火花放电原子发射光谱分析全流程正确度控制方法研究  

Research on trueness control method of full process in spark discharge atomic emission spectrometric analysis

作　　者：贾云海[1,2] 孙晓飞 JIA Yun-hai;SUN Xiao-fei(Central Iron & Steel Research Institute, Beijing 100081, China;NCS Testing Technology Co., Ltd., Beijing 100081, China)

机构地区：[1]钢铁研究总院,北京100081 [2]钢研纳克检测技术股份有限公司,北京100081

出　　处：《冶金分析》2020年第7期1-7,共7页Metallurgical Analysis

基　　金：国家重大科学仪器设备开发专项(2017YFF0106208)。

摘　　要：火花放电原子发射光谱法以临界差CD0.95为正确度验证上限值符合标准,测量偏倚不大于临界差,表明测量正确度合格。当实验室采用更精细的内控手段如类型标准化时,应采用更小的正确度临界差。在光谱分析流程中,未经类型标准化,采用CD0.95验证正确度。若仪器经类型标准化样品A测量n1次,正确度验证样品B测量n2次的临界差形式为r·√(1/2n1+1/2n2),当(n1,n2)组合为(3,2)或(4,2)时,临界差值为0.65r或0.61r(r为重复性限)。经类型标准化后,如果测量持续较长时间(1h以上),正确度验证的临界差为含时间因素的CD0.95(Rw),其数值约为CD0.95/2。月度平均值-标准偏差控制图中两倍标准偏差2S“警告限”可作为实验室的CD0.95(Rw)。当考虑类型标准化样品A和验证样品B扩展不确定度(U)时(包含因子k=2),样品B正确度验证临界差为√r^2*(1/2n1+1/2n2)+UA^2+UB^2。除火花放电原子发射光谱法外,任何采用类型标准化的方法短时间内都可以用相应的临界差验证正确度。The critical difference CD0.95 is used as tolerance of trueness verification in spark discharge atomic emission spectrometric analysis.When the measurement bias is not larger than the critical difference,it indicated that the measurement trueness is qualified.If more careful internal control means like type standardization are applied in the laboratory,the smaller critical difference of trueness should be adopted.For the process of spectral analysis without type standardization,CD0.95 can be used for trueness verification.If the instrument is measured by type standardization for n1 times,and the trueness verification is measured for n2 times,the formula for critical difference is r·√(1/2n1+1/2n2).The critical difference value of trueness verification was 0.65r or 0.61r(r means repeatability limit)when the(n1,n2)combination was(3,2)or(4,2).After type standardization,if the operation time lasts for relatively long time(more than 1h),the critical difference for trueness verification is CD0.95(Rw)which contained the time effect.The value was about CD0.95/2.CD0.95(Rw)of laboratory can be replaced by“warning limit”,i.e.,2S(standard deviation)in X-S monthly control chart.When the expanded uncertainty(U)of type standardization sample A and verification control sample B were considered(the coverage factor is k=2),the critical difference of trueness verification for sample B is√r^2*(1/2n1+1/2n2)+UA^2+UB^2.Except spark discharge atomic emission spectrometry,any method which was corrected by type standardization can use the same formula of critical value as trueness verification within a short time.

关 键 词：原子发射光谱分析 类型标准化 正确度验证 临界差 重复性限 中间精密度 

分 类 号：O657.31[理学—分析化学]