高纯四氯化锗测试样品的采集和制备方法研究

针对光纤级高纯四氯化锗(99.999999%)中痕量含氢杂质吸收峰红外透过率检测(FTIR)用试样的采集,以及痕量金属杂质的电感耦合等离子体质谱法(ICP-MS)测定用试样的制备方法进行了系统研究。设计开发了用于检测痕量含氢杂质吸收峰红外透过率的样品采集实验装置,实现了含氢杂质(如—OH、—CH、HCl等)吸收峰的红外透过率在线连续测试,试样采集过程全密闭进行,避免了采样过程的二次污染,采样过程流程简短,操作简便;实验优选了在制备ICP-MS法测定痕量金属杂质用的试样过程中消除四氯化锗基体干扰、防止砷等易挥发杂质损失以及防止样品处理过程污染试样的制样方法,实现了试样制备过程二次污染源的有效控制,制样过程试剂消耗量少,制备时间短,待测元素无损失。     

电感耦合等离子体-质谱法测定高纯ZnS粉末中痕量金属杂质

建立了用电感耦合等离子体-质谱(ICP-MS)法测定高纯ZnS粉末中Mg、Al、Mn、Ni等11种痕量金属杂质含量的方法。样品溶解后可直接进样分析。加标回收率为89%~120%。各金属杂质均为10 ng/mL的混合标准溶液平行7次进样的相对标准偏差均小于5%。方法能够满足纯度在99.99%~99.999%范围的ZnS样品中杂质测定的需要。     

一种简易的多次内反射红外装置的试制

通常的红外吸收光谱图是用红外光对样品进行透射(见图1a),样品吸收了其特征波长的光能,剩余部分的光进入分光器分光,再记录下来。这样,相当多的材料,如硫化橡胶、织物、涂层、纸张、泡沫塑料等样品,由于很难制备出很薄的试样,其厚度正适合于透射法可测的范围,试样厚度稍厚,红外全部透不过去,就难于得到其红外吸收光谱图。近年来由于 Harriek、Fahrenfort 等提出的内反射(Internal Reflection)技术的发展,上述困难就不复存在了,无须特殊制备试样,即可获得满意的谱图。内反射红外装置已成为近年来红外光谱仪必备附件之一。本文将介绍我们在 UR-10型红外光谱仪上,试制上述附件的情况。(一)原理先简要地介绍内反射原理。如将样品紧贴在一晶体表面上(晶体的材料是选择可以透过红外,折光指数又很大的物质,最常用的有 KRS-5晶体与锗晶体),当光束对样品与晶体的界面的入射角大于其临界角时,就发生全内反射(Total Internal Reflec-tion)即光能没有损失,全部反射了出去,其光路如图1b 所示,全内反射发生在样品完全不吸收红外时的情况。若样品对红外有特征吸收,那么反射出的能量就受到衰减,因为衰减是发生在试样的特征吸收峰处,所     

电感耦合等离子体光谱/质谱联机同时测定多金属结核中常量、微量、痕量元素

采用电感耦合等离子体质谱(ICP-MS)与等离子体光谱(ICP-OES)联机同时测定多金属结核样品中常量、微量、痕量元素。样品经高压密封溶样弹消解后,一次气动雾化进样,ICP-OES测定常量和微量元素,ICP-MS测定微量和痕量元素。详细探讨了不同浓度范围元素的测定方式、元素分析信号的采集模式、多原子离子干扰的校正因子。采用ICP-MS与ICP-OES二种方式同时测定Co、Cu、Ni、Zn、V、Ba、Sr,分析结果表明具有较好的一致性。所建立的ICP-MS与ICP-OES联机检测技术用于多金属结核标准样品的分析(Nod-A-1,GSPN-1,GSPN-2,GSPN-3),分析结果与推荐值符合,相对标准偏差小于10％。     

辉光放电质谱法在无机非金属材料分析中的应用

辉光放电质谱法(GDMS)作为一种固体样品直接分析技术,已广泛应用于金属、半导体等材料的痕量和超痕量杂质分析。近年来,随着制样方法和离子源装置的改进,GDMS同样也能很好地应用于玻璃、陶瓷、氧化物粉末等非导体材料的成分分析。简介了GDMS的基本原理和分析特点,概述了GDMS在无机非金属材料分析的方法以及应用情况。     

漫反射红外光谱法测定片剂中维生素B_1

采用新型制样法,应用漫反射傅里叶变换红外光谱(DRIFTS)法测定了维生素B_1片剂中维生素B_1的含量。选择波数1659cm~(-1)处的吸收峰作为定量吸收峰,片剂辅料中不含和含有酒石酸或枸橼酸的样品分别用1630~1690cm~(-1)范围内的峰面积和1654cm~(-1)处的单波数评估吸光度,吸光度与质量分数均呈良好的线性关系,相关系数0.98,相对标准偏差(RSD)≤6.2%。定量分析市售4种维生素B_1片剂,结果与药典中紫外分光光度(UV)法基本一致。DRIFTS法操作简便、快速、样品前处理简单、无试剂消耗、无废液产生,选择适合的吸光度评估方法和基线校正范围可排除可溶性杂质对分析测定的干扰,定量分析结果准确。     

真空升华法测定环戊二烯镧系金属络合物的红外光谱

镧系金属有机络合物对氧和水极不稳定,易被氧化和水解。进行这类固体样品的红外光谱测试时,一般在充干燥惰性气体的干燥箱中,用石蜡油糊法制样。Dubeck等曾报导用这种方法制样测得一系列二茂氯化镧系金属络合物的红外光谱,在3300厘米~(-1)附近都有吸收峰。我们用干燥箱法测定过很多与之类似的镧系元素环戊二烯络合物光谱,在3500厘米~(-1)附近也有吸收(图1a)。这类络合物按其结构不应在这里出现吸收,可能是干燥箱中残留的少量氧和水使络合物破坏而造成的。干燥箱操作的另一不足之处是需多次抽空充气,很费     

空气敏感固体化合物红外光谱测试方法

在红外光谱测试中对某些能升华而又对空气敏感的金属有机化合物可以经过真空处理得到合适的测试样品。但这种方法不适用于不能升华的样品。一般固体样品适用的红外常规压片和糊状制样方法,因其操作过程较长,故在空气敏感的样品制样中必需有保护环境。在上述二种方法中,以糊状法制样更适合于空气敏感样品。这时,油层包复在样品粒子表面,起着隔离空气的作用,使样品在光谱测量过程的短时间中免于(或不致很快)破坏。但油糊(石蜡油或氟油)制     

辉光放电质谱法在高纯材料分析中的应用

高纯材料是现代高新技术发展的基础,在电子、光学和光电子等尖端科学领域发挥着重要作用。采用固体样品直接分析的辉光放电质谱法(GDMS),在高纯金属、高纯半导体材料的痕量和超痕量杂质分析中有着非常广泛的应用。综述了GDMS法对高纯金属、高纯半导体材料进行的元素分析,并对分析过程中工作参数、溅射时间、干扰峰等因素的影响进行了阐述。同时,也详述了应用GDMS法对高纯金属钛、镉,高纯半导体硅,分别进行的痕量杂质元素分析,结果显示放电稳定性良好,典型元素含量的相对标准偏差均在较为理想范围内。GDMS应用前景广泛,未来,GDMS将在除固体样品之外的其他样品类型的分析领域中发挥重要作用。     

脉冲雾化火焰发射光谱法测定高纯铯中痕量锂、钠、钾和铷

纯金属铯中碱金属的测定大多采用火焰原子吸收或火焰发射光谱法,报导过纯度90～99%的金属铯中碱金属杂质的火焰发射测定方法。对于99.99～99.999%的高纯铯中痕量碱金属的测定,直接火焰原子吸收法的灵敏度不能满足要求,采用火焰发射法较为有利。为减少样品消耗量,克服高纯铯样品有限,又要测定多种痕量杂质的矛盾,并保证方法具有足够的灵敏度及较好的测定下限。本文采用微量溶液脉冲雾化技术与火焰发射法相结合,并利用简易标准加入法(或称标准加入法的二次     

Interference-free atomic spectrometric method for the determination of trace amounts of germanium by utilizing the vaporization of germanium tetrachloride

Trace amounts of germanium can be determined by atomic spectrometry by utilizing the vaporization of germanium tetrachloride at ambient temperature. Using an intermittent or continuous flow reactor, the sample solution was mixed with concentrated hydrochloric acid to form volatile germanium tetrachloride which can subsequently be determined by atomic spectrometry. The conditions for the volatilization of germanium chloride were investigated in detail and rapid method for the determination of trace amounts of germanium in real samples was proposed. A detection limit of 0.5 ng ml⁻¹ (3σ_n−1) was obtained by using atomic fluorescence spectrometric detection and the precision found was 0.8% for a germanium concentration of l00 ng ml⁻¹. Atomic emission and absorption spectrometric methods were also tested. Owing to the high selectivity of the reaction, no interference was found in the determination. The method was applied to the determination of germanium in several standard and certified reference materials; the results obtained were in good agreement with the certified values.     

萃取分离-ICP-MS测定高纯铝中痕量元素

利用吡咯烷二硫代氨基甲酸铵(APDC)-CHCl_3萃取分离体系结合ICP-MS对高纯铝中的Co、As、Mo、In、Sn、Sb、Cd、Ag、Pd、Au进行测定,建立了测定高纯铝中痕量元素的方法.实验分别考察了仪器工作参数,萃取酸度,络合剂用量对于杂质元素测定结果的影响,选择了最佳实验条件.各元素的回收率在77.6%～112.2%之间,检出限0.02～0.6 ng/mL,RSD为1.6%～7.2%.     

高纯钛的辉光放电质谱法多元素分析

采用辉光放电质谱法(GD-MS)测定高纯钛中Mg、Al、Cr、Fe、V、Mn、Co、Ni、Cu、Zn、As、Sn、Sb、Ta、W、Pb、Bi等痕量杂质元素,并对GD-MS工作参数及条件进行了优化。主要元素与内标校正ICP-MS法定量分析的结果一致,对结果差异的原因进行分析,论述了Element GD辉光放电质谱仪在痕量杂质元素分析方面的优势。     

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.     

Direct determination of rare earth impurities in high purity erbium oxide dissolved in nitric acid by inductively coupled plasma mass spectrometry

A novel method was developed for the direct determination of trace quantities of rare earth elements (REEs) in high purity erbium oxide dissolved in nitric acid by inductively coupled plasma mass spectrometry (ICP-MS) in this work. The mass spectra overlap interferences arose from Er matrix on the neighbouring and monoisotopic analytes of ¹⁶⁵Ho(100) and ¹⁶⁹Tm(100) were eliminated by adjusting instrumental peak resolution value from 0.7 to 0.3 amu. The matrix suppression effect of Er on the ion peak signals of REEs impurities was effectively compensated with spiking In as internal standard element. The limit of quantitation (LOQ) of REEs impurities was from 0.0090 to 0.025 μg g⁻¹, the recoveries of spiked sample for REEs were found to be in the range of 90.3-107% through using the proposed method and relative standard deviation (R.S.D.) varied between 2.5% and 6.7%. The novel methodology had been found to be suitable for the direct determination of trace REEs impurities in 99.999-99.9999% high purity Er₂O₃ and the results obtained from this method keep in good agreement with that acquired from high resolution ICP-MS.     

微波消解-石墨炉原子吸收光谱法测定纳米二氧化钛中痕量砷

建立了微波消解-石墨炉原子吸收光谱法（GF-AAS）测定纳米二氧化钛中痕量杂质元素砷的分析方法。采用由一定浓度和比例的氢氟酸、硝酸组成的混合试剂,结合应用高压密闭微波加热技术快速完全消解纳米二氧化钛样品,优选了最佳微波加热控制程序,不仅解决了二氧化钛难消解和待测元素砷高温消解过程中易挥发损失等难点,而且检测溶液酸度低,避免对GF-AAS石墨管的侵蚀。并且,通过基体效应影响实验,优化选择了石墨管类型、石墨炉升温原子化控制程序以及原子吸收光谱仪检测参数,消除热稳定性强的二氧化钛基体对测定易挥发痕量元素砷的影响。方法检出限为0.02μg/L,加标回收率为93.0%~106.0%,相对标准偏差9.4%,与ICP-MS检测方法结果对照一致。     

Substitute technology for reference substances in the analysis of impurities in cefonicid for injection with HPLC using a diode array detector

With HPLC using a diode array detector (DAD), a method of substitution for reference substances in impurity profiling control was developed that combined peak tracking by the correlation of spectra with application of correction factors for determination of each impurity. For qualitative analysis, two-dimensional (2D) standard spectrochromatographic data produced by HPLC-DAD were compared with sample data to develop 2D chromatographic spectral correlative maps so that the three target impurities were recognized without preparation and injection of reference solutions. For quantitative analysis, correction factors among cefonicid and the three impurities were established. The correction factors were 1.06 for 5-mercapto-1,2,3,4-tetrazole 1-methyl sulfonic acid detected at 255 nm, 0.77 for 7-aminocephalosporanic acid detected at 265 nm, and 0.97 for methoxycefonicid detected at 268 nm. The method could be used in analysis of related substances in cefonicid for injection without recourse to chemical reference standards of the three impurities.     

Determination of ultratrace impurity elements in high purity niobium materials by on-line matrix separation and direct injection/inductively coupled plasma mass spectrometry

The determination of 52 impurity elements in niobium materials (niobium metal, niobium oxide (V), and niobium pentaethoxide) was performed by inductively coupled plasma mass spectrometry (ICP-MS) with on-line anion exchange matrix separation as well as direct nebulization. Niobium material samples were decomposed with a mixture of hydrofluoric acid and nitric acid to prepare 10% niobium solutions. In the on-line anion exchange matrix separation/ICP-MS, the niobium and hydrofluoric acid concentrations in sample solution were adjusted to 5% and ca. 8 M, respectively. The solution was then injected into the carrier stream from the sample loop of injection valve to pass through an anion exchange resin column. In the anion exchange separation, niobium in the fluoro-complex form was adsorbed on the resin, while impurity elements were eluted. The eluted elements were introduced into ICP-MS for the determination of 25 impurity elements. On the other hand, 27 impurity elements could not be separated well from niobium matrix under the above anion exchange conditions, and then the sample solution with the niobium concentration of max. 0.2% containing internal standard elements was injected from the sample loop of injection valve directly to introduce into ICP-MS. As a result, 52 impurity elements in three kinds of niobium materials could be determined at the ng g⁻¹ level.     

-电感耦合等离子体质谱法测定硅锰冶炼渣中8种金属元素

实验采用HCl-HNO₃-HF-HClO₄混合酸为消解体系对样品进行前处理,加入1.0 mL盐酸羟胺溶液(100 g/L)溶解残渣,选择合适的同位素,以¹⁰³Rh为内标测定Cr、Co、Ni、Cu、Zn和Cd,以¹⁹³Ir为内标测定Tl和Pb,建立了电感耦合等离子体质谱(ICP-MS)法测定硅锰冶炼渣中8种重金属元素的方法。实验发现,样品前处理选择HCl∶HNO₃∶HF∶HClO₄=5∶5∶5∶1,并在复溶阶段加入1.0 mL盐酸羟胺溶液(100 g/L)可以完全消解样品,实验采用KED模式和干扰系数校正法消除质谱干扰,样品中待测元素的测定结果不受基体成分的干扰。通过绘制校准曲线及测定流程空白,各元素校准曲线的相关系数均大于0.9999,方法检出限为0.006~0.19 mg/kg,方法定量限为0.018~0.57 mg/kg。对硅锰渣实际样品进行测定,各元素的相对标准偏差(RSD,n=11)在0.83%~4.1%,加标回收率为94.7%~106%;经过人员比对实验,相对偏差为-4.54%~4.24%。测定结果稳定可靠,能满足硅锰冶炼渣中8种微量金属元素含量的分析检测要求。