编制说明-镍铂靶材合金化学分析方法 第2部分

PAGEPAGE11镍铂靶材合金化学分析方法第2部分:镁、铝、钛、钒、铬、锰、铁、钴、铜、锌、锆、银、钯、锡、钐、铅、硅含量的测定电感耦合等离子体质谱法编制说明(预审稿)2023年3月一、工作简况（一）任务来源根据2021年8月24日，国家标准化管理委员会关于下达2021年第二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】23号的要求，国家标准《镍铂靶材合金化学分析方法第2部分:镁、铝、钛、钒、铬、锰、铁、钴、铜、锌、锆、银、钯、锡、钐、铅、硅含量的测定电感耦合等离子体质谱法》制定项目由全国有色金属标准化技术委员会归口，计划号：20213154-T-610，项目周期为24个月，完成年限为2023年8月，标准起草单位为：北京有色金属与稀土应用研究所、有研亿金新材料有限公司、深圳市中金岭南有色金属股份有限公司、国标（北京）检验认证有限公司、北矿检测技术有限公司、铜陵有色金属集团控股有限公司、大冶有色设计研究院有限公司、紫金铜业有限公司、南京市产品质量监督检验院（高瑞峰）、山西北方铜业有限公司、广东省科学院工业分析检测中心。（二）主要参加单位和工作成员及其所作的工作2.1主要参加单位情况标准主编单位各验证单位，积极参加标准调研工作，针对标准的讨论稿和征求意见稿提出修改意见，主要负责标准中检测范围文本内容编写把关。针对镍铂合金分析条件试验、加标回收、精密度进行可靠的数据分析确定，承担标准中的试验验证工作，为标准技术要求提供有力保障。11家验证单位对镍铂合金分析精密度试验进行可靠的数据分析确定，承担标准中的试验验证工作，为标准技术要求提供有力保障。2.2主要工作成员所负责的工作情况本标准主要起草人及工作职责见表1。起草人工作职责李秋莹负责标准的工作指导、标准的编写、试验方案确定及组织协调负责资料调研分析测试标准条款内容编写及把关方法试验验证方法验证（三）主要工作过程1预研阶段1.1标准调研2020年8月，由全国有色金属标准化技术委员会发函组织标准编制组单位讨论技术要求，并征求相关企业意见，由主编单位整理后初步形成标准讨论稿。1.2标准工作会议由全国有色金属标准化技术委员会组织召开标准工作会议，会议对镍铂靶材合金化学分析方法第2部分：镁、铝、钛、钒、铬、锰、铁、钴、铜、锌、锆、银、钯、锡、钐、铅、硅含量的测定电感耦合等离子体质谱法》国家标准计划进行认真讨论，并提出进一步修改讨论稿意见。2立项阶段2020年10月,向全国有色金属标准化技术委员会提交了《镍铂靶材合金化学分析方法第2部分：镁、铝、钛、钒、铬、锰、铁、钴、铜、锌、锆、银、钯、锡、钐、铅、硅含量的测定电感耦合等离子体质谱法》国家标准项目建议书，标准草案及立项报告等材料，全体委员会讨论论证同意该国家标准立项。2021年8月，工业和信息化部下达了制定《镍铂靶材合金化学分析方法第2部分：镁、铝、钛、钒、铬、锰、铁、钴、铜、锌、锆、银、钯、锡、钐、铅、硅含量的测定电感耦合等离子体质谱法》国家标准的任务，计划号为20213154-T-610，完成年限到2023年8月，技术归口单位为全国有色金属标准化技术委员会。2021年10月，由中国有色金属工业标准计量质量研究所主持在江苏省常州市召开了任务落实会。3起草阶段3.1标准进度汇报及进度协调会受疫情影响无法召开标准进度汇报及进度协调现场会议，标准主编单位采取电子邮件、电话、微信等方式，相关单位相继汇报标准的进展完成情况及需要协调问题，请各参加单位配合验证把关，及时修改讨论稿，形成标准征求意见稿。3.2验证样品发放及数据反馈2022年9月，标准主编单位向验证单位发放验证样品及征求意见稿。在本标准的试验过程中，镍、铂基体对所测元素基本无影响，所以采用NiPt15样品做加标回收试验及精密度试验。根据验证单位返回的数据，统计方法的重复性及再现性，于202x年x月形成了标准讨论稿I及编制说明。4征求意见阶段4.1标准征求意见会议2023年2月，以电子邮件、电话、微信等形式征求验证单位意见，根据验证单位意见及试验数据，再次形成讨论稿II。4.2标准发函征求意见2023年3月以会议的形式召开工作会议以及通过网络、微信和电子邮件等方式在全国开展征求意见工作，对XX家相关研究院所、生产企业、下游用户以及第三方检测机构进行了征求意见，2023年x月xx日～x月xx日在xxx召开《镍铂靶材合金化学分析方法第2部分：镁、铝、钛、钒、铬、锰、铁、钴、铜、锌、锆、银、钯、锡、钐、铅、硅含量的测定电感耦合等离子体质谱法》预审会，发送《征求意见稿》的单位数XX个，收到《征求意见稿》后，回函的单位数XX个，回函并有建议或意见的单位数xx个。编制组单位根据回函意见，对标准稿进行了修改和完善，并于2023年x月形成了标准送审稿。回函意见见意见汇总表表：征求意见稿意见汇总处理表序号标准章条编号意见内容提出单位处理意见备注5审查阶段2023年x月x日～x月x日，在xxx召开了国家标准《镍铂靶材合金化学分析方法第2部分：镁、铝、钛、钒、铬、锰、铁、钴、铜、锌、锆、银、钯、锡、钐、铅、硅含量的测定电感耦合等离子体质谱法》审定会，根据与会专家及企业代表认真研究及讨论，形成审定会纪要，并在会议上经过专家审议通过，根据审定会纪要，修订标准的送审稿，编制《镍铂靶材合金化学分析方法第2部分：镁、铝、钛、钒、铬、锰、铁、钴、铜、锌、锆、银、钯、锡、钐、铅、硅含量的测定电感耦合等离子体质谱法》的报批稿。会议纪要如下：序号标准章条编号意见内容处理意见备注6报批阶段2023年x月，标准起草工作组根据审查会提出的修改意见和建议对标准进行了进一步的修改整理，形成了本标准的报批稿。报标委会秘书处。二、标准编制原则编制本标准的原则是以能满足YS/T937-2013镍铂靶材产品标准中NiPt3、NiPt5、NiPt10、NiPt15、NiPt30、NiPt45、NiPt60等杂质含量的准确、快速测定要求。本着分析技术的先进性、适用性和可操作性。制订本标准。三、标准主要内容的确定依据及主要试验和验证情况分析根据YS/T937-2013镍铂靶材合金产品标准中NiPt3、NiPt5、NiPt10、NiPt15、NiPt30、NiPt45、NiPt60等中杂质含量的准确、快速测定要求，电感耦合等离子体原子发射光谱下限不能满足产品要求，因此采用电感耦合等离子体质谱法测定。基本原理：试料以盐酸-硝酸聚四氟乙烯烧杯溶解，铁、硅以钪为内标，在反应池（DRC）工作模式下测定其同位素的信号强度；钒以钪为内标，在碰撞池（KED）工作模式下测定其同位素的信号强度；镁、铝、钛、铬、锰、钴、锌以钪为内标，在正常工作模式下测定其同位素的信号强度；铜、锆、钯、银、锡以钇为内标，在正常工作模式下测定其同位素的信号强度；钐、铅以铼为内标，在正常工作模式下测定其同位素的信号强度。3.1试液的制备称取0.10g（精确至0.0001g）NiPt15样品至100mL聚四氟乙烯烧杯中，加入6mL盐酸和2mL硝酸，低温加热溶解完全，冷却，转入100mL塑料容量瓶中，用水洗涤聚四氟乙烯杯盖及杯壁，合并洗涤液至100mL容量瓶中，加入2mL含1ug/mLSc、Y、Re混合内标溶液，用水稀释至刻度。混匀。待测。样品处理过程中，同时做三份空白溶液。3.2干扰和动态反应池（DRC）参数优化ICP-MS的谱干扰较多也较复杂，对于不同的分析对象仔细地判别谱干扰以选择合适的测定同位素，才能保证分析结果准确可靠。在高纯物质的纯度分析中，应考察同质异位素形成的干扰、背景离子形成的干扰（包括等离子体气产生的原子和分子谱，如Ar+,Ar2+；载气中的空气或杂质O+，O2+，CO2+，CO+，N+，N2+等；样品制备中使用的溶剂等，如SH+，SO+，Cl+，NOH+,，H2O+等；以上离子间的复合离子，如，ArO+，ArH+，ArN+，ArOH+，ArCl+，ArC+，NO+，ClO+等）；还有就是基体和上述离子间的衍生物以及基体的离子形成的干扰。同质异位素干扰通常可选择目的同位素的办法避开。背景离子的干扰大多发生在质量数小于84的待测杂质同位素，此类干扰较复杂，需通过实验进行判别。通过大量实验，确定待测元素铬有上述中ArC+干扰，Fe有ArO+干扰，硅有N2+及仪器本身的影响，基体镍、铂对所测元素没有影响，采用动态反应池（DRC）技术消除ArC+、ArO+、N2+对铁、硅测定的影响；采用碰撞反应模式（KED）技术消除对钒的影响。通过1ng/mL的铁、钒和10ng/mL的硅标准溶液测定来找到最佳DRC、KED参数。最终确定的DRC的氨气流量（L/min）28Si为0.2，RPq为0.6；56Fe为0.25，RPq为0.45；KED的氦气流量（L/min）51V为5，RPq为0.45。3.2镍、铂基体的影响由于基体镍、铂的存在会影响待测杂质的测定值，许多文献报道表明各种基体均普遍存在这种抑制效应。分离基体是克服基体影响的有效办法之一，但前处理复杂，流程长，许多元素容易沾污等弱点，因而直接测定方法更显得简单、快速。采用内标法可较好地克服镍、铂基体的抑制效应。考察了镍含量从0.1mg/mL到1mg/mL对待测元素的影响，结果列于表1，从表1可以看出镍含量从0.1mg/mL到1mg/mL所测元素影响不大，考察铂含量从0.1mg/mL到0.7mg/mL对待测Ti、V、Co、Zr、Sm元素的影响，结果列于表2，,从表2可以看出铂含量从0.1mg/mL到0.7mg/mL对Ti、V、Co、Zr、Sm元素影响不大（其余元素参照GB/T33909-2017纯铂化学分析方法，铂对其余所测元素基本没有影响）。表1镍基体对杂质元素测定值ng/mL的影响元素镍质量浓度mg/mL0.100.300.500.701.0Mg2.7863.8312.7553.4233.236Al1.3601.1861.2911.0831.384Ti-0.0090.0360.1310.2900.151V-0.0170.055-0.355-0.294-0.004Cr0.3280.2680.30703170.336Mn-0.061-0.004-0.0980.0780.215Co0.1250.1360.1410.1290.147Fe1.1131.2171.0871.2561.145Cu1.1010.9131.1521.0671.371Zn0.6810.6670.8210.5970.743Zr0.1780.3290.1130.1830.262Pd0.145-0.0060.1000.183-0.022Ag0.0980.3870.2750.4420.107Sn0.9170.6331.5271.0110.772Sm0.001-0.0010.0020.0020.009Pb1.0851.5591.0281.1231.184Si3.1253.2613.4383.2673.442表2铂基体对Ti、V、Co、Zr、Sm测定值ng/mL的影响元素铂质量浓度mg/mL0.10.300.500.70Ti1.8881.6221.9821.831V-0.376-0.571-0.672-0.541Co-0.317-0.348-0.353-0.384Zr0.1920.1790.1520.097Sm-0.001-0.002-0.001-0.0023.3内标选择及加标回收率采用内标法可较好地克服镍、铂基体的影响。考察了内标元素钪、钇、铼等对基体效应的补偿作用，根据实验中基体镍、铂对所测杂质元素基本没有影响，所以实验采用NiPt15样品来做实验加标回收实验。称取NiPt15样品11份，每份0.10g，三份做本底，另外8份（平行两份）加入4个等级不同含量的杂质标准溶液，按实验方法处理后进行测定，根据回收情况确定内标的选择，选择钪为Mg、Al、Ti、Cr、V、Cr、Mn、Co、Zn、Si的测定控制内标；钇为Cu、Zr、Pd、Ag、Sn的测定控制内标；铼为Sm、Pb的测定控制内标。结果见表3，从表3可以看出，NiPt15样品的加标回收率在89.6%～116.5%之间，对内标加入的质量浓度进行了选择，实验结果表明内标加入的质量浓度在10ng/mL～50ng/mL范围内，均可有效地补偿基体抑制效应，但考虑到大的质量浓度可能会引入新的潜在干扰，本文选择20ng/mL为内标元素钪、钇、铼加入的质量浓度。表3加标回收率测定同位素本底值ng/mL加标值ng/mL测定值ng/mL回收率%测定同位素本底值ng/mL加标值ng/mL测定值ng/mL回收率%24Mg1.2011.005.0050.00100.002.2296.05058.25117.71102.897.0114.1116.566Zn1.3500.505.0050.00100.001.8676.72356.82116.06103.4107.5110.9114.727Al2.6600.505.0050.00100.003.1747.77355.61109.92102.8102.3105.9107.391Zr0.1051.005.0050.00100.001.1434.92848.7198.19103.896.597.298.148Ti3.1370.505.0050.00100.003.5857.72956.98106.7389.691.8107.7103.6106Pd2.210.505.0050.00100.002.7247.31049.9495.65102.8102.095.593.451V-0.1680.505.0050.00100.000.4085.07250.1297.37115.2104.8100.697.5107Ag2.3510.505.0050.00100.000.8547.48853.75101.65100.6102.7102.899.352Cr1.7340.505.0050.00100.002.1957.08453.89106.4092.2107.0104.3104.7118Sn5.3250.505.0050.00100.005.85010.8056.13103.62105.0109.4101.698.355Mn0.2340.505.0050.00100.000.7565.67851.65104.71104.4108.9102.8104.5154Sm0.0470.505.0050.00100.000.5645.07354.4399.46103.4100.5108.899.459Co2.3211.005.0050.00100.003.2347.49955.92110.2491.3103.6107.2107.9208Pb-0.4790.505.0050.00100.00-0.0034.90052.18106.2296.4107.6105.3105.756Fe21.911.005.0050.00100.0023.0427.4069.37117.85113.0109.894.995.928Si3.3935.0050.00100.008.69457.69116.96106.0108.6111.463Cu6.3991.005.0050.00100.007.55011.4652.10104.52115.1101.291.498.13.4方法精密度采用NiPt15样品中加入杂质元素的方法(同时做三份本底取平均值，计算精密度时减去本底值)。配制低、中、高各11份样品，加入杂质的量列入表4，分别进行11份样品实验测定，计算平均值和RSD，结果列入表5。从表8可以看出，低、中、高11个样测定的相对标准偏差（RSD）分别为2.40%～13.07%、1.01%～6.33％、0.86%～5.49％。表7加入杂质元素的量ng/mL测定同位素低量中量高量24Mg11010027Al11010048Ti11010051V11010052Cr11010055Mn11010059Co11010056Fe11010063Cu11010066Zn11010091Zr110100106Pd110100107Ag110100118Sn110100154Sm110100208Pb11010028Si550100表8方法精密度(%)=测定同位素低量测定值%平均值%精密度%24Mg0.0001090.0001070.0001100.0001010.0001210.0001010.00009810.0001160.0001060.0001190.00009680.00010813.070.001090.0009670.001070.001060.001080.001000.001100.001000.001020.0009930.001020.001044.330.01020.009170.009510.009120.009020.009380.009270.009260.009300.009310.009290.009353.3227Al0.0001080.0001050.0001110.0001050.0001090.0001180.0001070.0001110.0001100.0001040.0001020.0001084.080.001160.001100.001090.001030.001170.001100.001020.0009810.001050.001040.001080.001075.390.01070.01060.009890.01040.01080.01070.01020.01020.01080.01080.01140.01063.8348Ti0.0001130.0001130.0001050.0001050.0001100.0001040.0001080.0001190.0001080.0001040.0001000.0001085.110.001030.001040.001030.001020.0009860.001020.0009940.001020.001000.001080.001090.001033.170.01070.01110.01070.01130.01080.01110.01110.01110.01130.01110.01100.01101.9351V0.00009930.0001080.0001000.0001100.00009950.0001070.00009910.0001120.0001060.0001090.0009510.0001045.400.001130.001190.001180.001080.001100.001130.001180.001130.001140.001140.001120.001142.990.009920.009860.01010.01020.01010.01020.009960.01020.01020.01010.01010.01011.2152Cr0.00009250.0001140.0001010.0001110.0001010.0001170.00009010.00009580.0001120.00009120.0001100.0001039.640.001070.001110.001150.001100.001130.001110.001150.001090.001090.001130.001090.001112.370.01020.01030.009970.01040.009850.01010.01020.01040.01050.01030.01020.01021.9055Mn0.0001170.0001020.0001030.0001080.00009380.0001020.0001030.00009440.0001040.0001120.0001030.0001046.410.001140.001110.001150.001160.001150.001190.001170.001110.001160.001140.001140.001152.080.01030.01040.01010.01050.01000.01030.01050.01050.01050.01040.01040.01041.9959Co0.0001080.0001050.0001050.00009670.0001030.00009460.0001080.00009300.00009480.00009820.0001050.0001015.600.001010.001020.001050.001060.001050.001060.001060.001000.001050.001050.001030.001042.060.01000.01030.009950.01040.009990.01020.01020.01040.01040.01030.01030.01021.6956Fe0.0001080.0001120.0001150.0001030.0001020.0001060.0001010.0001130.0001000.0001160.0001190.0001095.540.001050.001080.001010.001150.001020.001040.001040.001120.001020.0009880.001200.001076.160.00960.009530.009680.0100.009900.009890.01040.009520.009660.009640.01010.009812.8163Cu0.0001130.00009450.0001120.00009560.0001210.0001080.0001150.0001140.0001130.0001010.0001020.0001088.200.001160.001110.001100.001150.001150.001130.001160.001120.001100.001080.001090.001122.600.009570.009380.009570.009500.009460.009550.009570.009580.009510.009420.009580.009411.0066Zn0.00009990.0001000.0001150.00009750.0001120.0001070.00009650.0001120.0001030.00009380.00009600.0001037.180.001060.001000.001030.001110.0009940.001040.001120.0009880.0009970.001010.0009930.001034.580.009140.009300.009430.009030.009420.009510.009660.009830.009530.009560.009460.009442.3891Zr0.00009600.00009650.0001000.00009860.00009940.0001040.0001000.0001000.0001020.00009830.00009650.00009922.400.0009910.001000.001000.0009840.0009920.001000.001010.0009690.0009900.001000.001010.0009951.010.01020.01060.009970.009790.01030.01060.01020.009890.01010.01000.01010.01022.55106Pd0.00009430.0001030.0001020.0001090.00009610.00009380.00009340.0001030.00009730.0001070.0001180.0001017.680.0009320.0009340.0009790.0009770.0009180.0009590.0009410.0009550.0009500.0009540.0009350.0009491.990.009090.009020.008970.009200.009270.009130.009130.009060.009050.009060.009110.009100.92107Ag0.00008920.0001110.0001070.0001190.0001040.0001020.0001090.0001000.0001060.0001110.00009750.0001057.560.001010.0009960.001010.0009850.001010.001020.0009970.001000.0009930.001010.001030.001011.360.008750.008640.008800.008840.008700.008760.008690.008640.008780.008790.008570.008720.992118Sn0.00008930.00009490.00009740.0001020.00009680.0001090.0001010.0001030.0001010.0001070.0001140.0001026.80.0009870.001010.001080.001030.0009950.0009880.001010.001010.001030.0009910.00100.001012.690.01020.01040.01050.01080.01010.01040.01050.01030.01050.01020.01020.01042.02154Sm0.0001060.0001080.0001070.0001050.0001100.0001040.0001040.0001010.0001110.0001050.0001080.0001062.810.001030.001020.001030.001040.001040.001050.001020.0009960.001010.001050.001040.001031.640.01040.01040.01030.01050.01030.01040.01030.01050.01050.01030.01030.01040.86208Pb0.0001010.00009400.0001010.00009590.00009290.00009860.00009550.0001190.0001000.00009480.0001000.00009937.200.001000.001100.001000.001140.001140.001130.001150.0009910.001040.001020.001000.001066.330.01030.01030.01060.01080.01050.01040.01050.01070.01080.01040.01020.01051.9528Si0.0004910.0005630.0005120.0005780.0005240.0004970.0005790.0005890.0005340.0004930.0005690.0005397.010.005210.005020.004890.005230.004890.005240.005090.004930.005250.005030.005170.005092.740.009930.01010.01160.01080.01010.01140.01010.01070.009980.01040.01080.01055.49四、标准中涉及专利的情况本标准不涉及专利问题五、预期达到的社会效益等情况（一）项目的必要性简述半导体用溅射镍铂靶材对质量要求非常高,尤其是对化学纯度的控制,原因是杂质的存在将严重影响靶材及相应薄膜的质量,引起溅射时异常放电等现象。目前国内外镍铂合金靶材在纯度方面的差距显著，国内所生产的镍铂合金靶材能达到4N级，而日本相关靶材厂家制备的镍铂靶可以达到5N级以上。因此杂质元素分析结果的准确和分析方法的标准化是确保产品质量的必要条件之一，也是判定产品等级的重要指标，制订相关标准分析方法是非常有必要的。（二）项目的可行性简述目前生产镍铂靶材产品的厂家，主要是贵研铂业股份有限公司、有研亿金新材料有限公司等。贵研铂业股份有限公司建成了年产1000片镍铂靶产品示范生产线，形成了长方状、碗状和圆形3种外形，5种不同Pt含量的镍铂靶材产品，技术性能指标及尺寸精度满足了用户使用要求。产品不但实现了替代进口，还出口至美国知名半导体公司。2017年，产品获得第19届深圳高交会优秀产品奖。而我们对杂质的分析经过多年的实践，分析工作者进行了镍铂靶材合金中杂质分析测定的系统研究，ICP-AES测定杂质不能满足4N级以上要求，采用电感耦合等离子体质谱法测定镍铂靶材合金中杂质，是满足产品要求的，也可行的。（三）标准的先进性、创新性、标准实施后经济效益和社会效益经过资料搜索，YS/T937-2013镍铂靶材产品标准，附录C测定杂质含量，但此方法中没有说明内标元素对应要校正的所测元素，而且方法中没有重复性及再现性结果。本方法采用Sc、Y、Re为内标控制所对应要测定的元素，保证测定的准确性，且增加重复性及再现性结果计算。保证了方法的适用及准确。本标准的制定，对考察产品等级，公平、公正交易，维护行业最佳秩序，促进最佳共同效益和推广应用具有重要意义。同时，也为产品质量保证提供有力支撑。六、采用国际标准和国外先进标准的情况无采用。七、与现行法律、法规、规章及相关标准，特别是强制性国家标准的协调配套情况目前并未检索到国内相关国家标准或行业标准。本标准完全满足现行国家法律、法规等的要求，标准格式规范。八、重大分歧意见的处理经过和依据无。九、标准性质的建议说明根据标准化法和有关规定，建议本标准作为推荐性国家标准。十、贯彻标准的要求和措施建议1.首先应在实施前保证标准文本的充足供应，使每个检测机构以及相关单位等都能及时得到标准文本，这是保证新标准贯彻实施的基础。2.本次制定的《镍铂靶材合金化学分析方法第2部分：镁、铝、钛、钒、铬、锰、铁、钴、铜、锌、锆、银、钯、锡、钐、铅、硅含量的测定电感耦合等离子体质谱法》，不仅与检测机构有关，而且与产品生产、使用企业相关。对于标准使用过程中容易出现的疑问，起草单位有义务进行必要的解释。3.可以对相关部门进行标准的培训宣贯，以保证标准的贯彻实施。4.建议本标准批准发布6个月后实施。十一、废止现行有关标准的建议 本标准为首次起草，无废止/替代现行有关标准十二、其他应予说明的事项无。各验证单位验证数据1、北京有色金属与稀土应用研究所有限公司方法精密度测定同位素低量测定值%平均值%精密度%24Mg0.0000990.0001010.0001000.0001010.0001110.0001110.0001010.0001260.0001060.0001190.0001180.00011811.370.001190.0009370.0009770.001160.001180.001030.001110.001010.001120.0009990.001120.001104.630.01120.01270.009510.009120.009020.009380.009170.009260.009600.009310.009290.009853.1227Al0.00009860.0001250.0001210.00009050.0001090.0001080.00009960.0001110.0001100.0001040.0001020.0000982.880.001060.001000.001190.001030.001170.001100.001020.0009810.001150.001040.001180.001175.290.01180.000960.009890.01140.01080.01270.01020.01020.01080.01080.01140.01134.4348Ti0.0001230.0001030.0001050.0001050.0001000.0001040.0001180.0001090.0001080.0001040.0001000.0001184.910.001130.00009410.001030.001020.0009960.001000.0009940.001020.001000.001080.001190.001083.670.01000.01010.01030.01130.01080.01110.01110.01110.01130.01110.01160.01071.6351V0.0001030.0001180.0001030.0001160.0001050.0001070.00009980.0001120.0001060.0001090.0009510.0001075.410.001070.001090.001280.001080.001100.001130.001180.001130.001140.001140.001120.001092.790.009990.009950.01010.01020.01010.01020.009960.01020.01020.01010.01080.01031.3852Cr0.00009850.0001040.0001070.0001010.0001010.0001170.00009010.00009680.0001120.00009820.0001100.0001129.840.001010.001010.001050.001000.001180.001120.001050.001190.001190.001030.001010.001182.270.01010.01130.009970.01040.009800.09780.01020.01040.01090.01030.01120.00992.4555Mn0.0001200.0001120.0001130.0001080.00009380.0001020.0001030.00009140.00009840.0001120.0001030.0001046.210.001140.001110.001150.001160.001150.001190.001170.001110.001160.001140.001140.001152.080.009880.01040.01010.01050.009760.01030.01050.01050.01050.01040.009850.00981.5359Co0.0001080.0001050.0001050.00009670.0001030.00009460.0001080.00009300.00009480.00009820.0001050.0001015.600.001070.001120.001150.001060.001050.001060.001060.001000.001050.001050.001230.001141.860.01090.01070.009950.01040.009990.01020.01020.01140.01040.01030.01150.01221.7956Fe0.0001180.0001120.0001250.0001030.00009880.0001060.0001010.00009830.0001000.0001160.0001190.0001095.210.001000.001080.0009810.001150.001020.001040.001040.001120.001020.0009880.001200.000996.050.009640.009770.009980.0100.009900.009890.01120.009620.009660.009640.01010.01011.4563Cu0.0001230.00009850.0001120.00009960.0001270.0001080.0001150.0001040.0001230.0001010.0001020.0001147.100.001060.001010.001190.001250.001150.001030.001160.001120.0009980.001080.001190.001312.400.009540.009350.009550.009400.009360.009450.009470.009480.009310.009320.009280.009411.0066Zn0.00009990.0001230.0001150.00009950.0001120.0001070.00009650.0001120.0001030.00009480.00009600.0001137.080.001120.001000.001230.001110.0009940.001140.001120.0009880.0009990.001010.0009930.001214.080.009740.009900.009230.009730.009920.009810.009760.009830.009530.009960.009860.009841.7591Zr0.0001020.0001080.0001090.00009860.00009940.0001040.0001000.0001000.0001020.00009830.00009650.0001022.900.001080.001210.001000.0009840.0009920.001000.001010.0009690.0009900.001000.001010.001031.710.01090.01030.01060.009770.009830.01060.01020.009890.01010.01000.01010.00982.21106Pd0.00009980.0001030.00009810.00009650.00009610.00009380.00009340.0001030.00009130.0001070.0001180.00009885.380.0009220.0009340.0009790.0009670.0009280.0009590.0009810.0009550.0009300.0009540.0009350.0009561.830.009090.009020.008970.009200.009270.009130.009130.009060.009050.009060.009110.009100.92107Ag0.00008920.0001110.0001070.00009190.0001040.0001020.0001030.00009560.0001060.0001110.00009750.00009867.320.0009630.0009760.001010.0009850.001010.001020.0009970.001000.0009930.0009850.0009890.0009712.090.009860.009640.009800.009840.009700.009760.009020.008990.008780.008990.008570.009121.32118Sn0.00009460.00009030.00009940.0001020.00009680.0001090.0001010.0001030.00009630.0001070.00009860.00009897.630.0009870.001010.001080.001030.0009950.0009880.001010.001010.001030.0009910.00100.001012.690.01010.01040.009890.01080.009880.01040.01050.01030.009760.01020.009680.009163.78154Sm0.00009280.00009560.0001270.0001030.0001160.0001340.0001040.00009870.0001110.0001050.00009680.00009591.880.001000.0009980.001030.0009560.001040.001050.001020.0009960.001010.001050.001040.000981.240.01070.01040.01030.01050.01120.01040.01030.01050.01050.01030.01000.01120.82208Pb0.0001110.00009500.0001090.00009990.00009390.00009760.00009580.0001090.0001000.00009680.0001080.00009936.330.001000.001170.000980.001040.001240.001130.001150.0009910.001040.001020.001000.001166.170.01030.01030.01060.01080.01050.01040.01050.01070.01080.01040.01020.01051.9528Si0.0004210.0005730.0005020.0005560.0005390.0004890.0005190.0005890.0005340.0005860.0005690.0005496.520.005210.005020.004890.005230.004890.005240.005090.004930.005250.005030.005170.005092.740.009930.009860.01060.01080.01010.009970.01010.01070.009980.01040.01080.00956.032、测定同位素低量测定值%平均值%精密度%24Mg0.0001300.0001000.0001170.0001180.0001040.0001050.00011411.110.0000990.0001140.0001060.0001380.0001220.001130.001180.001000.001160.001060.001010.001048.390.000930.001030.000980.001090.000920.008960.008810.009330.008990.008850.009220.009022.050.008970.008990.008980.009330.0088427Al0.0001440.0001020.0001410.0001280.0000950.0001260.00012114.920.0001060.0001440.0001180.0001220.0001010.001120.001020.000970.001110.001150.001090.001087.110.000950.001190.001060.001150.001120.009230.009000.008890.009040.009220.008830.009072.010.008810.009310.008980.009240.0092348Ti0.0001210.0001060.0000960.0001090.0001440.0001030.00011614.910.0001110.0000990.0001430.0001080.0001350.001160.001140.001180.001010.001060.001070.001058.190.001070.000960.000970.001060.000910.009410.009400.008950.009280.009170.008890.009172.140.009350.009280.008860.009110.0091951V0.0000990.0001190.0001110.0001060.0000970.0001200.00011010.050.0001200.0000990.0000980.0001190.0001270.000950.000940.001030.001110.001060.001060.001038.050.001180.001100.000950.001060.000920.009410.008940.009150.009300.009200.008820.009112.280.009090.008850.008920.009120.0093952Cr0.0001080.0001090.0001260.0001200.0001020.0001310.00011911.550.0001400.0001190.0001230.0000960.0001340.001120.001110.001060.000960.001000.001030.001046.330.000980.001100.001020.000940.001100.009160.008930.009280.009240.009260.009140.009111.770.009330.008880.009050.008900.0090155Mn0.0001220.0001080.0001310.0001150.0001070.0001430.00012011.090.0001130.0001400.0001180.0001200.0001020.001040.001060.000920.000910.001130.001190.001068.720.000960.001060.001110.001120.001150.008990.009340.009100.009210.009160.008970.009141.960.009390.008870.009390.009020.0090859Co0.0001010.0001260.0001360.0001000.0001040.0001250.00012010.860.0001170.0001250.0001350.0001300.0001230.001100.000990.000920.001160.001070.000990.001048.190.001110.001000.000940.001170.001000.009360.009170.009150.009100.009210.009410.009171.860.009310.008830.008940.009260.0091656Fe0.001130.000920.001120.001000.001060.000960.001078.610.001170.001160.001130.001000.001180.009060.008980.009090.009280.008900.009320.009091.400.008990.009030.009160.009070.0091663Cu0.0005110.0005020.0004720.0005050.0005510.0004680.0005168.250.0005530.0005430.0005140.0004570.0005980.001080.000940.001000.001080.001020.000980.001057.180.001080.001090.000980.001150.001180.008950.008830.009270.009040.009300.008890.009012.060.008860.008820.008870.009260.0090266Zn0.0001420.0001130.0001060.0001130.0001230.0001220.00011711.380.0001340.0001230.0000980.0001170.0001020.000980.001100.001070.000940.000950.001130.001036.880.000960.001120.001030.001080.001000.009070.009350.008920.009300.009200.009040.009132.130.008850.009300.008850.009360.0092091Zr0.0001090.0001050.0001120.0001030.0001320.0001180.00011511.450.0001360.0001290.0001250.0001070.0000960.001130.000920.001050.000970.001100.001110.001047.610.000940.001080.001030.000970.001130.009400.008910.009000.009400.009200.009310.009201.700.009170.009090.009180.009310.00921105Pd0.0001030.0001270.0001070.0001430.0001060.0001150.00011712.210.0000990.0001050.0001340.0001230.0001260.000980.000990.001000.000980.000950.001050.001037.590.000940.001160.001130.001050.001140.009220.009150.009040.008950.009360.009170.009131.880.009360.008830.008990.009290.00907107Ag0.0001150.0000990.0001230.0001410.0001340.0001250.0001239.740.0001200.0001360.0001130.0001200.0001320.001080.000940.000980.001110.001060.001040.001026.350.000910.001000.001000.001090.000970.009120.009260.009340.009320.008950.009290.009112.180.008940.008940.008820.008920.00931118Sn0.0005660.0005900.0005410.0004670.0004570.0004620.0005349.470.0005160.0005630.0005840.0005570.0005740.001160.001090.001140.001150.001150.000920.001096.460.001100.001050.001040.001110.001070.008880.009340.009390.009410.008860.009420.009123.260.008800.009230.008720.008820.00942147Sm0.0001310.0000980.0001190.0001400.0001090.0001370.00012012.520.0001180.0001390.0001250.0001130.0000980.000920.001000.001060.000940.001020.000910.000996.380.001080.000930.000950.001070.000970.009150.008980.009000.008810.009040.009010.009142.040.009350.009240.009380.009360.00924208Pb0.0001320.0001190.0001060.0001090.0001080.0001160.00011912.160.0001360.0000980.0001370.0001370.0001080.000920.001080.001000.000960.001030.001100.001046.570.001030.000980.001090.001070.001140.008930.009380.008860.009290.009050.009240.009171.970.009050.009090.009400.009300.0092328Si0.0005650.0004610.0005540.0004960.0005860.0005100.0005188.200.0004930.0004860.0004860.0004910.0005700.005590.005710.005550.005480.005860.005970.005634.650.005650.005860.005840.005080.005350.009160.009230.008760.008890.009400.008610.009163.060.009390.009250.009320.009420.009363、深圳市中金岭南有色金属股份有限公司测定同位素低量测定值%平均值%精密度%24Mg0.00120.00120.00100.00110.00100.00130.00120.00110.00110.00120.00130.001158.970.01110.01080.01210.01230.01130.01030.01060.01100.01020.01030.01030.01096.3327Al0.001150.001380.001080.001120.001050.001280.001210.001120.001080.001170.001040.001158.990.01010.01080.01110.01230.01130.01030.01040.0110.01020.01030.01030.01075.8548Ti0.0001030.0001030.0001020.0001090.0001110.0001120.0001110.0001130.0001140.0001080.0001090.0001083.710.001050.001060.001110.001130.001070.001060.001080.001040.001110.001050.001070.001072.710.01050.01040.01020.01090.01050.01120.01040.01050.01050.01030.01030.01052.7551V0.0001040.0001010.0000980.0001040.0001130.0001030.0001040.0001010.0000970.0001010.0001030.0001033.880.001060.001020.001060.001020.001050.001030.0010.001040.001040.001020.001030.001021.800.009960.01020.009780.01020.01040.01020.01040.01020.01050.01030.01030.01021.9152Cr0.0001130.0001130.0001080.0001240.0001210.0001150.0001110.0001230.0001140.0001180.0001090.0001154.520.001020.001060.001160.001120.001070.001060.001080.001040.001110.001050.001070.001083.700.01030.01020.01020.01110.01050.01020.01040.01050.01050.01030.01030.01042.3755Mn0.0000950.0000970.0000920.0000910.0000980.0000960.0000950.0000950.0000910.0000960.0000950.0000952.350.001010.000950.000960.000990.000940.000960.001020.000980.000960.000920.000940.000951.050.01050.01020.01110.01020.01240.01120.01060.01120.01080.01030.01030.01085.8059Co0.0001030.0001010.0000980.0001040.0001030.0001030.0001040.0001010.0000970.0001010.0001030.0001022.190.001070.001030.001060.001020.001070.001030.0010.001040.001040.001020.001030.001042.110.01050.01020.01010.01020.01060.01020.01060.01020.01050.01030.01030.01031.6656Fe0.00110.00120.00110.00100.00100.0010.00120.00110.00110.00120.00130.001128.370.01210.01020.01210.01230.0110.01030.01060.0110.01080.01030.01030.01106.9563Cu0.0001080.0001010.0000980.0001040.0001030.0001030.0001040.0001010.0000970.0001010.0001030.0001022.810.001040.001070.001060.001020.001070.001030.001000.001040.001040.001020.001030.001062.100.01050.01020.01010.01020.01060.01020.01060.01090.01050.01030.01030.01042.2166Zn0.0001090.0001080.0001050.0001040.0001060.0000900.0001040.0001070.0001050.0001010.0001050.0001044.690.001050.001060.001010.001030.001070.001060.001050.001040.001010.001050.001070.001042.020.01050.01010.01020.01040.01040.01020.01040.01050.01050.01030.01030.01031.2391Zr0.0001130.0001030.0001020.0001140.0001110.0001150.0001110.0001130.0001140.00