Surface composition of alloys

The practical importance of alloy surfaces in catalysis, corrosion andother aspects of materials performance is widely recognized. What is needed now is sufficient knowledge of the relationship between externally controllable factors — alloy composition, temperature, environment — and surface properties — composition, structure, chemical activity — to control materials performance in these applications. Our purpose here is to review progress in determining and predicting the relationship between one surface property, composition, and certain externally controllable variables: overall composition, temperature, environment and physical form.We find that theoretical treatments of metal alloy surface composition now include essentially all significant physical effects and can predict values for most parameters of interest. Though improvements are still possible, the accuracy of predictions is more often limited by uncertainties or absence of the basic data for the calculations (e.g., thermochemical values) than by the models themselves.Alloy surface composition can now be measured well. The first monolayercomposition of large alloy slabs can be determined quantitatively over a wide temperature range in ultra-high vacuum. Difficulties with specimens of practical interest still challenge experimentalists. Among these are supported catalysts, surfaces under chemisorbed layers and composition of layers below the first. Significant progress is being made and we expect the next few years will see success.     

Microstructure and magnetocaloric effect in cast LaFe11.5Si1.5Bx (x=0.5, 1.0)

Phase formation, structure, and the magnetocaloric effect (MCE) in as-cast LaFe_11.5Si_1.5B_x (x=0.5, 1.0) compounds have been studied. The Curie temperatures, T_C, are ∼211 and 230 K for x=0.5 and 1.0, respectively, which are higher than that of annealed LaFe_11.5Si_1.5 (T_C=183 K), while the maximum magnetic entropy changes at the respective T_C under a magnetic field change of 0-5 T are 7.8 and 5.8 J/(kg K). Wavelength dispersive spectrometry (WDS) analysis shows that only a small fraction of boron atoms is dissolved in the NaZn₁₃-type structure phase, and that the compositions of the as-cast LaFe_11.5Si_1.5B_x (x=0.5, 1.0) alloys are much different from the intended nominal compositions. These as-cast alloys exhibit second-order magnetic phase transitions and low MCEs. However, based on the relative cooling power, the as-cast LaFe_11.5Si_1.5B_x alloys are promising candidates for magnetic refrigerants over a wide temperature range.     

Spectral Interferences in Light Element Analysis

 Interferences (overlaps) occurring when lines of other elements affect either peak or background measurements can cause errors in quantitative WD analysis, but may be minimised by suitable choices of analysis conditions such as spectrometer crystal, background offsets, and pulse-height analyser settings. Computer spectrum-simulation is much more effective than reference to wavelength tables for investigating interferences. The ‘Virtual WDS’ simulation program developed by the present authors, hitherto applied only to ‘ordinary’ elements (Z ≥ 11), has been extended to light elements for which evaporated multilayers are used in place of true crystals. ‘Virtual WDS’ utilises experimentally recorded light-element K spectra and L and M spectra of heavier elements in the same wavelength range. It is impractical to record all high-order peaks, so computed line profiles are used, with widths and intensities interpolated from a limited set of observations. The relative positions of first and higher order peaks are affected significantly by the refractive index of the multilayer, requiring modification of the Bragg equation. Suppression of high orders by pulse-height analysis is less effective than for ‘normal’ wavelengths, owing to the breadth of the pulse-height distribution for low X-ray energies. Simulation using a Gaussian expression aids optimisation of threshold and window-width settings.     

电子显微分析在表征纳米晶体化学组分中的应用

纳米材料的化学组分及含量影响其光、电、声、热、磁等物理性能,电子显微分析是表征纳米晶体化学组分的重要方法之一.本文综述了X-射线能谱(EDS)、X-射线波谱(WDS)、电子能量损失谱(EELS)和选区电子衍射(SAED)等现代电子显微分析技术在表征纳米晶体化学组分、形貌、尺寸和结构等方面的应用及其研究进展,并比较了这些分析方法存在的差异,提出了其应用中存在的不足及今后的研发方向.     

X-ray scattering and polarization in wavelength-dispersive spectrometers

Background suppression is discussed in wavelength-dispersive polarization X-ray spectrometer (WDPXRS), in which the goniometer scans in plane perpendicular to primary and secondary beams. Background suppression coefficients in WDPXRS and energy-dispersive polarization X-ray spectrometer are determined by different expressions (in “The scattering suppression of X-rays with energy of 20–200 keV in spectrometers with Barkla polarizers,” doi: 10.1002/xrs.3046 ). It is proposed to install silicon drift detectors in WDPXRS and implement energy-dispersive and wavelength-dispersive modes in one channel.     

Quantitative Trace Analysis by Wavelength-Dispersive EPMA

 “Trace” elements may be defined as elements whose concentrations are of a similar order to the detection limit. In WD analysis the detection limit is a function of the ‘figure of merit’ P²/B, where P is the pure-element peak intensity and B the background intensity. With normal analysis conditions detection limits of ∼100 ppm are typical, but substantial improvements can be achieved by using higher values of accelerating voltage and beam current. Long counting times are also advantageous, but should preferably be divided into relatively short alternating peak and background measurements to minimise the effect of instrumental drift. Using separate routines for trace and major element analysis is desirable owing to their different requirements. As the statistically defined detection limit is reduced, errors due to background nonlinearity and interferences (overlaps) from other elemental peaks become more probable. Spectrum simulation is useful for optimising background offsets and choice of crystal to minimise interferences, and estimating interference corrections when these are necessary. ‘Blank’ standards containing none of the trace elements of interest are also useful for quantifying background nonlinearity.     

Influence of Second-Order Lines on the Quantitative Wavelength Dispersive Spectrometry Analysis at Low Accelerating Voltages

The study covers a problem frequently encountered in the quantification of the results of wavelength-dispersive spectrometry (WDS) for the composition analysis of thin films. The characteristics of a Parallel Beam Spectrometer and traditional WDS systems were examined and olivine mineral – (Mg, Fe)₂SiO₄ (O – 44.03 wt%, Mg – 31.1 wt%, Si – 19.56 wt%, Fe – 5.06 wt%, Ni – 0.16 wt%, Mn – 0.09 wt%) was used as a reference material. Low accelerating voltage at 7 kV and beam current 400 nA were applied. Both methods yielded 30–35% of Mn. This is attributed to the overlapping of the MnLα first-order and the MgKα second-order lines. Studies of the influences of the second- and the third-order lines show that the second-order lines from Kα and Lα X-ray counts affected significantly the obtained WDS spectra when the influence of Mα counts was insignificant. Furthermore, the third-order lines did not have a marked effect on the analysis results.     

环带钾长石、榍石和锆石的显微结构与微区组成特征分析

南秦岭沙河湾石英二长岩中的钾长石、榍石和锆石具有明显的成分环带。利用电子探针(EPMA)波谱仪(WDS)、扫描电子显微镜(SEM)及其附带的能谱仪(EDS)和激光剥蚀电感耦合等离子体质谱(LA-ICP-MS)对造岩矿物环带钾长石、榍石和锆石的显微结构与微区组成进行表征。结果表明：钾长石中K+被Na+,Ca2+,Ba2+,Fe2+和Ce3+不同程度替代。榍石中Ca2+被V3+,Ce3+和Ba2+等替代,Ti4+被Fe2+和Al3+等替代。锆石含Fe,Th,U,Nb,Ta,Y,Hf,Yb和Pb等稀土和微量元素。钾长石中元素浓度由高到低为Si,Al,K,Ca,Na,Mg和Ba,其中K和Na互补,较亮处Ba含量高,越靠近边缘,Si升高、K升高与Na降低趋势越明显。榍石中元素浓度由高到低为Ca,Si,Ti,Ba,V,Ce,Al和Fe,较亮处Fe含量较高。锆石中元素浓度由高到低为Zr,Si,Nd,Ce,Hf,U,Pb和Th,Hf与Zr呈明显的互补关系,核部Zr含量较边部高,核部Hf、U和Th含量较边部低。     

波谱仪与能谱仪性能的比较

用实验测量数据对波谱分析与能谱分析这两种技术在元素定性与定量分析方面的性能差异进行了比较,说明各自的长处与不足,为材料科学工作者在分析测试中如何选择提供参考。     

Oxide and nitride protective layers on stainless steel studied by AES,WDS and XPS

Protective surface layers on AISI 321 stainless steel were prepared by thermal treatments at two different temperatures in air and two controlled atmospheres. Different oxide and/or nitride layers were formed. Surface morphology of the layers was investigated by scanning electron microscopy (SEM). Auger electron spectroscopy (AES) depth profiling of the samples was performed. Since depth profiling suggested layer thicknesses of the order of hundreds of nanometres, an attempt was made to obtain some fast, averaged information about the layer compositions using wavelength dispersive spectroscopy (WDS) at two different beam energies to obtain probing depths best suited to the layer thickness. X‐ray photoelectron spectroscopy (XPS) profiling of one layer was also performed to obtain information about the chemical states of the elements inside the layer. The analysed samples showed considerable differences with respect to their surface morphology, oxide/nitride layer thicknesses, compositions and layer–metal interface thickness. Copyright © 2007 John Wiley & Sons, Ltd.