编制说明：金化学分析方法 第12部分 电感耦合等离子体原子发射光谱法

GB/T11066.12—202×金化学分析方法第12部分：银、铜、铁、铅、铋、锑、镁、镍、锰、钯、铬、铂、铑、钛、锌、砷、锡、硅、钴、钙、钾、锂、钠、碲、钒、锆、镉、钼、铼、铝含量的测定电感耦合等离子体原子发射光谱法编制说明（预审稿）紫金矿业集团股份有限公司2023.04GB/T11066.12—202×根据国家标准化管理委员会《关于下达2021年第三批推荐性国家标准计划及相关标准外文版计划的通知》（国标委发[2021]28号）的要求，国家标准《金化学分析方法第12部分银、铜、铁、铅、铋、锑、镁、镍、锰、钯、铬、铂、铑、钛、锌、砷、锡、硅、钴、钙、由全国有色金属标准化技术委员会归口，紫金矿业集团股份有限公司牵头起草，项目计划编本文件起草单位有：紫金矿业集团股份有限公司、北矿检测技术有限公司、大冶有色金属集团控股有限公司、深圳市中金岭南股份有限公司韶关冶炼厂、山东恒邦冶炼股份有限公其中紫金矿业集团股份有限公司负责统一样品的收集和分发，分析方法的实验研究，样品测试结果的收集和处理，标准文本、试验报告和编制说明的撰写。北矿检测技术有限公司、大冶有色金属集团控股有限公司、深圳市中金岭南股份有限公司韶关冶炼厂为一验单位，负责对试验报告中的条件实验进行验证，提供精密度和准确度测试数据，并对标准文本提出修改意见。山东恒邦冶炼股份有限公司、紫金铜业有限公司、华津国检（深圳）金银珠宝检验中心有限公司、东北大学为二验单位，负责提供精密度试验数据，并对标准文本提出修改意见。在本标准起草过程中，紫金矿业集团股份有限紫金矿业集团股份有限公司是以金铜等金属矿产资源勘查和开发及工程技术应用为主的大型跨国矿业集团，运营管理着紫金矿业集团分析测试中心和国家重点实验室，拥有一支基础理论扎实、实践经验丰富的研究和服务队伍。目前，紫金矿业集团股份有限公司测试中心取得了“中国计量认证（CMA）”、“中国合格评定国家认可委员会（CNAS）”、“THELONDONBULLIONMARKETASSOCIATION（LBMA）”和“中国地质勘查资质证书”等资质认证。测试中心自2007年参加国家/行业标准方法制修订工作以来，已负责和参加2项国际国有色金属工业协会、中国有色金属学会有色金属工业科学技术奖一等奖2项、二等奖2项、三等奖1项，全国有色金属标准化技术委员会技术标准优秀奖二等奖6项、三等奖6项。制订企业标准133项；取得国家发明专利5项GB/T11066.12—202×表1各单位及其工作职责负责单位工作职责紫金矿业集团股份有限公司样品收集、起草试验研究，数据处理；标准文本、试验报告和编制说明的撰写北矿检测技术有限公司、大冶有色金属集团控股有限公司、深圳市中金岭南股份有限公司韶关冶炼厂试验方案和试验条件的验证；提供精密度和准确度测试数据；对标准文本提出修改意见山东恒邦冶炼股份有限公司、紫金铜业有限公司、华津国检（深圳）金银珠宝检验中心有限公司、东北大学提供精密度测试数据；对标准文本提出修改意见紫金矿业集团股份有限公司在接到本标准制订任务后，立即组织骨干人员成立了标准编制组，制定了该标准的研究内容、技术路线、任务分工和进度安排。主要工作过程经历以下准计划及相关标准外文版计划的通知》，对《金化学分析方法第12部分银、铜、铁、铅、铋、锑、镁、镍、锰、钯、铬、铂、铑、钛、锌、砷、锡、硅、钴、钙、钾、锂、钠、碲、钒、锆、镉、钼、铼、铝含量的测定电感耦合等离子体原子发射光谱法》标实，确定了由紫金矿业集团股份有限公司负责起草工作，北矿检测技术有限公司、大冶有色金属集团控股有限公司、深圳市中金岭南股份有限公司韶关冶炼厂、紫金铜业有限公司、山东恒邦冶炼股份有限公司等单位、华津国检（深圳）金银珠宝检验中心有限公司协助起草。确定采用电感耦合等离子体发射光谱法测定金锭中Ag：0.0002~0.05%、Cu：0.0002~0.05%、Fe：0.0002~0.05%、Pb：0.0002~0.05%、Bi：0.0003~0.05%、Sb：0.0005~0.05%、Mg：0.0002~0.05%、Mo：0.0002~0.05%、Re：0.0002~0.05%、Al：0.0002~0.05%杂质元素和测定GB/T11066.12—202×2022年4月，紫金矿业集团股份有限公司开展试验样品的成分设计和制备，共研制金锭中银、铜、铁、铅、铋、锑、镁、镍、锰、钯、铬、铂、铑、钛、锌、砷、锡、硅、钴、钙、钾、锂、钠、碲、钒、锆、镉、钼、铼、铝含量不同梯度的4种试验样品，另通过标准2022年5月~9月，紫金矿业集团股份有限公司开展了大量试验研究工作，包括仪器条件实验、试样量的确定实验、试样介质实验、定容酸度实验、标准基体的选择实验、干扰实验、杂质元素的检出限试验、方法比对实验、样品全过程加标回收以及精密度试验，形成了2022年9月下旬~2022年10月上旬2023年1月下旬，收到6家验证单位发来的验证报告和反馈意见，采用GB/T6379对精密度试验数据进行汇总、统计和分析，完善标标准化技术委员会研讨会。本次研讨会对本方法进行了讨论1）测定范围中铬的范围书写有误，应由“0.00012）“试样量的确定试验”增加“1%1#含量、2%1#含量、4%1#含量”在金基体标准曲线条件3）调整测定范围下限。综合各验证单位提交的定量下限试验数据，将Te测定下限由4）条件实验中“干扰实验”需调研各产家ICP是否均具备多谱线拟合功能。据各验证单位反馈及查找各大品牌ICP厂家资料，安捷伦、赛默飞、斯派克、PE等厂家的ICP均有此功5）条件实验中“方法比对实验”可增加低含量标准样品进行ICP-MS与本方法的比较。该GB/T11066.12—202×通过结合金锭生产和应用的实际需求，确定测定方法和测定范围，提高了本标准的适用性。经充分调研，采用操作简便、灵敏度高、精密度和准确好、在行业内普及的分析方法（电感耦合等离子体发射光谱法能很好地满足行业对金锭中银、铜、铁、铅、铋、锑、镁、镍、锰、钯、铬、铂、铑、钛、锌、砷、锡、硅、钴、钙、钾、锂、钠、碲、钒、锆、镉、钼、铼、铝含量的分析测试需求，提高了本标准的本文件是首次制定，并且是在充分调研金锭中银、铜、铁、铅、铋、锑、镁、镍、锰、钯、铬、铂、铑、钛、锌、砷、锡、硅、钴、钙、钾、锂、钠、碲、钒、锆、镉、钼、铼、3.1测定范围的确定本标准适用于金锭中银、铜、铁、铅、铋、锑、镁、镍、锰、钯、铬、铂、铑、钛、锌、砷、锡、硅、钴、钙、钾、锂、钠、碲、钒、锆、镉、钼、铼、铝含量的测定。高纯度的金锭杂质含量很低，为了适用于较高纯度金锭需求，故本标准的测定范围确定为Ag：3.2测定方法的确定现有检测金中杂质元素的方法主要有火焰原子吸收光谱法、火花原子发射光谱法、乙酸乙酯萃取-ICP-AES法、砷和锡量测定氢化物-原子荧光光谱法、硅量的测定钼蓝分光光度法GB/T11066.12—202×等。高纯金测定杂质元素的主要方法有：乙酸乙酯萃取分离-ICP-AES法、ICP-MS标准加入校正-内标法、乙醚萃取分离-ICP-AES法。萃取法检测元素较多但操作繁琐、毒性大、时间长，原子吸收法消解时间短但检测元素较少。本方法选择使用王水消解试料，基体匹配后电感耦合等离子体发射光谱法测定，结合两者优点并扩展元素3.3仪器条件选择测试条件的不同，会直接影响实验的测试结果，需确认仪器的最优测试条件。配制金20mg/mL、杂质元素1.0μg/mL的溶液，于冷却气、辅助气、进样速率、观测高度不变的条件下，按不同分析功率、雾化气流量等仪器表2仪器工作条件由于测定微量元素时存在金基体的影响，在厂家推荐的仪器工作条件下，每个待测元素选择2～4条谱线。检测混合杂质元素标准溶液，制作工作曲线，再测定金基体溶液。根据每一条谱线测得的强度值、波峰形状和基线情况，波峰尖锐、基线平滑、无干扰峰或干扰峰较小的谱线作为测定谱线、综合曲线线性系数和空白值确定最合适的谱线。如Li670.784nm受重叠干扰峰影响，检测结果异常偏高，应选择610.362nm。各杂质元素测定推荐谱线波长见表3待测元素的推荐谱线选择NaKVNi光谱仪有自动背景校正功能，检测试样，参照计算机屏幕上所显示的每条谱线子陈列图及标识的谱线，背景与校正后的强度值，在谱线峰两侧选择背景扣除的最低值波长位置，并7GB/T11066.12—202×3.4试样量的确定在其他条件一定的情况下，分别称取0.5000g、1.0000g、2.0000g高纯金样品1#加入含1.00μg/mL各杂质元素溶液（A、B两组标准中间液分别加入，定容体积均为50mL分表4试样量的确定试验/%1121314151617181911K1111Ni1Na111V111111111111而影响溶液雾化效果，样品检测信号净强度有所下降。试样量少，试液中各元素浓度过低。GB/T11066.12—202×酸度影响试液提升速率和谱线强度。在其他条件一定的情况下，分别用盐酸（1+9）、混合酸（1+9）冲洗表面皿和杯壁，移入50mL塑料容量瓶中，加入含1.00μg/mL混合标准溶表s试样介质试验序号元素量L（1+9）盐酸(μg/mL）（1+9）混合酸(μg/mL）%/%值%1121314151617181911K1111Ni1Na111V111111111111GB/T11066.12—202×表6定容酸度试验元素均值μg%/%%/%%/%1121314151617181911K1111Ni1Na111V11111111111GB/T11066.12—202×10.00%~5.85%。在（1+9）盐酸介质下，回收率在90.90%~114（1+4）盐酸介质下，回收率在84.60%~115.35度对所测元素影响不大，综合考虑选择稀盐酸（3.7标准基体的选择用无金基体标准曲线和金基体标准曲线测定各元素的浓度，分析对各杂质元素回收率的影表7无金基体标准曲线测定各元素的浓度回收率/mL1121314151617181911K11111Ni1Na111111111GB/T11066.12—202×11V111表8金基体标准曲线测定各元素的回收率/mL1121314151617181911K11111Ni1Na11111111111V111表7、表8结果表明：采用无金基体标准曲线分别检测1%、2%、4GB/T11066.12—202×钾、钼、锑、钒等）回收率偏低。标准溶液含金基体时，一定程度上降低仪器灵敏度，消除针对金锭中所含杂质元素之间的相关干扰，分别对三十种待测元素（0.1μg/mL）加入其他二十九种元素（20mg/L）检测目标元素的回收率。采用无金基体标准曲线检测，钯、砷、锌、碲等元素回收率偏低，铂、钼、硅等元素回收率偏高，详见表3数据。根据谱线分析，20μg/mL锆对Pd340.458nm有负干扰，20μg/mL铂对Mo202对Si251.611nm有严重正干扰，20μg/mL钯对As188.979nm有较严重正干扰，20μg/mL钒本方法需同时测定30种元素，涉及金锭中已知的绝大部分杂质且含量较低，无法通过化学前处理方法进行分离。采用金基体匹配、调整背景校正后能消除大部分干扰，大部分元素续处理。ICP测定中多谱拟合法（MSF法）是基于建立待测元素和共存元素光谱的数学模型，并通过数学模型把待测元素光谱从干扰背景光谱中剥离出来，从而校正干扰元素光谱干扰的一种方法，将MSF模型建立完成后，后续实验可直接使用，方便批量处理。对部分谱线当选用波长As188.979nm进行砷含量测定时，Pd对其存在正干扰进行铂含量测定时，V对其存在正干扰、当选用波长Pd340.458nm进行钯含量测定时，Zr对其存在负干扰、当选用波长Mo202.031nm进行钼含量测定时，Pt对其存在正干扰。使用MSF法处理后整体回收率处于80%~120%之间，回收效果良好。选用波长Si251.611nm进行3.9杂质元素的检出限试验在上述仪器条件下，通过标准溶液制作工作曲线，用20mg/mL金基体溶液测定其在各杂表9金基体标准曲线测定各元素的回收率GB/T11066.12—202×元素浓度(μg/mL）123456789KNiNaV表10杂质元素的检出限及定量下限KVGB/T11066.12—202×NiNa3.10方法比对实验为了证实本方法的准确性，使用本方法与GB/T25934.1-2010《高纯金化学分析法第1部分：乙酸乙酯萃取分离-ICP-AES法测定杂质元素的含量》检测1#、2#、3#样品，数据见表11方法比对实验（1#）Ni表12方法比对实验（2#）Ni表13方法比对实验（3#）GB/T11066.12—202×Ni本方法与GB/T25934.1-2010《高纯金化学分析法第1部分》均涉及的元测定范围为0.00002~0.001%，选择低含量段范围进行比对结果符合金锭产品标准中相关质量称取高纯金样品9份，每份1.0000g，3份做本底，另外6份加入不同含量的杂质标准溶表14样品全过程加标回收试验元素/%/%/%KGB/T11066.12—202×NiNaV3.12起草及验证单位精密度试验为了考察本方法的精密度，7家验证单位按照起草单位制定的实验方案进行了验证试表15各验证单位精密度试验数据n12345671234567各单位1#样品As精密度试验数据（%）n1234567123456GB/T11066.12—202×7n12345671234567n12345671234567n12345671234567n12345671234567各单位1#样品Fe精密度试验数据（%）n123456712345GB/T11066.12—202×67n12345671234567n12345671234567各单位1#样品Mn精密度试验数据（%）n12345671234567n12345671234567n12345671234GB/T11066.12—202×567n12345671234567各单位1#样品Pt精密度试验数据（%）n12345671234567各单位1#样品Re精密度试验数据（%）n12345671234567n12345671234567n1234567123GB/T11066.12—202×4567n12345671234567n12345671234567n12345671234567各单位1#样品Zn精密度试验数据（%）n12345671234567n123456712GB/T11066.12—202×34567n12345671234567n12345671234567各单位2#样品Co精密度试验数据（%）n12345671234567各单位2#样品Cr精密度试验数据（%）n12345671234567各单位2#样品Cu精密度试验数据（%）n12345671GB/T11066.12—202×234567各单位2#样品Fe精密度试验数据（%）n12345671234567n12345671234567各单位2#样品Mn精密度试验数据（%）n12345671234567n12345671234567n1234567GB/T11066.12—202×1234567n12345671234567各单位2#样品Pt精密度试验数据（%）n12345671234567n12345671234567n12345671234567各单位2#样品Sn精密度试验数据（%）nGB/T11066.12—202×12345671234567各单位2#样品Te精密度试验数据（%）n12345671234567各单位2#样品Zn精密度试验数据（%）n12345671234567n12345671234567各单位3#样品Cu精密度试验数据（%）n12345671234567GB/T11066.12—202×n12345671234567各单位3#样品Mn精密度试验数据（%）n12345671234567各单位3#样品Mo精密度试验数据（%）n12345671234567n12345671234567各单位3#样品Pt精密度试验数据（%）n12345671234567GB/T11066.12—202×n12345671234567n12345671234567n12345671234567各单位4#样品Co精密度试验数据（%）n12345671234567n1234567123456GB/T11066.12—202×7n12345671234567n12345671234567各单位4#样品Sn精密度试验数据（%）n12345671234567各单位4#样品Te精密度试验数据（%）n12345671234567各单位4#样品Zn精密度试验数据（%）n123456712345GB/T11066.12—202×67各单位5#样品As精密度试验数据（%）n12345671234567各单位5#样品Ca精密度试验数据（%）n12345671234567各单位5#样品Cr精密度试验数据（%）n12345671234567各单位5#样品Fe精密度试验数据（%）n12345671234567n12345671234GB/T11066.12—202×567n12345671234567n12345671234567各单位6#样品As精密度试验数据（%）n12345671234567各单位6#样品Ca精密度试验数据（%）n12345671234567n1234567123GB/T11066.12—202×4567n12345671234567各单位6#样品Mo精密度试验数据（%）n12345671234567各单位6#样品Na精密度试验数据（%）n12345671234567各单位6#样品Re精密度试验数据（%）n12345671234567n123456712GB/T11066.12—202×34567n12345671234567n12345671234567各单位6#样品Zr精密度试验数据（%）n12345671234567n12345671234567各单位7#样品Ca精密度试验数据（%）n12345671GB/T11066.12—202×234567各单位7#样品Cr精密度试验数据（%）n12345671234567n12345671234567各单位7#样品Mo精密度试验数据（%）n12345671234567各单位7#样品Na精密度试验数据（%）n12345671234567n1234567GB/T11066.12—202×1234567n12345671234567各单位7#样品Zr精密度试验数据（%）n12345671234567n12345671234567n12345671234567各单位8#样品Na精密度试验数据（%）nGB/T11066.12—202×12345671234567各单位8#样品Re精密度试验数据（%）n12345671234567n12345671234567n12345671234567各单位8#样品Zr精密度试验数据（%）n12345671234567GB/T11066.12—202×3.13试样量的确定-补充试验在其他条件一定的情况下，分别称取0.5000g、1.0000g、2.0000g金样品1#加入含1.00μg/mL各杂质元素溶液(A、B两组标准中间液分表16试样量的确定试验-补充试验1121314151617181911K1111Ni1Na111V111111111111量大，不利于测定、称样量少，所含杂质元素会达不到测定工作曲GB/T11066.12—202×3.14基体残留情况分析表17-1基体残留情况试验（紫金）第一步123456789表17-2基体残留情况试验（北矿检测数据）第一步12345GB/T11066.12—202×6789表17-3基体残留情况试验（大冶）第一步测定金基体前空白溶液金含量/ug/ml第二步测定金基体后空白溶液金含量/ug/ml第三步矩管及中心管清洗后空白溶液金含量/ug/mL第四步清洗后标准溶液金含量/ug/ml1-0.00780.06950.01310.09350.19720.48441.0071.9644.9721.0442-0.00820.04740.00690.09990.20520.51091.0072.0004.9741.0463-0.00270.03780.00290.10470.20060.49910.9831.9764.9411.0264-0.00510.03280.00140.10560.19650.49631.0191.9744.9721.0285-0.00410.03590.00290.10660.20090.50011.0131.9854.9471.0186-0.0060.02980.00511.0167-0.00340.02730.00281.0298-0.00250.02790.00140.9999-0.00620.0240.00071.020-0.00950.02490.00161.012-0.00570.02590.0021.0110.02140.0021.0170.02320.00520.9960.0218-0.00151.0050.0172-0.00121.0310.02050.00531.0150.0160.00151.0150.0229-0.00121.0100.02320.00261.003200.01650.00460.993标准偏差0.0050.0030.0090.0130.0140.0160.014RSD/%5.3231.7361.9041.3400.6840.3201.411GB/T11066.12—202×根据GB/T6379.2—2004《测量方法与结果的准确度（正确度与精密度）第2部分：确定标准测量方法重复性与再现性的基本方法》对7家实验室精密度数据进行统计、分析和处理。以一个实验室和一个水平组合为精密度试验的一个单元，进行测试结果的一致性和离群值检表18各实验室精密度数据单元平均值统计B单位：%实验室i水平j1AgAsBiCdCoCuFeLiMgMnNiPbPdPtReRhSbSnTeVZn10.0010230.0005760.0008990.0008100.0009010.0011040.0017270.0007640.0002060.0010630.0009940.0009440.0008600.0009140.0001670.0008240.0006800.0007770.0006690.0001910.00091720.0010210.0006310.0009030.0007830.0008140.0011890.0016090.0007690.0002710.0010200.0009800.0009210.0008930.0009570.0002540.0008710.0007760.0007710.0007290.0001970.00090430.0010510.0005540.0007830.0007730.0008080.0010930.0017780.0007640.0002060.0010030.0009670.0009230.0007790.0008360.0002990.0008290.0006630.0007530.0006990.0001540.00091340.0010210.0005670.0007810.0006860.0007560.0009500.0016610.0008610.0002700.0009170.0009190.0008600.0008960.0007100.0002060.0008860.0005900.0008570.0004640.0001500.00079750.0010390.0005290.0006060.0007230.0007960.0011730.0017860.0007430.0001860.0008660.0009340.0009630.0008730.0008110.0001410.0008040.0007190.0007640.0007560.0001260.00080460.0009690.0005870.0009010.0007430.0007130.0010560.0016160.0005640.0002510.0008530.0008810.0008740.0008400.0007590.0001570.0008130.0006630.0007660.0007590.0001390.0007967-0.0004070.0009060.0006110.0008070.0011060.0018110.0009110.0001030.0008130.0009200.0009360.0007300.0009390.0002090.0008100.0007510.000804-0.0001290.000910总平均值0.0010210.0005500.0008260.0007330.0007990.0010960.0017210.0007680.0002130.0009330.0009420.0009170.0008390.0008470.0002050.0008340.0006920.0007850.0006790.0001550.000863实验室i水平j2AgBiCdCoCrCuFeLiMnNiPbPdPtRhSbSnTeZn10.0095390.0081800.0081130.0085160.0093810.0099470.0165240.0099440.0095430.0095960.0090210.0082200.0083160.0080840.0072810.0073060.0079360.00857720.0097310.0080100.0080790.0084340.0099370.0099090.0165570.0104390.0095390.0093560.0088630.0086910.0085040.0087530.0070740.0070340.0079570.00834430.0089200.0079970.0077960.0083710.0090240.0093760.0163960.0099430.0092570.0094500.0086610.0082130.0080840.0080730.0068510.0075700.0077210.00877940.0089030.0074990.0075610.0078990.0088440.0092640.0163070.0099070.0086410.0090130.0095440.0085840.0078070.0083610.0074810.0075490.0070360.00806050.0103590.0076230.0073690.0079660.0088560.0092740.0152440.0106310.0084630.0085510.0083830.0082640.0083370.0079490.0072870.0073460.0074960.00786960.0087790.0081590.0075560.0075700.0087690.0092430.0152570.0102360.0091800.0094970.0089410.0081470.0080610.0083900.0075170.0070610.0078190.00842470.0095140.0090130.0091800.0086360.0105670.0098960.0176490.0103610.0098160.0101390.0104000.0081440.0081070.0084470.0071440.0072500.0074400.009007总平均值0.0093920.0080690.0079500.0081990.0093400.0095580.0162710.0102090.0092060.0093720.0091160.0083240.0081740.0082940.0072340.0073020.0076290.008437实验室i水平j34CdCuLiMnMoPbPtRhAgBiCoNiPdTeZn10.0639560.0629210.0491100.0546890.0426570.0555060.0623040.0435190.0512710.0508670.0542960.0506010.0534590.0533700.0525970.0476100.05474120.0639570.0628060.0492930.0545390.0434640.0553060.0626900.0433200.0513710.0511610.0543100.0506430.0532570.0537440.0539010.0482910.05496130.0640730.0617010.0479130.0548660.0437530.0548260.0629110.0427000.0506000.0491860.0540430.0499410.0539680.0535900.0537210.0468860.05443940.0601040.0590290.0487290.0517030.0412330.0528540.0613790.0403930.0488170.0517230.0537760.0492330.0546360.0544140.0544730.0477870.05364750.0620390.0604530.0508040.0529900.0426400.0529630.0599430.0427160.0502110.0520130.0545260.0492390.0546240.0527670.0550990.0495260.05419060.0628770.0607990.0506810.0524790.0428610.0532770.0610590.0439370.0497910.0512570.0516530.0492690.0530970.0538270.0533910.0494010.05369670.0638260.0632800.0489600.0549570.0436310.0552570.0617870.0444510.0508060.0511630.0543270.0503990.0529960.0537460.0534330.0494460.055540总平均值0.0629760.0615700.0493560.0537460.0428910.0542840.0617250.0430050.0504100.0510530.0538470.0499030.0537190.0536370.0538020.0484210.054459实验室i水平j56AsCaCrFeMgVAlAsCaKMgMoNaReTiVZr10.0504610.0483270.0573310.0625060.0464060.0500490.0100640.0099890.0102130.0103790.0099100.0098340.0102210.0102960.0088970.0098240.0104030.01002920.0505540.0480710.0571160.0629690.0464300.0499660.0099610.0097370.0101970.0115430.0100160.0103130.0109200.0106270.0090510.0100710.0101100.00997430.0513710.0497090.0580330.0652810.0491790.0513700.0096100.0102590.0102430.0093990.0097330.0101730.0101030.0102290.0091030.0100290.0098470.01013640.0469260.0477730.0559230.0644410.0502790.0503890.0104480.0100200.0102690.0103100.0101630.0102260.0102010.0102930.0101930.0101340.0100930.01015350.0501560.0482710.0565500.0644300.0459860.0491300.0107930.0100500.0107110.0091230.0107190.0096140.0100640.0101460.0087760.0094890.0100110.00962GB/T11066.12—202×360.0488960.0480940.0542990.0637440.0460530.0491030.0098060.0102060.0101060.0100990.0096840.0095260.0100400.0106730.0091600.0091510.0099370.00963370.0515400.0492630.0575190.0631840.0475510.0505740.0094490.0092490.0109170.0101060.0091700.0101070.0101640.0107240.0083240.0096370.0108440.009730总平均值0.0499860.0485010.0566810.0636860.0474120.0500830.0100190.0099300.0103790.0101370.0099130.0099700.0102450.0104270.0090720.0097620.0101780.009897实验室i水平j78AlCaCrKMoNaTiZrAlKNaReTiZr10.0002670.0002640.0002410.0002740.0002670.0002400.0002860.0002330.0002860.0501510.0493300.0535500.0496160.0477860.0487760.04817320.0004260.0003100.0003300.0003710.0002570.0002740.0002890.0002400.0003130.0495560.0498100.0534040.0490290.0478540.0484730.04829030.0003400.0004900.0003200.0004440.0002810.0002100.0003910.0002940.0002800.0509710.0500530.0546730.0488970.0482670.0497860.04901340.0003840.0003800.0003260.0003460.0003360.0003300.0003270.0003310.0003240.0507610.0507460.0504200.0501640.0503640.0503260.05039650.0005000.0001190.0003190.0006640.0003300.0001200.0001510.0002710.0002690.0496140.0477870.0533410.0499830.0470140.0475530.04884660.0003330.0002140.0002170.0002990.0003970.0002770.0002970.0002600.0003170.0500860.0498900.0517160.0482560.0474900.0470900.04762370.0002010.0003800.0002140.0004600.0002070.0001790.0001060.0001060.0003060.0504360.0478490.0537370.0482000.0474760.0492210.048574总平均值0.0003500.0003080.0002810.0004080.0002970.0002330.0002640.0002480.0002990.0502250.0493520.0529770.0491630.0480360.0487460.048702表19各实验室精密度数据单元离散度统计C实验室i水平j1AgAsBiCdCoCuFeLiMgMnNiPbPdPtReRhSbSnTeVZn10.00002210.00006780.00006540.00002940.00003480.00002820.00014490.00005620.00002370.00003640.00004160.00002760.00003960.00002070.00003450.00002990.00006160.00003990.00007710.00003670.000035520.00003390.00010760.00008750.00002360.00003690.00009860.00010750.00005050.00004880.00004280.00004730.00011250.00003350.00007870.00005740.00007080.00007610.00004880.00004880.00005470.000037430.00007900.00017510.00006100.00003720.00004630.00008240.00007570.00008100.00003150.00003700.00006370.00006920.00003080.00011750.00004670.00005180.00004310.00010130.00004100.00003460.000033040.00004020.00002430.00003480.00002700.00003150.00001830.00009120.00003130.00002000.00003300.00002910.00006430.00003310.00001630.00000980.00002640.00003000.00003300.00003510.00001150.000045450.00007860.00007690.00010450.00001700.00001990.00005440.00006600.00004820.00000790.00004200.00004080.00011350.00002690.00006310.00001460.00003360.00003240.00004540.00004790.00000530.000021560.00006470.00010240.00009620.00003450.00004070.00008680.00013000.00005620.00005150.00004500.00005980.00004310.00003560.00005210.00004390.00002140.00005380.00006400.00004980.00003630.000045470.00000760.00000980.00000690.00002500.00000790.00001350.00002270.00000490.00001600.00002160.00005440.00005070.00007800.00002270.00001000.00006790.00000530.00002270.0000100联合单元内标准差0.00005750.00009550.00007280.00002690.00003460.00006340.00009860.00005240.00003180.00003720.00004560.00007560.00003640.00006910.00003670.00003960.00005460.00005540.00005170.00003280.0000347标准偏差平方和（10-1986263890371485065838928181680211925270719662145764004892903345794141097120905215051601475248424实验室i水平j2AgBiCdCoCrCuFeLiMnNiPbPdPtRhSbSnTeZn10.00017620.00025570.00018140.00029580.00017790.00025460.00055360.00033280.00024270.00021470.00016890.00022790.00028250.00027580.00018050.00033230.00016430.000226120.00063490.00049470.00025180.00022000.00042710.00046290.00061060.00041860.00029620.00037260.00019340.00030260.00039760.00023900.00033510.00051280.00015120.000869330.00066690.00057940.00032930.00019990.00027790.00049810.00092380.00046950.00016160.00040900.00034750.00012150.00042820.00054810.00033140.00043240.00020190.000325840.00006820.00014170.00010610.00023210.00013750.00013530.00055280.00036650.00021800.00016480.00017920.00011390.00013670.00010620.00020070.00013660.00013020.000144750.00077810.00007830.00005010.00007110.00008830.00025530.00041140.00012850.00008180.00007060.00021320.00024460.00028650.00022130.00027540.00023700.00048060.000057060.00016990.00067050.00020660.00016690.00064100.00042910.00051800.00044370.00018080.00015220.00021260.00023160.00017030.00038610.00023160.00023430.00034810.000240770.00006550.00006470.00005480.00023170.00010550.00013820.00010350.00044520.00008890.00007650.00004620.00006240.00067340.00003900.00011190.00030010.00006610.0000559联合单元内标准差0.00046630.00040100.00019430.00021260.00032510.00034100.00057150.00038770.00019550.00024300.00021100.00020300.00037880.00030340.00024990.00033380.00025750.0003776标准偏差平方和（10）15221761125667264224316310739995813876228643810523142675934133333115522885831004505644429437014780081464038998167实验室i水平j34CdCuLiMnMoPbPtRhAgBiCoNiPdSbTeZn10.00096040.00133650.00112420.00062310.00091590.00056090.00133380.00080650.00190070.00204440.00092090.00092350.00174320.00107180.00084760.00187260.002081820.00102610.00175950.00105290.00096000.00118930.00143180.00090050.00100560.00180990.00186600.00127670.00088480.00173450.00086410.00135910.00070830.001743930.00131740.00110910.00075540.00130250.00142210.00161670.00109410.00192170.00198240.00193170.00103400.00127810.00090540.00168280.00161520.00162520.001566440.00047300.00028120.00021380.00032700.00150070.00032140.00018610.00035650.00062490.00057480.00077060.00063650.00078490.00084230.00099080.00086060.000473650.00032420.00035200.00067700.00035030.00056520.00051980.00028380.00120390.00134340.00116430.00075550.00028010.00093070.00108120.00109580.00141610.000735860.00085380.00112800.00059470.00090120.00075920.00035530.00065100.00138190.00123890.00147760.00132420.00051940.00065530.00086540.00104810.00092470.001336170.00024590.00042780.00021860.00034120.00026810.00104340.00069710.00031340.00051050.00066530.00044260.00022210.00027640.00038210.00026080.00046550.0002157联合单元内标准差0.00083060.00105360.00074150.00077130.00103480.00096850.00082910.00113000.00145450.00149790.00097550.00076270.00112470.00103510.00110350.00122290.0013324GB/T11066.12—202×标准偏差平方和（10）482890577704763848605416458674954956566452481195289389051480931015704995666102440717528855172750056785235951046757112426395实验室i水平j56AsCaCrFeMgVAlAsCaKMgMoNaReTiVZr10.00119750.00192280.00095810.00166510.00139300.00161100.00056260.00062960.00074880.00071990.00031290.00027140.00097330.00039200.00039400.00034670.00040170.000308820.00278680.00194980.00162350.00119390.00250420.00121030.00056160.00063690.00036940.00043060.00018130.00100410.00103050.00042200.00039280.00044100.00036890.000391230.00323200.00206110.00064980.00141110.00135700.00133080.00054860.00040770.00078070.00045910.00025110.00034490.00078410.00037250.00028850.00020470.00060240.000317740.00057220.00049080.00036230.00120110.00031520.00029060.00013850.00013440.00019720.00019360.00019230.00013670.00014670.00020440.00017660.00012190.00012190.000176450.00067620.00097750.00137250.00064240.00059760.00051100.00014950.00006430.00014590.00021010.00008930.00022680.00043220.00009500.00012000.00010270.00010820.000086460.00112370.00136800.00106210.00091070.00143570.00066360.00017510.00048720.00051550.00082990.00032150.00026610.00023010.00029550.00036460.00035890.00036800.000209270.00034750.00063600.00027980.00024040.00055750.00048790.00017610.00009580.00014580.00029000.00005890.00012070.00046880.00011040.00023410.00014070.00017730.0001296联合单元内标准差0.00176530.00147450.00101400.00103430.00135650.00098960.00038470.00042040.00048610.00050270.00022220.00044020.00066600.00029780.00029910.00027530.00034920.0002531标准偏差平方和（10）218141761521937671970867488848128812906855043103611312368991653752176905234565213563193105061620771626045530571853705448510实验室i水平j78AlCaCrKMoNaSiTiZrAlKNaReSiTiZr10.00003860.00010500.00002540.00004350.00003990.00006830.00006370.00002630.00000790.00119980.00237560.00214770.00135890.00108500.00103630.000842920.00007250.00010820.00009810.00007560.00005350.00008140.00006990.00005000.00005190.00125470.00076770.00125060.00057730.00082640.00069940.000678630.00007330.00008290.00012210.00008200.00005430.00004470.00008070.00002510.00002710.00151850.00173920.00197620.00112120.00151940.00207840.001058140.00003210.00003060.00001990.00000980.00001400.00001730.00001800.00001350.00002230.00038000.00054190.00034480.00051510.00029010.00024050.000226050.00005770.00000380.00000900.00001900.00004800.00001000.00004140.00000380.00000690.00144780.00191850.00071970.00100190.00047410.00085330.000884660.00002750.00005060.00004150.00003930.00004460.00005280.00005150.00004830.00003860.00148330.00101740.00079030.00077270.00105240.00041040.000539570.00000900.00003460.00001810.00004900.00000760.00002610.00000790.00000980.00000530.00067000.00073420.00068500.00048520.00070520.00066680.0005262联合单元内标准差0.00004970.00007000.00006290.00005170.00004130.00004950.00005370.00003030.00002820.00120770.00145440.00129900.00088950.00093220.00101990.0007262标准偏差平方和（10173193430527710187431193817167202146443554810209090148061241181265255385816082433728181936920573.14.1测试结果一致性检查表20实验室间一致性统计h实验室i水平j1AgAsBiCdCoCuFeLiMgMnNiPbPdPtReRhSbSnTeVZn10.0758870.3616700.6509261.1489371.7624140.1082940.172437-0.035531-0.1272691.3525281.3030000.7232400.3437310.720745-0.667966-0.300702-0.185908-0.211388-0.0946391.2641510.90047420.0252961.1515560.6891090.7458540.2594171.173188-1.2366500.0037400.9803120.9046000.9453140.1095820.8722951.1766380.8821501.1772161.343758-0.3713580.4473861.4630060.68639931.0877190.057867-0.3800100.5952290.143612-0.0360980.781910-0.035531-0.1272690.7239360.6233960.147935-0.959294-0.1150591.669914-0.166346-0.459878-0.8912590.176373-0.0284080.82911540.0252960.240149-0.392738-0.696757-0.750795-1.841003-0.6085030.8546020.956234-0.170426-0.592737-1.5396240.918257-1.4523450.0181511.625070-1.6242512.028185-1.940105-0.177549-1.09755950.632395-0.306696-1.958234-0.145170-0.0608940.9746490.868493-0.231883-0.464358-0.707939-0.1992821.2218370.550560-0.373398-1.125377-0.9276970.430524-0.5713200.692587-1.022684-0.9786286-1.8465930.5236980.6763820.151838-1.489973-0.505373-1.151765-1.8681570.643222-0.842317-1.522722-1.1560880.021996-0.935666-0.845848-0.658985-0.459878-0.5313270.718398-0.575260-1.1213457-2.0282440.714564-1.7999300.1362200.1263431.1740781.312759-1.860873-1.260383-0.5569690.493118-1.7475440.9790850.068975-0.7485560.9556340.548467-0.9232560.781543实验室i水平j2AgBiCdCoCrCuFeLiMnNiPbPdPtRhSbSnTeZn10.2587460.2271150.2668080.8109600.0612661.1483620.298420-0.9282530.6814710.453949-0.142000-0.4684110.618475-0.7569810.2038790.0164530.9305710.35457820.599296-0.1193810.2104970.6026060.8790461.0344300.3379630.8064920.672813-0.032248-0.3792771.6649271.4407351.657693-0.684263-1.2707350.995599-0.2351793-0.833536-0.145586-0.2540710.441772-0.464300-0.5395190.143684-0.9332670.1045560.158758-0.680683-0.499441-0.390662-0.798258-1.6397801.2697680.2776970.8647364-0.863808-1.161780-0.638865-0.768140-0.729185-0.8686560.037088-1.058610-1.139606-0.7268140.6403741.180077-1.5991350.2439741.0613951.168148-1.800575-0.95518951.706714-0.908460-0.955616-0.596340-0.712367-0.839118-1.2420651.483343-1.500358-1.661584-1.097522-0.2680060.711913-1.2471390.2283790.206144-0.404656-1.4400206-1.0832730.183439-0.648250-1.608865-0.840605-0.931952-1.2265910.094544-0.0515770.254261-0.261707-0.798108-0.4903300.3471651.214523-1.1420170.575089-0.03256370.2158621.9246532.0194981.1180071.8061440.9964531.6515010.5357511.2327011.5536791.920816-0.811038-0.2909950.553547-0.384132-0.247760-0.5737261.443638实验室i水平j34CdCuLiMnMoPbPtRhAgBiCoNiPdSbSnTeZn10.6660790.866577-0.2351370.709558-0.2709011.0215680.5603810.3914400.961499-0.2043240.4499001.065346-0.374426-0.534983-1.493971-0.7694940.41204320.6670500.792389-0.0601510.5966500.6623850.8543220.9333100.2400611.0730890.1194510.4642281.128581-0.6635280.2151390.122959-0.1229560.73321630.7457140.084394-1.3807470.8428980.9960550.4529301.147399-0.2325930.212249-2.0542390.1962940.0579400.356119-0.094072-0.100188-1.456695-0.0300914-1.952176-1.629264-0.600146-1.537863-1.917778-0.334650-1.991429-1.7772470.737137-0.071640-1.0236041.3150751.5579140.831362-0.6014225-0.637222-0.7161071.386215-0.568999-0.290723-1.722775-0.220613-0.2213591.0561970.680582-1.0148821.298673-1.7431951.6070631.048131-0.3929756-0.067149-0.4944581.268647-0.953963-0.034688-0.842034-0.6440430.710536-0.6900380.224756-2.200786-0.969091-0.8931690.381196-0.5092910.93020970.5777031.096469-0.3786800.9117190.8556500.8137050.0603791.1025980.4418070.1210230.4814220.755710-1.0387450.218002-0.4579320.9722271.577860GB/T11066.12—202×实验室i水平j56AsCaCrFeMgVAlAsCaKMgMoNaReTiVZr10.295918-0.2461180.519060-1.315507-0.593965-0.0426640.0970620.170625-0.542109