用智能波长校正的扫描式电感耦合等离子体光谱仪测定高炉渣中7种元素成份

本文利用作者所在实验室发现的，光栅单色仪的出射光谱线峰漂移与温度变化以及波长变化间的非线性函数关系，以及在此基础上所开发的扫描式ICP－AES光谱仪的智能波长校正装置，取代传统的局部恒温系统，测定了高炉位中的Si，Ca．Mg，Mn，Fe，Ti，Al7种元素成份。测定结果与标样的鉴定值一致，测量的相对标准偏差（RSD）为1．X％。智能波长校正装置的波长校正结果与话线峰描迹结果的比较表明，该智能彼长校正装置是有效的，具有省时、安全、结构简单的特点，有广泛的应用前景。     

电感耦合等离子体光谱仪点火电路维修

介绍了澳大利亚ＬＡＢＴＡＭ公司生产的８４０１型电感耦合等离子光谱仪点火电路故障分析，检查及故障排除的方法。     

Kalman滤波技术校正电感耦合等离子体原子发射光谱分析中严重重叠的谱线干扰

针对ICP-AES中严重重叠谱线干扰的校正, 研究了若干因素对Kalman滤波器性能的影响。减小扫描步长可以增强Kalman滤波法解析重叠谱线的能力。当重叠线轮廓基本相同且扫描窗口内干扰元素只有一条谱线时, Kalman滤波法能分辨的重叠线对的最小峰间距为扫描步长的2～3倍。扫描窗口内较多的干扰元素谱线和重叠线对轮廓的显著差异有利于Kalman滤波器正确识别分析信号和干扰信号, 可以利用这两个因素有效地分辨峰间距很小甚至完全重叠的谱线。     

电感耦合等离子体原子发射光谱法中Kalman滤波法解析重叠谱线的研究

考察了Kalman滤波技术校正ICP-AES中谱线重叠干扰的潜力。以新息序列的平均平方和为评价函数优化扫描光谱的峰位, 消除扫描过程中可能产生的波长定位误差, 从而保证滤波结果的准确性, 并使实际检出限显著改善。在中等分辨率光谱仪和扫描步长为1.5pm的条件下, 滤波器能有效地分辨峰间距只有4.8pm且峰形基本相同的重叠线对。对峰间距为9.8pm的重叠线时, 当线背比低至0.05左右时仍能获得满意结果。连续背景用理论描述, 因而样品溶液和纯组分溶液的光谱扫描无需扣除溶剂空白。     

用国产单道扫描电感耦合等离子体发射光谱仪分析海绵铂

铂族元素具有相似的电子层结构和化学性质,使很多试剂能同时与多种铂族元素发生相似反应并产生相互干扰,很难找到特效的试剂,因此分离和测定十分困难.我国贵金属行业测定海绵铂纯度用直流电弧发射光谱法或进口电感耦合等离子体原子发射光谱仪.     

自模型曲线分辨法校正电感耦合等离子体原子发射光谱中严重谱线重叠干扰

对严重重叠的光谱干扰校正,采用较小间隔的光谱扫描测量,并用间隔扫描点的数据计算,可减小计算结果的误差,提高结果的准确性。本方法用于校正Nd359.259nm对Sm359.260nm和V328.939nm对Yb328.937nm谱线重叠干扰,得到了满意的结果。     

电感耦合等离子体发射光谱仪高电离能元素进样系统的研制

设计开发了一套电感耦合等离子体发射光谱仪（ICP-OES）高电离能元素进样系统.系统既保留了ICP-OES原有的检测功能,又利用超声波振动空化作用的物理方法与氢化反应的化学方法有机结合,有效增加单位体积内待测元素检测浓度,使高电离能元素的检测灵敏度在原有基础上提高3~5倍.系统的研制扩展了ICP-OES关于高电离能元素的检测功能.     

电荷注入检测器电感耦合等离子体光谱仪测定铂族元素的性能

研究了用电荷注入检测器等离子体光谱仪测定铂族元素的分析性能。结果表明铂族元素有较好的检出限和10^4以上的线性动态范围，铂族元素间光谱干扰很少，在元素浓度＞1mg/L时测量精度可优于1％，钠对铂族元素的影响是轻微的。     

乙醇溶液的电感耦合等离子体发射光谱研究 Ⅰ.乙醇对稀土元素谱线强度的影响

以稀土元素为主要对象,研究乙醇导入ICP对谱线强度的影响。结果表明,随乙醇浓度增大,经溶液进炬速率校正后的稀土元素离子线强度(校正强度)单调减小;原子线的校正强度则在乙醇浓度为20vol％时出现最小值。乙醇对谱线校正强度的影响程度与谱线激发电位呈线性关系。据此,确定了稀土元素38条未分类谱线的电离态,估算了它们的激发电位。     

Evaluation of inductively coupled plasma optical emission spectrometers with axially and radially viewed configurations

The analytical performance of two inductively coupled plasma optical emission spectrometers with axially and radially viewed configurations, equipped with charge coupled device solid-state detectors was evaluated using Ar, Ba, Mg, and Ni as test elements. Both instruments have similar Echelle optical arrangements and radio-frequency generators, differing only in the viewing mode and in the diameter of the central injector tube, i.e. 2.3 for the axially and 1.4 mm for the radially viewed ICP. The figures of merit evaluated were: warm-up time, short- and long-term stabilities, UV and VIS spectral resolution and limit of detection (LOD) for Ni in 0.14 mol l⁻¹ HNO₃ and 1000 mg l⁻¹ Cr media, respectively. The influence of residual carbon content on background equivalent concentration (BEC) and sensitivity attained for Al, As, Ca, Cd, Co, Cr, Cu, Fe, Mg, Mn, Se and Zn was also investigated in both viewing modes. The robustness, short- and long-term stabilities, and UV and VIS spectral resolutions were similar for both configurations. For the radially viewed equipment, the warm-up time was at least a factor of 2 shorter than that for the axially viewed configuration. On the other hand, the sensitivity attained for Ni with the axially viewed arrangement was approximately 20 times better than that with the radially viewed. In both viewing modes, and for most of the evaluated elements, the values of BEC and LOD were similar for all studied carbon concentrations (from 10 to 10 000 mg l⁻¹ C) when working with robust plasma conditions. The Mg II/Mg I ratio at an applied power of 1.3 kW and a nebulizer gas flow-rate of 0.90 and 0.70 l min⁻¹ for axially and radially viewed configurations were 10.6 and 13.7, respectively. Quantitative determinations were successfully performed using both systems.     

Energy transport in the inductively coupled plasma

Time- and space-resolved electron density measurements, made both above the load coil and in the load coil region of a pulsed inductively coupled plasma, are presented. These data, coupled with argon and calcium emission data, give values for the rates of both radial and vertical transport in the plasma. The data indicate that analyte emission behavior is governed primarily by the rate at which the central channel can be heated through radial transport processes. The electron densities measured in the load coil region agree well with electron densities calculated by models assuming local thermodynamic equilibrium, but agree poorly with non-equilibrium models. Some of the timedependent emission behavior observed in previous work with modulated plasmas is explained by non-uniform heating of argon in the load coil region.Presented in part at the 1989 European Winter Conference on Plasma Spectrochemistry, Reutte, Austria     

Applications of inductively coupled plasma mass spectrometry and laser ablation inductively coupled plasma mass spectrometry in materials science

Inductively coupled plasma mass spectrometry (ICP-MS) and laser ablation ICP-MS (LA-ICP-MS) have been applied as the most important inorganic mass spectrometric techniques having multielemental capability for the characterization of solid samples in materials science. ICP-MS is used for the sensitive determination of trace and ultratrace elements in digested solutions of solid samples or of process chemicals (ultrapure water, acids and organic solutions) for the semiconductor industry with detection limits down to sub-picogram per liter levels. Whereas ICP-MS on solid samples (e.g. high-purity ceramics) sometimes requires time-consuming sample preparation for its application in materials science, and the risk of contamination is a serious drawback, a fast, direct determination of trace elements in solid materials without any sample preparation by LA-ICP-MS is possible. The detection limits for the direct analysis of solid samples by LA-ICP-MS have been determined for many elements down to the nanogram per gram range. A deterioration of detection limits was observed for elements where interferences with polyatomic ions occur. The inherent interference problem can often be solved by applying a double-focusing sector field mass spectrometer at higher mass resolution or by collision-induced reactions of polyatomic ions with a collision gas using an ICP-MS fitted with collision cell. The main problem of LA-ICP-MS is quantification if no suitable standard reference materials with a similar matrix composition are available. The calibration problem in LA-ICP-MS can be solved using on-line solution-based calibration, and different procedures, such as external calibration and standard addition, have been discussed with respect to their application in materials science. The application of isotope dilution in solution-based calibration for trace metal determination in small amounts of noble metals has been developed as a new calibration strategy. This review discusses new analytical developments and possible applications of ICP-MS and LA-ICP-MS for the quantitative determination of trace elements and in surface analysis for materials science.     

Determination of arsenic species by inductively coupled plasma mass spectrometry with ion chromatography

Five arsenic species, trimethylarsine oxide, dimethylarsenic acid, monomethylarsonic acid, arsenobetaine and sodium arsenite, in urine were analysed by inductively coupled plasma mass spectrometry with ion chromatography (IC ICP MS). Since the toxicities of different arsenic compounds are different, speciation of arsenic compounds is very important in the investigation of metabolisms. In this paper, we applied ion chromatography (IC) as a separation device and inductively coupled plasma mass spectrometry (ICP MS) as a detection device. For separation of the five arsenic compounds, an anion-exchange column and, as mobile phase, tartaric acid were used. The eluent from the IC column was introduced directly into the nebulizer of the ICP MS and analysed at 75 amu. Detection limits were from 4 to 9 pg as arsenic.     

A new continuous calibration method for inductively coupled plasma spectrometry

A new calibration method was developed and applied to inductively coupled plasma atomic emission spectrometry. External calibration was performed as follows. A container was filled with a given volume of deionized (V _p) water. Then a concentrated standard was introduced at a controlled rate (Q _e) into the tank by means of a peristaltic pump. The resulting solution was stirred throughout the experiment. Simultaneously, the solution inside the tank was pumped from the vessel to the plasma at a given rate (Q _s). The signal was continuously recorded. The variation of the concentration of the solution leaving the tank with time was determined by applying a basic equation of stirred tanks. The representation of the emission intensity versus the time and the further conversion of the time scale into a concentration scale gave rise to the calibration line. The best results in terms of linearity were achieved for V _p=15 cm³, Q _e=0.6–0.75 ml min⁻¹ and Q _s=1–1.2 ml min⁻¹. Graphs with more than 40 standards were obtained within about 10 min. The results found were not statistically different from those afforded by the conventional calibration method. In addition, the new method was faster and supplied better linearity and precision than the conventional one. Another advantage of the stirred tank was that procedures such as dynamic calibration and standard additions could be easily and quickly applied, thus shortening the analysis time. A complete analysis following these procedures based on the measurement of 30 standards took about 5 min. Several synthetic as well as certified samples (i.e., bovine liver, mussel tissue and powdered milk) were analyzed with the stirred tank by applying four different calibration methodologies (i.e., external calibration, internal calibration, standard additions and a combination of internal standardization and standard additions), with the combination of internal standardization and standard additions being the method that provided the best results. The element concentrations obtained were not significantly different from the actual or certified values.     

Simultaneous multielemental determination using a low-resolution inductively coupled plasma spectrometer/diode array detection system

This work presents a versatile method for simultaneous multielemental analysis using detection with photodiode arrays and multivariate calibration techniques. A multidetection system based on an array of 1024 photodiodes was built and adapted to a commercial plasma emission scanning spectrometer. Spectral data were acquired at low resolution, allowing simultaneous monitoring of a broad spectral range and resulting in very informative but considerably overlapped spectra. Partial least squares and principal component regressions were employed to minimize overlapping problems. A numerical procedure for window selection was also developed.

The new method was applied to the simultaneous determination of manganese, molybdenum, nickel, chromium and iron in steel samples, resulting in average relative prediction errors of 2.1% for Mn, 3.4% for Mo, 0.6% for Cr, 1.5% for Ni and 0.8% for Fe. These errors are comparable to those observed with conventional scanning detection systems and separate univariate calibrations, but the new method allows simultaneous determination of the five elements, with data acquisition significantly faster than in scanning instruments.     

Determination of inorganic contaminants in glue by inductively coupled argon plasma optical emission spectrometry

A closed vessel method using a microwave oven was developed for the determination of As, B, Ba, Bi, Cd, Cr, Cu, Fe, Hg, Ni, Pb, Se, Sn and Sb by Inductively Coupled Argon Plasma Optical Emission Spectrometry (ICP OES). The method was applied to samples of polyvinyl acetate-based glue in water emulsions. Parameters such as wavelength, nebulization pressure and RF power were optimized and the residual acidity after the digestion process was determined. The addition of internal standards was evaluated and the accuracy of the proposed method was verified with addition and recovery experiments and also with certified reference materials, achieving good results. Using a nebulization flow rate of 0.73 L min⁻¹and a RF power of 1200 W it was possible to obtain adequate values for limit of detection and limit of quantification as well as recovery values in the range of 80-106%, for all the analytes. The analysis of coloured glue samples (white, black, blue, yellow, red and green), widely used by children, showed no contamination by the elements studied.     

电感耦合等离子体质谱激光烧蚀固体进样技术新进展

本文简单地介绍了电感耦合等离子体质谱(LA-ICP-MS)的基本原理及装置。分别对LA-ICP-MS在飞秒激光器、紫外激光器、固液气溶胶混合进样、集合式小样品标样、原位统计分布技术上的技术新进展进行了详细的评述。