Topical Problems in Elemental Analysis of Advanced Ceramic Materials

Selected prominent problems in the analysis of advanced ceramic materials are surveyed. The importance of reliability of results is discussed in the field of elemental trace- and microanalysis in view of its interaction with economy, power of detection, local resolution and speciation selectivity. Particular problems in the analysis of major constituents, trace components and microlocal distributions are based on the striking propertics of ceramics; they are exemplified. Analytical assistance must start from the beginning of the production processing, in the preparation of the powdered base materials. Determination of the stoichiometry requires high accuracy and differentiation of chemical species in bulk and surface analysis of ceramic base powders. Element trace determination by direct instrumental methods requires standard reference materials for calibration; these are currently inavailable in a sufficient variety. For optimum reliability and power of detection, element traces must be prepared in isolated form in a small excitation volume for analysis. A review on the state-of-the-art of wet-chemical combined procedures is presented. Decomposition position procedures are emphasized, due to their risk of contributing severe systematic error. Combustion in elementary fluorine is presented for decomposition of refractory materials. The performance of some direct procedures is discussed. Very efficient methods are available for element trace determinations in ceramic materials, offering high detection power. Several approaches for high-resolution local microanalysis in non-conductive ceramic materials are identified as the most promising development in the analysis of sintered compact ceramic products and devices.     

N掺杂对非晶C薄膜的电子结构与光学性质的影响

用直流磁控溅射法制备了非晶C薄膜及N掺杂非晶C(a-C∶N)薄膜,用紫外-可见分光光谱仪、椭圆偏振仪、俄歇电子能谱(AES)等对薄膜进行了检测。结果表明：随源气体中N气含量的增加,透过率和折射率变小, 而光学带隙先增大后减小; 当薄膜中N的含量很少,N的掺入对sp3杂化C起稳定作用,使得薄膜光学带隙E_g增大。而较高量N的掺入抑制了sp3杂化C的形成,提高了薄膜中sp2键含量,使得薄膜光学带隙变小。参数D定义为俄歇电子能谱(AES)中最大正峰和最低负峰之间的距离,用俄歇电子能谱中的D值来计算薄膜的sp2键的百分含量,俄歇电子能谱(AES)表征也表明：较高量的N的掺入抑制了sp3杂化C的形成。所以应该考虑在较低N分压条件下掺N来改善非晶C薄膜的光学性能。     

A quantum circuit design of AES requiring fewer quantum qubits and gate operations

Advanced Encryption Standard (AES) is one of the most widely used block ciphers nowadays, and has been established as an encryption standard in 2001. Here we design AES-128 and the sample-AES (S-AES) quantum circuits for deciphering. In the quantum circuit of AES-128, we perform an affine transformation for the SubBytes part to solve the problem that the initial state of the output qubits in SubBytes is not the |0>^⊗8 state. After that, we are able to encode the new round sub-key on the qubits encoding the previous round sub-key, and this improvement reduces the number of qubits used by 224 compared with Langenberg et al.’s implementation. For S-AES, a complete quantum circuit is presented with only 48 qubits, which is already within the reach of existing noisy intermediate-scale quantum computers.     

ICP—AES法中稀土元素间的相互干扰研究

稀土元素的谱线较复杂,相互间存在着不同程度的干扰。本文着重研究了ＩＣＰ－ＡＥＳ法中,它们间的干扰情况,并用几种校正方法进行了比较。     

Rheological Properties of Anionic Surfactant Solutions in the Presence of Al3+ Counterion

Aqueous solutions of ionic surfactants with strongly binding counterions exhibit wormlike or network properties. The properties of anionic micelles of sodium dodecyltrioxyethylene sulfate (AES) in the presence of multivalent counterion Al³⁺ were investigated by dynamic rheological methods. The steady-shear viscosity and stress, the zero-shear viscosity, the complex viscosity, and the dynamic shear modulus have been determined as a function of the surfactant and salt concentrations. Some interesting and noticeable results have been obtained, which can express the micellar growth and structure. The formation of wormlike micelles or network structure in surfactant solutions becomes much easier with increasing surfactant and salt concentrations. The Cox-Merz rule and the Cole-Cole plot are not applicable perfectly to the systems studied. The nonlinear viscoelasticity and non-Newtonian behavior can be found in all solutions according to the comparison with the simple Maxwell model. The technique of freeze-fracture transmission electron microscopy (FF-TEM) was also applied to confirm the formation of these interesting structures.     

骨中铊的微波消解ICP/AES标准加入测定法

建立骨骼的微波消解和金属毒物铊的ICP/AES标准加入分析方法。取0.2g骨粉于聚四氟乙烯消解管中,加入3.0mL浓硝酸及0.5mL双氧水,进行微波消解。结束后,用2%硝酸定容至10.0mL。根据标准加入法进行ICP-AES定量分析。方法的回收率为99.4%,检出限为5.1ng/g,线性范围为5~500 ng/mL。该方法操作简便,回收率高,检出限低,线性范围宽,可多元素同时测定,结果可靠。     

Summary of ISO/TC 201 standard: XXI. ISO 21270:2004—Surface chemical analysis—X‐ray photoelectron and Auger electron spectrometers—Linearity of intensity scale

This International Standard specifies two methods for determining the maximum count rate for an acceptable limit of divergence from linearity of the intensity scale of Auger and x‐ray photoelectron spectrometers. It also includes methods to correct for intensity non‐linearities so that a higher maximum count rate can be employed for those spectrometers for which the relevant correction equations have been shown to be valid. Copyright © 2004 John Wiley & Sons, Ltd.     

Surface oxidation behavior of MgNd alloys

The oxidation kinetics of MgNd alloys oxidized in pure O₂ at high temperatures has been investigated. The results revealed two stages of the reaction: A fast initial oxidation was followed by a slow oxide growth with a parabolic kinetics. For MgNd alloys (Nd = 25 wt.%), the oxidation rate increased with the enhancement of the oxidation temperature. A sudden ignition was found for this alloys oxidized at 873 K up to about 80 min. Moreover, the increase of the Nd content would harm the oxidation resistance of the MgNd alloys. By Auger electron spectroscopy (AES), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD) and scanning electron microscopy (SEM) analysis, it was found that a triplex structure of oxide film formed. The outer layer was composed of MgO, Nd₂O₃ and Nd(OH)₃, the middle layer mainly consisted of MgO and Nd₂O₃, and the inner layer was the transitional layer made of MgO, Nd₂O₃ and the content of the substrate. The protective oxidation was associated with the formation of the dense Nd₂O₃/MgO layer during isothermal oxidation process. The oxidation mechanisms for the formation of oxide film are discussed.     

Surface-enhanced Raman scattering (SERS) activity of Ag, Au and Cu nanoclusters on TiO2-nanotubes/Ti substrate

Tubular arrays of TiO₂ nanotubes (ranging in diameter from 40 to 110 nm) on a Ti substrate were used as a support for Ag, Au or Cu deposits obtained by the sputter deposition technique, where the amount of metal varied from 0.01 to 0.2 mg/cm². Those composite supports were intended for surface-enhanced Raman scattering (SERS) investigations. Composite samples were studied with the aid of scanning electron microscopy (SEM) and Auger electron spectroscopy (AES) to reveal their characteristic morphological and chemical features. Raman spectra of pyridine (as a probe molecule) were measured at different cathodic potentials ranging from −0.2 down to −1.2 V after the pyridine had been adsorbed on the metal-covered TiO₂ nanotube/Ti substrates. In addition, SERS spectra on a bulk standard activated Ag, Au and Cu substrates were also measured. The SERS activity of the composite samples was strongly dependent on the amount of metal deposit, e.g. at and above 0.06 mg Ag/cm², the intensity of SERS signal was even higher than that for the Ag reference substrate. The high activity of these composites is mainly a result of their specific morphology. The high SERS sensitivity on the surface morphology of the substrate made it possible to monitor very small temporal changes in the Ag metal clusters. This rearrangement was not detectable with microscopic (SEM) or microanalytical (AES) methods. The SERS activity of Au or Cu clusters was distinctly lower than those of Ag. The spectral differences exhibited by the three kinds of composites as compared to the reference metal samples are discussed.     

铸造锌合金中铝、铜、镁、铁、硅、镉的 ICP-AES法测定

采用ICP-AES法测定了铸造锌合金的铝、铜、镁、铁、硅、镉6种元素。并研究了基体对6种被测元素以及被测元素间的干扰。进行了酸度与内标用量试验,以及精密度、准确度、回收率试验,获得了满意的结果。