镍合金化学分析方法 第10部分：痕量元素含量的测定 辉光放电质谱法 编制说明

1根据全国有色金属标准化技术委员会《关于2有限公司运营管理着国家有色金属及电子材料分析测试中心和国家有色金属质2004年至今共承担了国家科技支撑计划、国家863计划、国家自然科学基金、军工配套等省部级科技项目40余项；曾获国家科技进步奖6项，国家发明奖3利20余项；负责和参加起草制订分析方法国家标准、行业标准300余项；国家标准物质/标准样品120个，在国内外科技期刊上发表论文800余篇，撰写论著表1人员分工表参与单位主要职责国标（北京）检验认证有限公司标准工作前期调研、申报、样品搜集、实验方案的确定、标准文本和编制说明的编写、数理统计计算重复性限和再现性限深圳市中金岭南有色金属股份有限公司、紫金矿业集团股份有限公司、昆明冶金研究院有限公司、上海有色金属工业技术监督监测中心有限公司、峨嵋半导体材料研究所、国合通用（青岛）测试评价认证股份公司承担一验的主要工作，包括对实验条件试验、实验步骤、试剂材料等的验证，并进行实验样品精密度试验并提供精密度数据标准文本、编制说明提出修改意见。金川集团股份有限公司、钢研纳克检测技术股份有限公司、广东先导稀材股份有限公司、山东恒邦冶炼股份有限公司、宁波江丰电子材料股份有限公司承担二验的主要工作，进行实验样品精密度试验并提供精密度数据，对标准文本、编制说明提出修改意见。金川集团股份有限公司提供部分统一样品。3委员会提交了《镍合金化学分析方法第10部分：痕量元素含量年有色金属国家标准制（修）订项目计划及征集起草单位的通知》（有色标委），法第10部分：痕量元素含量的测定辉光放电质谱法》，项目计划编号为司、山东恒邦冶炼股份有限公司、宁波江丰电子材料股份有4公司为二验单位，负责提供精密度试验数据，并对标专家对《镍合金化学分析方法第10部分：痕量元素含其中4个标准样品，4个对应牌号的待测样品，金川可补充提供几个牌号的镍合2024年7月底，主编单位将每块统一样品切成两份，分别寄送给两家验证5金化学分析方法第10部分：痕量元素含量的测定辉光预审会，来自XX等单位的XX名专家代表参会，对本文件的预审稿、编制说明进行了充分、细致的讨论，并提出修改意见。制组依据各家单位的意见和对标准文本进行修改，结构和起草规则》、GB/T20001.4-2015《标准编写规则准》、GB/T6379.2-2004《测量方法与结果的准确度（正确度与精密度)第2部的测定》、GB/T223《钢铁及合金化学分析方法》系列标准、国军标GJB87816另外，GB/T14992-2005《高温合金和金属间化合物高温材料的分类和牌号》中对镍基高温合金中元素含量有明确的规定，如镍基高温合金DD404中过预溅射可除去样品表面的污染物。GDMS基体干扰小，测定下限可低至ng/g定已有非常成熟的应用，并形成检测标准。本标准发挥GDMS技术的优势，来量限值的要求，如镍铬钴系合金要求Ag含量不大于0.0005%，Bi含量不大于放电条件直接影响样品测定结果的准确性和可靠7电压设置的是最大放电电压，一般设置1200V就可满足绝大多数基体的测试需），8表2标准样品单位：mg/kg值度值度值度值度值度值度度度B//////////////26/////33//////////////2024//////////////P////45//////////2//////////////////////V/////////1////////////2//////////473//553282//////////1/////////////////////////////////////////////////Y///////////////////////////////Nb////////////////////////3////////////////////////////////////32//////////////////////////////////////////////////////////////////////////////////////Hf/////////////////4//////////W/////////475////////////////////////////////////////////////////9表3检出限单位：mg/kg值123456789B000P0V0000000Y0000Nb00000000HfW形成的质谱干扰较多，对元素含量的测定可能产生一定所示。然而，理论存在的质谱干扰的强度还与合金元素种类、合关，因此本标准只能给出推荐的测定分辨率，实际检测中还要根表4质谱干扰情况元素质量数干扰离子强度/%理论所需分辨率测定分辨率Zn6668As7577YZr9091Ag93Nb16O+99.7631474高分辨，或Ag107中分辨Cd中分辨Te中分辨中分辨中分辨Ce高分辨按照标准文本的分析步骤对8个牌号的镍合金统一样中32种痕量元素含量进行测定。），表52#镍合金测定结果的精密度单位：mg/kg元素第一点第二点123平均RSD123平均RSDB29.7729.6229.6729.690.2528.3227.6627.6727.88Mg5.025.465.355.284.45.095.585.445.374.68Al////////////////////P72.3472.3772.3572.350.0270.6170.8970.9470.810.25Ca0.160.160.154.720.190.170.200.19Ti//////////V//////////Mn//////////Cu//////////Zn4.104.294.214.202.284.504.354.524.42Ga3.68As9.088.979.159.079.088.929.089.03<0.5<0.5<0.5<0.5/<0.5<0.5<0.5<0.5/Y0.1380.1390.1340.1370.1430.140Zr5.395.595.475.485.585.485.495.52Nb//////////Mo//////////Ag0.2140.2170.2230.2182.100.2340.2130.2240.2204.70Cd<0.1<0.1<0.1<0.1/<0.1<0.1<0.1<0.1/8.288.558.558.468.768.898.778.810.782.412.422.412.410.322.592.652.642.63Te<0.01<0.01<0.01<0.01/<0.01<0.01<0.01<0.01/La<0.01<0.01<0.01<0.01/<0.01<0.01<0.01<0.01/Ce<0.01<0.01<0.01<0.01/<0.01<0.01<0.01<0.01/Yb<0.01<0.01<0.01<0.01/<0.01<0.01<0.01<0.01/Hf0.0130.0130.0170.0140.0110.0140.0150.013Ta58.1758.7758.5658.500.5259.5860.4659.5859.970.75W37.0237.5937.1337.250.8238.5738.0538.0538.220.78Tl<0.01<0.01<0.01<0.01/<0.01<0.01<0.01<0.01/Pb0.720.710.730.720.730.690.730.723.19Bi0.0240.0170.0190.0200.0270.0200.0200.022表64#镍合金测定结果的精密度单位：mg/kg元素第一点第二点123平均RSD123平均RSDB38.7638.2238.7838.590.8240.1339.0039.2439.46Mg0.230.240.230.232.720.220.220.230.223.16Al//////////2.00.45P0.53Ca0.0660.0490.0540.0560.0620.0490.0530.055Ti//////////V//////////Mn64.2364.3464.4064.3265.9465.5565.6765.720.30Cu52.5753.7353.5553.2854.6554.4255.1354.730.66Zn0.210.230.220.225.940.210.220.260.23Ga8.938.838.858.870.639.259.179.139.180.66As2.012.062.022.033.53<0.5<0.5<0.5<0.5/<0.5<0.5<0.5<0.5/Y0.510.520.540.523.350.530.580.560.56Zr//////////Nb206.5209.2208.3208.00.67205.5201.3202.6203.1Mo//////////Ag0.520.560.490.536.390.660.620.630.643.2Cd<0.5<0.5<0.5<0.5/<0.5<0.5<0.5<0.5/7.037.166.847.012.276.936.906.886.910.370.780.800.770.782.180.780.840.820.814.05Te<0.01<0.01<0.01<0.01/<0.01<0.01<0.01<0.01/La<0.01<0.01<0.01<0.01/<0.01<0.01<0.01<0.01/Ce<0.01<0.01<0.01<0.01/<0.01<0.01<0.01<0.01/Yb<0.01<0.01<0.01<0.01/<0.01<0.01<0.01<0.01/Hf0.710.9560.9540.9340.948Ta0.962.72W//////////Tl<0.01<0.01<0.01<0.01/<0.01<0.01<0.01<0.01/Pb0.1010.1180.0980.1060.0990.0970.1060.1014.70Bi<0.01<0.01<0.01<0.01/<0.01<0.01<0.01<0.01/表76#镍合金测定结果的精密度单位：mg/kg元素第一点第二点123平均RSD123平均RSDB//////////Mg24.9225.4525.3525.2425.5125.5725.5225.53Al////////////////////P//////////Ca0.5090.4800.4130.4670.6000.5980.5890.5960.98Ti//////////V0.190.74Mn//////////Cu//////////Zn6.216.160.725.956.096.136.06Ga20.3720.1520.2920.270.5520.6320.5820.8420.680.66As4.564.764.704.672.224.204.234.274.230.86<0.5<0.5<0.5<0.5/<0.5<0.5<0.5<0.5/Y0.0610.0640.0590.0614.100.0670.0720.0690.0693.63Zr2.222.202.272.232.892.842.912.88Nb//////////Mo//////////Ag//////////Cd//////////6.817.166.996.992.458.267.788.078.033.032.28Te0.0150.0150.0170.0167.370.0760.0530.0530.06121.9La0.0280.0280.0300.0294.030.0430.0460.0400.0436.98Ce<0.01<0.01<0.01<0.01/<0.01<0.01<0.01<0.01/Yb<0.01<0.01<0.01<0.01/<0.01<0.01<0.01<0.01/Hf//////////Ta95.5996.5995.9796.050.53W//////////Tl<0.01<0.01<0.01<0.01/<0.01<0.01<0.01<0.01/Pb0.8370.8100.8100.8190.8550.8910.9250.893.93Bi0.0100.0190.0070.01252.00.0090.0150.0100.01128.4表88#镍合金测定结果的精密度单位：mg/kg元素第一点第二点123平均RSD123平均RSDB45.0344.1044.5344.5542.5942.3241.8542.250.89Mg2.742.772.742.750.642.672.742.812.742.63Al74.6574.7073.9474.430.5773.7574.3675.5274.54//////////PCa2.342.02Ti2.852.13V//////////Mn//////////Cu//////////Zn7.016.987.267.082.176.987.096.866.98Ga0.620.76As27.4127.1527.3327.300.4927.3727.4927.0527.300.84<0.5<0.5<0.5<0.5/<0.5<0.5<0.5<0.5/Y//////////Zr4.814.814.964.865.025.265.345.213.17Nb//////////Mo20372025204620360.5120452083205720620.95Ag3.733.793.923.812.623.923.904.033.95Cd<0.1<0.1<0.1<0.1/<0.1<0.1<0.1<0.1/30.2031.1531.2530.8731.9232.6431.9032.157.427.227.517.382.027.447.437.597.49Te<0.01<0.01<0.01<0.01/<0.01<0.01<0.01<0.01/La0.0590.0610.0660.0625.820.0700.0670.0680.0682.23Ce0.1290.1250.1330.1293.100.1380.1370.1450.140Yb<0.01<0.01<0.01<0.01/<0.01<0.01<0.01<0.01/Hf0.1350.1340.1250.1314.190.1430.1370.1402.18Ta36.5735.9336.8436.4538.3138.1838.0738.20.32W//////////Tl<0.01<0.01<0.01<0.01/<0.01<0.01<0.01<0.01/Pb2.420.27Bi<0.01<0.01<0.01<0.01/<0.01<0.01<0.01<0.01/表910#镍合金测定结果的精密度单位：mg/kg元素第一点第二点123平均RSD123平均RSDB0.7820.7890.7860.7860.520.7030.6520.6940.6834.05Mg30.9231.2331.4831.210.8931.5631.6832.3331.86Al////////////////////P0.190.71Ca6.156.266.356.256.676.697.056.803.17Ti//////////V2.632.642.642.640.342.652.552.572.59Mn//////////Cu48.3248.7049.3348.7849.4948.9048.85Zn5.416.89Ga3.423.463.493.463.543.473.473.49As6.256.135.926.102.716.136.066.22<0.5<0.5<0.5<0.5/<0.5<0.5<0.5<0.5/Y<0.01<0.01<0.01<0.01/<0.01<0.01<0.01<0.01/Zr0.1450.1510.1560.1513.670.1470.1610.1690.159Nb0.88Mo//////////Ag0.1040.0700.0810.08520.20.0880.1090.1100.102Cd<0.1<0.1<0.1<0.1/<0.1<0.1<0.1<0.1/0.9190.8890.9390.9162.770.9130.8400.9920.9158.290.7590.7760.7140.7504.270.8220.7650.7850.7913.69Te<0.01<0.01<0.01<0.01/<0.01<0.01<0.01<0.01/La0.0820.0820.0810.0820.430.0830.0830.0940.0877.37Ce0.1600.1580.1580.1590.890.1670.1690.1630.166Yb<0.01<0.01<0.01<0.01/<0.01<0.01<0.01<0.01/Hf<0.01<0.01<0.01<0.01/<0.01<0.01<0.01<0.01/Ta0.0500.0570.0620.0570.0570.0500.0450.051W3.073.023.073.163.273.283.23Tl<0.01<0.01<0.01<0.01/<0.01<0.01<0.01<0.01/Pb2.75Bi<0.01<0.01<0.01<0.01/<0.01<0.01<0.01<0.01/表1012#镍合金测定结果的精密度单位：mg/kg元素第一点第二点123平均RSD123平均RSDB0.3870.3800.3690.3782.430.3720.3530.3380.3544.80Mg2.953.002.912.952.752.762.802.770.99Al////////////////////P2.06Ca//////////Ti//////////V0.100.24Mn0.590.84Cu//////////Zn8.949.71GaAs3.033.043.003.020.753.032.972.912.97<0.5<0.5<0.5<0.5/<0.5<0.5<0.5<0.5/Y0.0170.0190.0190.0195.400.0190.0170.0200.0198.06Zr0.1100.1010.0980.1036.070.1090.1186.50Nb//////////Mo//////////Ag0.1040.0840.1030.0970.1250.0830.1200.10921.3Cd<0.1<0.1<0.1<0.1/<0.1<0.1<0.1<0.1/0.5220.5800.5190.5406.430.5490.5890.4810.5400.1200.1360.1328.610.1350.1139.04Te<0.01<0.01<0.01<0.01/<0.01<0.01<0.01<0.01/La<0.01<0.01<0.01<0.01/<0.01<0.01<0.01<0.01/Ce<0.01<0.01<0.01<0.01/<0.01<0.01<0.01<0.01/Yb<0.01<0.01<0.01<0.01/<0.01<0.01<0.01<0.01/Hf<0.01<0.01<0.01<0.01/<0.01<0.01<0.01<0.01/Ta3.613.723.693.673.943.843.893.89W52.3353.0851.9352.4554.8154.7254.9354.820.19Tl0.0080.0140.0150.01231.40.0140.0130.0140.0136.20Pb0.103.03Bi<0.01<0.01<0.01<0.01/<0.01<0.01<0.01<0.01/表1114#镍合金测定结果的精密度单位：mg/kg元素第一点第二点123平均RSD123平均RSDB0.3940.4430.3930.4136.490.4190.4450.4160.4273.78Mg5.57Al23.2823.1623.3323.260.3825.2723.9322.7824.095.83//////////P0.310.30Ca3.252.993.184.223.173.082.883.045.01Ti4.414.484.474.450.874.534.544.524.530.21V0.73Mn//////////Cu55.2955.7455.1355.390.5755.9156.2556.5356.230.55Zn0.200.200.170.190.220.230.220.22Ga5.085.105.160.805.255.245.315.270.77As7.077.137.100.387.437.367.317.370.812.282.68Y0.0110.0120.0110.0116.660.0120.0130.0090.011Zr0.4410.3840.4240.4177.100.4410.4270.4120.4273.40Nb0.3900.4110.4120.4040.4190.4100.4200.416Mo20.2320.000.99Ag0.0650.0670.0840.0720.0740.0730.0890.079Cd<0.1<0.1<0.1<0.1/<0.1<0.1<0.1<0.1/4.454.204.274.313.034.464.684.554.572.442.24Te<0.01<0.01<0.01<0.01/<0.01<0.01<0.01<0.01/La0.0240.0230.0220.0235.930.0230.0210.0250.023Ce0.0500.0480.0520.0504.340.0570.0470.0430.049Yb<0.01<0.01<0.01<0.01/<0.01<0.01<0.01<0.01/Hf<0.01<0.01<0.01<0.01/<0.01<0.01<0.01<0.01/Ta0.0380.0380.0320.0369.050.0280.0300.0280.0294.51W0.76Tl<0.01<0.01<0.01<0.01/<0.01<0.01<0.01<0.01/Pb0.2710.2810.2840.2750.3040.2760.3050.2955.60Bi<0.01<0.01<0.01<0.01/<0.01<0.01<0.01<0.01/表1216#镍合金测定结果的精密度单位：mg/kg元素第一点第二点123平均RSD123平均RSDB0.3230.3810.3210.3410.3540.3410.3310.3423.45Mg0.9120.9040.8860.9010.9680.9710.8630.9346.60Al//////////P7.527.837.867.742.477.587.667.727.650.88Ca0.0990.1160.1097.700.0830.1020.1320.10623.6Ti6.566.656.586.590.716.656.706.696.680.37V0.8010.8020.8100.8040.670.8010.8020.8000.801Mn//////////Cu27.3427.2527.2727.290.1627.3227.4527.3727.380.24Zn0.2100.1400.1980.18320.60.1510.1360.2200.16926.7Ga0.72As2.943.023.063.013.073.032.963.028.958.35Y<0.01<0.01<0.01<0.01/<0.01<0.01<0.01<0.01/Zr0.0980.1010.1060.1023.910.1080.1030.0870.099Nb4.224.224.154.200.944.334.284.274.290.79Mo//////////Ag0.0620.0640.0860.0710.0840.0500.0590.06427.6Cd<0.1<0.1<0.1<0.1/<0.1<0.1<0.1<0.1/0.9880.9840.9960.9900.620.400.4690.4600.4750.4680.4910.4850.4950.490Te<0.01<0.01<0.01<0.01/<0.01<0.01<0.01<0.01/La0.0660.0650.0620.0653.430.0620.0870.0830.078Ce<0.01<0.01<0.01<0.01/<0.01<0.01<0.01<0.01/Yb<0.01<0.01<0.01<0.01/<0.01<0.01<0.01<0.01/Hf<0.01<0.01<0.01<0.01/<0.01<0.01<0.01<0.01/Ta0.0380.0330.0440.0380.0370.0380.0360.037W0.800.73Tl0.0340.0330.0270.0320.0290.0240.0120.02240.2Pb0.2770.2710.2710.2730.2770.2930.3200.2977.44Bi<0.01<0.01<0.01<0.01/<0.01<0.01<0.01<0.01/表13实验室序号及名称序号单位名称1国标（北京）检验认证有限公司2钢研纳克检测技术股份有限公司3金川集团股份有限公司4宁波江丰电子材料股份有限公司5国合通用（青岛）测试评价认证股份公司6广东先导稀材股份有限公司7深圳市中金岭南有色金属股份有限公司8上海有色金属工业技术监督监测中心有限公司9紫金矿业集团股份有限公司昆明冶金研究院有限公司峨嵋半导体材料研究所山东恒邦冶炼股份有限公司在每个样品水平中将各实验室精密度测试结果的平均值重新组成一组新的数据组，视表14格拉布斯检验结果元素样品号实验室序号λ(0.05,n)Gmax有无离群值是否舍去B22N否44N否24N否43N否63Y是82Y是44N否P21N否44N否87N否84N否84N否V6Y是44N否41N否22N否45N否23N否26N否Nb42N否85N否22N否45N否64N否85N否22N否45N否Hf45N否25N否46N否63Y是W25Y是采用科克伦（Cochran）检验法对每个样品剔除离群值后的不同实值之间进行等精度检验。先计算m组数据的各表15科克伦检验结果统计C(0.05,n)C43Y是86Y是P27Y是87Y是86Y是Nb46Y是86Y是45Y是22Y是44Y是根据GB/T6379.2-2004的要求对每个样品水平的测试数据进行统计，计算方法的重复表16重复性限和再现性限计算结果总平均值x/(mg/kg)/////////再现性方差sR2///////////////总平均值x/(mg/kg)//////再现性方差sR2////////总平均值x/(mg/kg)////////////再现性方差sR2////////////////////总平均值x/(mg/kg)////////////再现性方差sR2////////////////////总平均值x/(mg/kg)//////再现性方差sR2//////////总平均值x/(mg/kg)////////////再现性方差sR2////////////////////总平均值x/(mg/kg)////////////再现性方差sR2////////////////////总平均值x/(mg/kg)////////////再现性方差sR2////////////////////总平均值x/(mg/kg)////////////再现性方差sR2///////////////////总平均值x/(mg/kg)////////////再现性方差sR2////////////////////总平均值x/(mg/kg)/////////再现性方差sR2///////////////总平均值x/(mg/kg)////////////再现性方差sR2////////////////////总平均值x/(mg/kg)////////////再现性方差sR2////////////////////总平均值x/(mg/kg)////////////再现性方差sR2////////////////////总平均值x/(mg/kg)////////////再现性方差sR2////////////////////总平均值x/(mg/kg)///再现性方差sR2/////总平均值x/(mg/kg)/////////再现性方差sR2//////////////总平均值x/(mg/kg)/////////再现性方差sR2///////////////总平均值x/(mg/kg)///再现性方差sR2/////总平均值x/(mg/kg)/////////再现性方差sR2///////////////表17各样品水平的平均值、重复性限（r）和再现性限（R）R/(mg/kg)R/(mg/kg)BNbPHfVW镍合金作为一类重要的战略性材料，具有良好的高温强度和优良的耐磨损、耐高温、抗热震冲击、抗氧化性能抗腐蚀、抗疲劳性能，主要用于石油、化工、环保、航天以及核工业等行业的各类零部件的制造、修复和预保护。《中国制造2025》等战略规划将高温合金和金属间化合物高温材料的分类和牌号》中对镍基高温合金中元素含量有明确的规定，w(Zn)≤0.0005%，w(Pb)≤0.0002%，w(Sb)≤0.0005%，w(As)≤0.0005%，w(Ag)≤0.0005%，然而，目前，镍合金中痕量元素的分析方法主要有基于分离技术的分光光度法、原子杂，受到的光谱和质谱干扰严重，受到仪器及方法特性的影响，测定下限较高，无法满足镍合金中痕量元素的分析要求。迫切需要一种高灵敏度、低检出限、固体直接进样的分析除去样品表面的污染物。GDMS基体干扰小，分辨率高，可分辨绝大多数质谱干扰，测定有辉光放电质谱仪，辉光放电质谱法在高纯镍、高纯钴、高纯铜、高纯铝、高纯锌、高纯钛、高纯铼、高纯钨、高纯铌、高纯钽等有色金属中痕量元素含量的测定已有非常成熟的应用，并形成检测标准。本标准正是基于GDMS技术的优势，结合镍合金测需求提出的，采GDMS法对镍合金中痕量杂质元素进行测定。本标准对于价体系、提升产品质量、指导产品应用具、促镍合金因其独特的物理化学性质和广泛的应用领域，市场需求持续攀升。特别是在航空航天、石油化工、能源电力、海洋工程等关键领域，镍合金的应用日益广泛，推动了市场规模的不断扩大。新能源汽车和高端装备制造等新兴领域的快速发展，进一步增加了对根据产品标准的要求，不同牌号的镍合金中元素含量有明确的限制，本标准属于分析金化学分析方法》等标准的补充完善,与以上标准相比，降低了检测下限，能够满足镍合金镍合金产业的快速发展离不开分析技术的支持,镍合金分析检测标准的制定与完善将带本文件充分考虑了目前国内镍合金生产、研发、应用和检测的实际技术水平。本文件颁布执行后，能够推动镍合金检测的标准化，提高数据的准确度和一致性，助力我国镍合金产本文件与有关的现行法律、法规和强制性国家标准没有冲突。标准涉及内容全面、条工镍及镍合金牌号和化学成分》、GB/T1499建议向镍合金研发、生产、销售、检测的相关企业123456B123456789123456789P123456789123456789123456789123456789123456789123456789Y123456789123456789123456789123456789123456789123456789123456789123456789123456789123456789Hf123456789123456789W123456789123456789123456789123456789123456B123456789123456789123456789P1234567891234567891234567891234567891234567891234567891234567891<0.5<0.5<0.5<0.5<0.5<0.52<0.5<0.5<0.5<0.5<0.5<0.53<0.5<0.5<0.5<0.5<0.5<0.54<0.5<0.5<0.5<0.5<0.5<0.55<0.5<0.5<0.5<0.5<0.5<0.56<0.5<0.5<0.5<0.5<0.5<0.57<0.5<0.5<0.5<0.5<0.5<0.589Y123456789Nb123456789123456789123456789123456789123456789123456789123456789123456789123456789Hf123456789123456789123456789123456789123456789123456123456789123456789V123456789123456789120.3720.1520.2920.6320.5820.842321.4621.2520.97432.1734.3334.8537.7138.1738.35520.0720.6920.5720.226721.2721.0121.1321.3620.8920.34891234567891<0.5<0.5<0.5<0.5<0.5<0.52<0.5<0.5<0.5<0.5<0.5<0.53<0.5<0.5<0.5<0.5<0.5<0.54<0.5<0.5<0.5<0.5<0.5<0.55<0.5<0.5<0.5<0.5<0.5<0.56<0.5<0.5<0.5<0.5<0.5<0.57<0.5<0.5<0.5<0.5<0.5<0.589Y123456789123456789123456789123456789123456789123456789123456789123456789123456789123456789123456789123456B123456789123456789123456789P1234567891234567891234567891234567891234567891234567891<0.5<0.5<0.5<0.5<0.5<0.52<0.5<0.5<0.5<0.5<0.5<0.53<0.5<0.5<0.5<0.5<0.5<0.54<0.5<0.5<0.5<0.5<0.5<0.55<0.5<0.5<0.5<0.5<0.5<0.56<0.5<0.5<0.5<0.5<0.5<0.57<0.5<0.5<0.5<0.5<0.5<0.589123456789123456789123456789123456789123456789123456789123456789123456789123456789123456789Hf123456789123456789123456789123456789123456789表B.1格拉布斯检验数据统计元素B的质量分数/%/1////2////3////4////5////6//7//////s/%////λ(α,n)λ(0.05,10)=2.507λ(0.05,10)=2.507//λ(0.01,10)=1.472λ(0.01,10)=1.472/NN//元素Mg的质量分数/%/1////2////3////4////5////6//7//////s/%//λ(α,n)元素Al的质量分数/%/1//2//3//4//5//6/7///s/%//λ(α,n)λ(0.05,10)=2.507/λ(0.01,10)=1.472Y/元素Si的质量分数/%/1////2////3////4////5////6//7//////s/%////λ(α,n)λ(0.05,10)=2.507//λ(0.01,10)=1.472/N//元素P的质量分数/%/1//2//3//4//5//6/7///s/%//λ(α,n)λ(0.05,10)=2.507λ(0.05,10)=2.507λ(0.05,10)=2.507/λ(0.01,10)=1.472λ(0.01,10)=1.472λ(0.01,10)=1.472NNN/元素Ca的质量分数/%/1//2//3//4//5//6/7///s/%//λ(α,n)λ(0.05,10)=2.507/λ(0.01,10)=1.472N/元素Ti的质量分数/%/1//2//3//4//5//6/7///s/%//λ(α,n)λ(0.05,10)=2.507/λ(0.01,10)=1.472N/元素V的质量分数/%/1////2////3////4////5////6//7//////s/%////λ(α,n)λ(0.05,10)=2.507//λ(0.01,10)=1.472/NNY//元素Mn的质量分数/%/1////2////3////4////5////6//7//////s/%////λ(α,n)λ(0.05,10)=2.507//λ(0.01,10)=1.472/N//元素Cu的质量分数/%/1////2////3////4////5////6//7//////s/%//N//元素Ga的质量分数/%/1////2////3////4////5////6//7//////s/%////λ(α,n)λ(0.05,10)=2.507λ(0.05,10)=2.507//λ(0.01,10)=1.472λ(0.01,10)=1.472/NN//元素As的质量分数/%/1////2////3////4////5////6//7//////s/%////λ(α,n)λ(0.05,10)=2.507//λ(0.01,10)=1.472/N//元素Zr的质量分数/%/1////2////3////4////5////6//7//////s/%////λ(α,n)λ(0.05,10)=2.507//λ(0.01,10)=1.472/N//元素Nb的质量分数/%/1////2////3////4////5////6//7//////s/%////λ(α,n)λ(0.05,10)=2.507//λ(0.01,10)=1.472/N//元素Mo的质量分数/%/1//2//3//4//5//6/7///s/%//λ(α,n)λ(0.05,10)=2.507/λ(0.01,10)=1.472N/元素B的质量分数/%/1//2//3//4//5//6/7///s/%//λ(α,n)λ(0.05,10)=2.507λ(0.05,10)=2.507λ(0.05,10)=2.507λ(0.05,10)=2.507/λ(0.01,10)=1.472λ(0.01,10)=1.472λ(0.01,10)=1.472λ(0.01,10)=1.472NNNN/元素Sb的质量分数/%/1////2////3////4////5////6//7//////s/%//λ(α,n)元素Hf的质量分数/%/1////2////3////4////5////6//7//////s/%////λ(α,n)λ(0.05,10)=2.507//λ(0.01,10)=1.472/N//元素Ta的质量分数/%/1////2////3////4////5////6//7//////s/%////λ(α,n)λ(0.05,10)=2.507λ(0.05,10)=2.507λ(0.05,10)=2.507//λ(0.01,10)=1.472λ(0.01,10)=1.472λ(0.01,10)=1.472/NNY//元素W的质量分数/%/1////2////3////4////5////6//7//////s/%////λ(α,n)λ(0.05,10)=2.507//λ(0.01,10)=1.472/Y//表C.1各元素科克伦检验结果B元素科克伦（Cochran）检验结果样品编号2#4#6#8#单位序号s/(mg/kg)s2ns/(mg/kg)s2ns/(mg/kg)s2n10.0760.00630.3183///第2点0.37830.5950.3543///20.01330.890.7873///第2点0.02130.590.3513///30.700.49530.403///第2点0.250.06030.610.3733///40.890.79430.960.9173///第2点0.710.50631.9073///50.040.00230.353///第2点0.3830.0323///60.540.29731.0733///第2点0.210.04230.780.608370.460.21430.730.5283第2点0.4531.0783Cmax0.27000.2272C(α,m,n-1)C(0.05,14,2)=0.3346C(0.05,14,2)=0.3346///C(0.01,14,2)=0.4069C(0.01,14,2)=0.4069///结论等精度等精度///Mg元素科克伦（Cochran）检验结果样品编号2#4#6#8#单位序号s/(mg/kg)s2ns/(mg/kg)s2ns/(mg/kg)s23s/(mg/kg)s2n10.2290.05230.00580.0000330.2820.0793///第2点0.2520.06430.00580.0000330.0320.0013///20.03830.01050.0001130.050.0033///第2点0.090.00830.00750.0000630.0383///30.220.04930.01370.0001930.250.061////第2点0.040.00130.01660.000283//3///40.01030.01050.0001130.600.3623///第2点0.090.00830.01350.0001830.070.0063///50.010.00030.00700.0000530.0263///第2点0.080.00730.00400.0000230.343///60.060.00430.00580.0000330.750.5633///第2点0.02230.01150.0001330.700.490370.3530.05030.002530.790.6253第2点0.070.00530.04510.002030.6250.0393Cmax0.31240.43770.4377C(α,m,n-1)C(0.05,14,2)=0.3346C(0.05,14,2)=0.3346C(0.05,13,2)=0.3924///C(0.01,14,2)=0.4069C(0.01,14,2)=0.4069C(0.01,13,2)=0.4751///结论等精度有离群值等精度///Al元素科克伦（Cochran）检验结果样品编号2#4#6#8#单位序号s/(mg/kg)s2ns/(mg/kg)s2ns/(mg/kg)s2ns/(mg/kg)s2ns/(mg/kg)s2n10.425///第2点0.8990.808///2/////第2点3.7213.816///30.700.496///第2点0.720.520///41.851///第2点///51.297///第2点2.242///60.470.217///第2点4.9824.77470.070.006第2点2.566.546Cmax0.4435C(α,m,n-1)C(0.05,13,2)=0.3346///C(0.01,13,2)=0.4069///结论有离群值///Si元素科克伦（Cochran）检验结果样品编号2#4#6#8#单位序号s/(mg/kg)s2ns/(mg/kg)s2ns/(mg/kg)s2n12.9098.4633///第2点0.6430.4133///21.0813///第2点3///3101.9823///第2点2.626.8523///47.7560.0833///第2点0.770.5963///58.9780.3793///第2点0.383///64.4533///第2点2.836373.9415.5073第2点2.9133Cmax0.3530C(α,m,n-1)C(0.05,14,2)=0.3346///C(0.01,14,2)=0.4069///结论有离群值///P元素科克伦（Cochran）检验结果样品编号2#4#6#8#单位序号s/(mg/kg)s2ns/(mg/kg)s2ns/(mg/kg)s2ns/(mg/kg)s2ns/(mg/kg)s2n10.0150.00030.0710.00531.4982.2433///第2点0.03230.03131.5502.4033///20.8490.72230.080.00632.4473///第2点0.4990.24930.250.06230.730.5293///30.7660.58730.450.20130.343///第2点0.7700.59430.230.05430.200.0383///44.63530.200.03832.7793///第2点0.7360.54230.240.06030.760.5733///50.3090.09530.070.00530.670.4523///第2点0.3070.09430.210.04430.640.4093///61.5662.45430.4130.990.9733///第2点1.37930.720.52530.310.093373.0619.36730.03331.3211.7453第2点5.04425.44430.4790.22932.8077.8793Cmax0.55080.35970.3474C(α,m,n-1)C(0.05,14,2)=0.3346C(0.05,14,2)=0.3346C(0.05,14,2)=0.3346///C(0.01,14,2)=0.4069C(0.01,14,2)=0.4069C(0.01,14,2)=0.4069///结论有离群值有歧离值等精度///Ca元素科克伦（Cochran）检验结果样品编号2#4#6#8#单位序号s/(mg/kg)s2ns/(mg/kg)s2ns/(mg/kg)s2ns/(mg/kg)s2ns/(mg/kg)s2n10.2800.0783///第2点0.2620.0693///20.270.0753///第2点0.363///30.353///第2点0.0103///40.353///第2点0.570.3263///50.0273///第2点0.0233///61.0213///第2点0.300.088370.0333第2点1.7593.0933Cmax0.5922C(α,m,n-1)C(0.05,14,2)=0.3346///C(0.01,14,2)=0.4069///结论有离群值///Ti元素科克伦（Cochran）检验结果样品编号2#4#6#8#单位序号s/(mg/kg)s2ns/(mg/kg)s2ns/(mg/kg)s2ns/(mg/kg)s2ns/(mg/kg)s2n14.23417.9233///第2点3.26510.6633///23.2710.7233///第2点2.7833///32.2803///第2点3.5812.8043///42.797.7973///第2点0.680.4633///51.6473///第2点3.7714.2143///612.78163.2433///第2点4.2818.303370.7200.5193第2点2.7887.7753Cmax0.6021C(α,m,n-1)C(0.05,14,2)=0.3346///C(0.01,14,2)=0.4069///结论有离群值///V元素科克伦（Cochran）检验结果样品编号2#4#6#8#单位序号s/(mg/kg)s2ns/(mg/kg)s2ns/(mg/kg)s2ns/(mg/kg)s2ns/(mg/kg)s2n10.2310.0533///第2点0.9870.9733///2//////第2点//////31.4553///第2点//////42.673///第2点0.950.9063///50.343///第2点0.0323///62.888.3203///第2点2.204.853370.353第2点1.7253Cmax0.3239C(α,m,n-1)C(0.05,11,2)=0.3924///C(0.01,11,2)=0.4751///结论有离群值///Mn元素科克伦（Cochran）检验结果样品编号2#4#6#8#单位序号s/(mg/kg)s2ns/(mg/kg)s2ns/(mg/kg)s2ns/(mg/kg)s2ns/(mg/kg)s2n10.0860.0073///第2点0.2000.0403///20.333///第2点0.610.3673///30.970.9353///第2点0.423///41.3883///第2点0.520.2743///51.6633///第2点0.640.4143///60.710.4983///第2点0.530.284371.4011.9623第2点0.0333Cmax0.2408C(α,m,n-1)C(0.05,14,2)=0.3346///C(0.01,14,2)=0.4069///结论等精度///Cu元素科克伦（Cochran）检验结果样品编号2#4#6#8#单位序号s/(mg/kg)s2ns/(mg/kg)s2ns/(mg/kg)s2ns/(mg/kg)s2ns/(mg/kg)s2n10.6240.3903///第2点0.3623///20.540.2923///第2点0.0253///30.383///第2点0.0203///40.720.5183///第2点0.510.2633///50.060.0043///第2点0.353///61.3523///第2点3.219371.3741.8893第2点4.4493Cmax0.3470C(α,m,n-1)C(0.05,14,2)=0.3346///C(0.01,14,2)=0.4069///结论有歧离值///Ga元素科克伦（Cochran）检验结果样品编号2#4#6#8#单位序号s/(mg/kg)s2ns/(mg/kg)s2ns/(mg/kg)s2ns/(mg/kg)s2ns/(mg/kg)s2n10.5800.33730.0530.0033///第2点0.03830.0610.0043///20.030.00130.020.0003///第2点0.080.00730.0103///30.230.05330.413///第2点0.02230.260.0693///40.02530.060.0033///第2点0.4330.090.0083///50.030.00130.080.0063///第2点0.01430.050.0023///60.3330.250.0633///第2点0.610.37330.270.075370.520.26930.230.0513第2点0.02430.220.0493Cmax0.25640.3314C(α,m,n-1)C(0.05,14,2)=0.3346C(0.05,14,2)=0.3346///C(0.01,14,2)=0.4069C(0.01,14,2)=0.4069///结论等精度等精度///As元素科克伦（Cochran）检验结果样品编号2#4#6#8#单位序号s/(mg/kg)s2ns/(mg/kg)s2ns/(mg/kg)s2ns/(mg/kg)s2ns/(mg/kg)s2n10.0910.0083///第2点0.0920.0093///20.270.0723///第2点0.090.0083///30.353///第2点0.250.0653///40.210.0443///第2点0.0103///50.050.0033///第2点0.0183///60.060.0043///第2点0.020370.270.0713第2点0.250.0623Cmax0.2378C(α,m,n-1)C(0.05,14,2)=0.3346///C(0.01,14,2)=0.4069///结论等精度///Zr元素科克伦（Cochran）检验结果样品编号2#4#6#8#单位序号s/(mg/kg)s2ns/(mg/kg)s2ns/(mg/kg)s2ns/(mg/kg)s2ns/(mg/kg)s2n10.0103///第2点0.0550.0033///20.260.0683///第2点0.040.0013///30.060.0043///第2点0.050.0023///40.230.0553///第2点0.423///50.0343///第2点0.060.0043///60.0123///第2点0.240.060370.530.2823第2点0.250.0613Cmax0.3631C(α,m,n-1)C(0.05,14,2)=0.3346///C(0.01,14,2)=0.4069///结论有歧离值///Nb元素科克伦（Cochran）检验结果样品编号2#4#6#8#单位序号s/(mg/kg)s2ns/(mg/kg)s2ns/(mg/kg)s2ns/(mg/kg)s2ns/(mg/kg)s2n11.3751.8903///第2点4.6233///22.5263///第2点2.375.6303///31.4393///第2点2.918.4823///45.7332.8513///第2点2.3133///54.263///第2点1.2983///66.9247.8643///第2点11.01121.228375.3728.8203第2点2.094.3473Cmax0.4308C(α,m,n-1)C(0.05,14,2)=0.3346///C(0.01,14,2)=0.4069///结论有歧离值///Mo元素科克伦（Cochran）检验结果样品编号2#4#6#8#单位序号s/(mg/kg)s2ns/(mg/kg)s2ns/(mg/kg)s2ns/(mg/kg)s2ns/(mg/kg)s2n110.536111.003///第2点19.425377.333///243.251870.423///第2点32.911082.793///3230.083///第2点7.5456.843///40.000.003///第2点50.542554.333///584.393///第2点14.21202.023///6118.2113973.293///第2点171.6029445.94373.26510.663第2点17.039290.333Cmax0.5855C(α,m,n-1)C(0.05,14,2)=0.3346///C(0.01,14,2)=0.4069///结论有离群值///Sn元素科克伦（Cochran）检验结果样品编号2#4#6#8#单位序号s/(mg/kg)s2ns/(mg/kg)s2ns/(mg/kg)s2ns/(mg/kg)s2ns/(mg/kg)s2n10.02430.02630.03130.5800.3363///第2点0.0720.00530.0250.00130.2420.05830.4223///20.03130.03030.01330.580.3363///第2点0.040.00230.03430.02230.590.3473///30.3230.3530.02630.0113///第2点0.4030.02830.03530.270.0703///40.02730.01130.01430.820.6