S_e for Ti are used for the irradiation of samples at the fluences 1?×?10¹³–1?×?10¹⁴ ions/cm². Different techniques like Rutherford backscattering spectroscopy, atomic force microscopy and grazing incidence X-ray diffraction were used to characterize the pristine and irradiated samples. The mixing effect is explained in the framework of the thermal spike model. It has been found that the mixing rate is higher for low-velocity Au ions in comparison to high-velocity Ag ions. The result could be explained as due to less energy deposition in thermal spike by high-velocity ions.