应用手持式XRF分析仪快速测定白铜中的Cu、Ni、Co含量

采用国产手持式XRF分析仪快速分析了白铜合金主元素的含量,探讨了白铜合金基体效应对测量结果的影响,采用经验系数法中多元回归分析建立数学模型,较好地校正基体效应,分析白铜合金中铜、镍、钴的平均相对误差分别为0.39%、1.83%、1.59%。     

X射线荧光光谱法测定新研制土壤标准物质中11种元素的含量北大核心CSCD

用粉末压样机将5.0 g经105℃烘干的样品制成样片,采用X射线荧光光谱法(XRF)测定其中铅、砷、铜、锌、铬、镍、钴、钒、锰、锡和钼等11种元素的含量。以经验系数法和康普顿散射内标法校正基体效应和谱线重叠干扰,选择65种土壤、沉积物及岩石国家标准物质用于绘制校准曲线。结果显示,11种元素的质量分数在一定范围内与其对应的荧光强度呈线性关系,检出限(3s)为1.0~3.9μg·g^(-1),测定值的相对标准偏差(n=10)为0.64%~9.2%。对新研制的30个农用地土壤成分标准物质进行测定,按照HJ 780-2015的质量控制标准评估各元素的测定准确度,结果表明:铅、铜、锌、铬、镍、钒、锰的测定合格率均为100%,说明XRF可用于土壤中这7种元素的测定;钴的测定合格率为93.3%,这是由于样品中高含量铁的影响;砷的测定合格率为80.0%,当砷的质量分数小于13μg·g^(-1)时准确度较差;锡、钼的测定合格率不足50.0%,因此不建议用XRF测定土壤中锡和钼的含量。     

分光光度法测定合金钢中镍含量

镍是合金钢中重要元素之一 ,它可以增加钢的的弹性、延展性和抗腐蚀性 ,使钢具有较高的机械性能。目前测定合金钢中的镍 ,不论是 JIS1 2 1 6-82 [1] 法还是 GB2 2 3,2 4 - 82 [2 ] 法 ,均需沉淀或萃取 ,使镍与合金钢中其它元素分离 ,因此手续复杂 ,操作时间长 ,而且使用试剂较多。本法用磺基水杨酸掩蔽铁、铜、铝等元素后直接用分光光度计测定镍。此法不需沉淀或萃取分离 ,可用于测定进口合金钢中的镍含量。1　实验部分1 .1　试剂与仪器过硫酸铵 ( 343g/L) ,丁二酮肟 ( 1 0 g/L) ,氢氧化钠 ( 5 0 g/L) ,磺基水杨酸 ( 32 4 g/L) ,镍标准…     

同位素源激发X-射线荧光分析合金样品的吸收-增强效应的数学校正—基本参数法

本文叙述了利用基本参数法校正源激发合金元素荧光分析的基体效应的基本原理、基体效应的修正方法。讨论了当激发源的能量比元素的吸收限大很多时,吸收系数的散射修正,利用~(241)Am源激发,测量了铅锡合金和高合金钢样品中各元素的荧光强度,并用自编数据处理程序计算了元素含量,结果与标准含量进行比较。计算含量误差一般小于10％。     

X射线荧光光谱法测定合金中的磷

采用X射线荧光光谱法测定铁基和镍基合金中磷的含量。选用钨的Mα线和钼的Lα线作为测量重叠干扰系数时的参照线。选用合金系统中不存在的钾和钪元素作为校正元素代替钨和钼,这两个元素实际测量的分别是钨的Mα线和钼的Lα线。分别用只含钼和同时含钼、钨的两套标准样品测定了重叠干扰系数,并制定了分析磷的校准曲线。方法应用于标准样品的测定,测定值与认定值相符,测定值的相对标准偏差(n=10)为0.68%。     

X射线荧光光谱法测定石油焦中主量元素硫和痕量元素的含量

提出了粉末压片制样-X射线荧光光谱法测定石油焦样品中硫、钠、镁、铝、硅、磷、氯、钾、钙、钡、钛、钒、铬、锰、铁、镍、铜和锌等18种元素含量的方法。将粒径小于0.076mm的石油焦粉末经105℃烘干后置于模具中,以160MPa压力制成厚度小于4mm的样品。以经验系数法和康普顿散射线内标法校正基体效应和元素间的谱线重叠干扰。对石油焦样品连续11次测定,各元素测定值的相对标准偏差均小于8%。方法用于标准样品的分析,测定结果与认定值相符。     

X射线荧光光谱分析水基标样替代油基标样的实现

用水基标样替代油基标样,建立X射线荧光光谱测定石油及其产品中微量元素含量的方法。以钒、锰、铁、镍为研究对象,采用乳化技术制备试样,用乳化剂司班80将水基标样和油结合起来,合成油包水型乳状液;采用理论α影响系数法和内标法校准油水差异校正基体效应。实验发现,如果基体组成已知,理论α影响系数法可以校正水基和油基的基体差异,水基标样和油基标样可直接互换;如果基体组成未知,采用内标法校正基体效应,需要将样品合成油水混合液校正才能成功。用原油和燃料油样品进行对比实验,测得结果与标准方法一致。     

亚硝基R盐分光光度法测定合金钢中钴

本文改进了亚硝基R盐分光光度法测定合金钢中钴的分析方法,并详细探讨了该方法中吸收波长、缓冲溶液、氧化剂、消解酸种类、加热时间、共存离子等测定条件对结果准确度和精密度的影响.结合示差光度法,在不需分离铁、铜、镍、铬等干扰元素的条件下,可适用于测定合金钢中高含量钴,相对误差在3%以下,相对标准偏差小于1%.测定高含量钴标准...     

X射线荧光光谱法测定镍基高温合金中合金组分的通用工作曲线的制作——基本参数(FP)法虚拟合成标准样品的应用

应用基本参数(FP)法虚拟合成标样制作了X射线荧光光谱法(XRFS)测定不同类型的镍基高温合金中18种合金元素和4种杂质元素的通用工作曲线。选择了最佳的仪器工作条件和合理的待测元素的分析线系,测定了9种元素受共存元素分析线重叠干扰的校正系数,用瑞利散射线扣除背景及通道材料的影响。在设定虚拟合成标样中各元素的含量,并算得在此设定值下的荧光强度后,用FP法计算各元素在其定值下的最终强度,从而完成了FP法工作曲线。应用此虚拟合成单标工作曲线对多种标准样品进行测定,证明该工作曲线可通用于各种类型的镍基高温合金的分析。     

土壤、沉积物系列标准物质中38种元素的ICP-MS定值

探讨了电感耦合等离子体质谱测定土壤元素的基体效应及元素间的基体干扰，采用模拟土壤元素天然组成比值的校正溶液，利用^115In-^103Rh双内标校正系统有效地抑制了分析信号的动态漂移，建立了测定土壤中元素的ICP－MS方法；对GBW07410－07416土壤、沉积物系列标准物质进行定值，测定结果与XRF分析结果比较，同时用于GBW07404、GBW07405、GBW07408、GBW07309管理样分析，结果令人满意。     

萤石成分分析方法的标准现状与研究进展

萤石是一种重要的战略性非金属矿产资源,本文对中国国家标准、行业标准、国际标准（ISO）、美国标准（ASTM）以及俄罗斯标准（GOST）中的萤石成分分析标准方法的现状进行了介绍。对近年来X射线荧光光谱法（XRF）、电感耦合等离子体发射光谱法（ICP-AES）、电感耦合等离子体质谱法（ICP-MS）、激光诱导击穿光谱法（LIBS）等技术在萤石成分分析中的应用以及标准物质/标准样品研制情况进行了总结和评述。文章认为,萤石分析测试技术标准体系相对完备,XRF、ICP-AES、ICP-MS等仪器分析测试技术已普遍应用于萤石样品实验室分析,建议尽快研究并建立萤石中稀土等微量元素测定的标准方法,并开展相应标准物质/标准样品的研制,同时应大力开展原位在线分析技术的研究与开发,以适应工业在线自动化监测的需求,LIBS与在线XRF技术联合在萤石在线分析方面具有良好的应用潜力。     

X射线荧光光谱分析不锈钢时的数学校正方法

本文探讨了用XRF法分析不锈钢时，用个别交叉项系数校正Cr、Fe、Ni之间的交叉效应，从而有效地修正了它们之间的吸收一增强效应，使分析结果得到改善，最大误差不超过0．5％。与C－Q方程相比，该法计算简便，具灵活性和实用性，可推广使用。     

Application of thermal analysis techniques to study the oxidation/reduction phenomena during sintering of steels containing oxygen-sensitive alloying elements

For the consolidation of steel parts manufactured by powder metallurgy (PM) techniques, removal of the surface oxides covering metallic powder particles is a necessary prerequisite. In PM steels with conventional compositions, reduction of the oxides is easily achieved in traditional sintering furnaces. However, processing steels containing alloying elements with a high oxygen affinity represents a big challenge that requires a deeper understanding of the chemical processes occurring during sintering. In the present work, thermogravimetry analysis coupled with mass spectrometry is used to describe the oxidation/reduction phenomena that take place when sintering steel powders and how these processes are modified by the addition of admixed particles containing oxygen-sensitive elements. Carbothermal reduction processes are studied using pure oxides (Fe₂O₃, MnO₂, Cr₂O₃ and SiO₂) as well as water-atomized Fe powders mixed with small amounts—4 mass/%—of Cr, Mn and Si powders or Fe–Mn–Si–(Cr) master alloy powders. The results show that there is an oxygen transfer from the base iron particles to the oxidation-sensitive elements—“internal getter effect”—taking place mostly through the gas phase. Different alloying elements (Cr, Mn, Si) show different temperature ranges of susceptibility to oxidation. Combination of these oxygen-sensitive alloying elements in the form of a master alloy powder reduces their sensitivity to oxidation. Also, the use of master alloys promotes the concentration of the oxides on the surface of the alloying particles and not in the grain boundaries of the surrounding iron particles—as occurs when using Mn carriers—which should have a beneficial impact on the final mechanical performance.     

直读光谱法测量镁合金中锰含量的测量不确定度评定

根据GB/T13748.21-2009镁及镁合金化学分析方法(光电直读发射光谱分析方法测定元素含量)对镁合金中锰元素含量进行了分析,对锰含量测量的不确定度来源进行了分析,并对测量过程中产生的不确定度进行了评定.此外,指出了该方法影响锰元素测量不确定度的主要原因,以期为镁合金中锰元素含量的光谱分析提供参考.     

The atomic absorption determination of antimony,arsenic, bismuth, cadmium, lead, and tin in iron, copper,and zinc alloys with the graphite furnace

Antimony, arsenic, bismuth, cadmium, lead, and tin can be determined in metallurgical samples by flame atomic absorption spectrometry at levels of 0.005 wt%, but lower concentrations frequently necessitate preconcentration. The graphite furnace allows determination of these elements at concentrations 1–2 orders of magnitude lower than is possible with flame techniques. All six elements have detection limits at or below 1μg g⁻¹ in a variety of alloys. Calibration for antimony and load was done with standards containing the principal component of the alloy as a synthetic matrix. Bismuth, cadmium, and tin could be determined accurately only by the standard addition method. Arsenic could be determined in iron alloys with synthetic standards, but standard additions were required for copper alloys.     

X射线荧光光谱法测定彩涂板涂层中铅、镉和总铬

自行制备了12块校准样品,其涂层厚度和涂层中铅、镉和铬含量均按梯度分布。涂层的厚度采用GB/T 13448-2019标准所推荐的DJH法测定和定值。分析这系列样品时,测定涂层中铅、镉和总铬时用IEC 62321-5的微波法溶解后,按电感耦合等离子体原子发射光谱法定值。应用上述校正样品试验,并提出了直接测定彩涂板涂层中铅、镉和总铬含量的X射线荧光光谱法(XFS)彩涂板的基板为冷轧板,在其外表面有镀锌层。在这2种材料中都可能含有与有机涂层中待测定的含量近似的相同元素,将对测定造成干扰。此外,有机涂层中的基体元素钛及硅也对测定造成干扰。利用XRF仪器自带的薄层分析软件和基本参数法软件对上述干扰分别予以校正,使铅、镉、铬校准曲线的线性相关系数达到0.9。所提出方法测定铅、镉、铬的检出限(3s)依次为5×10^-4%,3×10^-4%,5×10^-4%。随机取3个校正样品,按所提出方法测定其中铅、镉与总铬的含量,并用IEC 62321-5标准方法进行校对分析。结果表明:两种方法的结果相互一致,所得测定值的相对标准偏差(n=6)为8.5%(铅),9.2%(镉)和11%(铬),均分别小于IEC标准方法测定值的相对标准偏差(n=6)为29%,14%,17%。本方法达到快速、准确的要求,适合用于RoHS规定对彩涂层的检量检测。     

Corrosion and oxidation resistance properties of titanium-containing low-alloy steel

An innovative technique of using conventional low-alloy steel as the prefabricated starting material and pure titanium and aluminium as alloying additions has been employed in this study for obtaining titanium-containing corrosion and oxidation resistant low-alloy steel. Corrosion resistant iron-titanium alloys have also been developed, which may find use in the hardware of phosphoric acid making plants and other equipment. The corrosion and oxidation resistance properties of these alloys have been exhaustively studied using modern electrochemical techniques. Initially the alloying element compatibility range was worked out for titanium in iron, by determining the optimum physicochemical properties of the iron-titanium matrix corresponding to a particular titanium percentage. This value was then extrapolated to the low-alloy steel matrix, assuming the prefabricated low-alloy steel (SAE 8620) to be an impure iron (due to the lower concentration of alloying elements like Mn, Si, P, S, Cr, Ni, Mo, etc.), for obtaining a resistant low-alloy steel. Ti 5%-SAE 8620 low-alloy steel matrix revealed superior resistance to oxidation and corrosion compared to SAE 8620 alloy. Received: 31 May 1999 / Accepted: 19 October 1999     

Colorimetric determination of chromium in titanium alloys

Chromium-titanium alloys are becoming increasingly important because of their strength and corrosion, resistance. Therefore, accurate methods for the determination of chromium in this type of alloy are needed. A colorimetric procedure for the determination of chromium in titanium alloys is proposed. In this method the chromium is oxidised to the chromate state by means of ammonium persulfate and potassium permanganate in the presence of silver nitrate as a catalyst. Diphenylcarbazide is then added to an aliquot of the solution, and the violet color read in 10 to 40 minutes at 580 millimicrons. None of the elements found in commercial titanium alloys, including iron, vanadium, molybdenum, and tungsten, interferes with the method. The proposed method is superior to the volumetric method for the determination of small amounts of chromium. The method is designed for titanium. alloys containing 0.02 to 4 per cent chromium.     

Monte Carlo simulations of XRF intensities in non-homogeneous matrices

In this paper a quantitative explanation is formulated for many discrepancies in the analysis of non-homogeneous materials. Metal alloys are the examples by excellence of such materials. Fe-Cr and Zn-Al alloys with a dispersed phase containing one of the elements only or both elements in a concentration different from the bulk, are simulated. Monte Carlo methods are used for generating the dispersions as well as for simulating the XRF processes.