硼鐵 鋁含量的測(cè)定 EDTA滴定法、鉻天青S分光光度法和電感耦合等離子體發(fā)射光譜法 編制說(shuō)明

《硼鐵鋁含量的測(cè)定EDTA滴定法、鉻天青S分光光度法和電感耦合等離子體發(fā)射光譜法》編制說(shuō)明根據(jù)國(guó)家標(biāo)準(zhǔn)化管理委員會(huì)國(guó)標(biāo)委發(fā)[2023]58號(hào)“國(guó)家標(biāo)準(zhǔn)化管理委員會(huì)鐵鋁含量的測(cè)定EDTA滴定法、鉻天青S分光光度法和電感耦合等離子體發(fā)射2025年1月：完成精密度數(shù)據(jù)的統(tǒng)計(jì)，并根據(jù)協(xié)作單位返回的的建議編制試驗(yàn)方法標(biāo)準(zhǔn)》、GB/T6379.1-2004《測(cè)量方法與結(jié)果的準(zhǔn)確度（正確度與精（2）充分考慮產(chǎn)品生產(chǎn)技術(shù)及應(yīng)用領(lǐng)域的發(fā)展，本著檢測(cè)分析方法的技術(shù)目前國(guó)標(biāo)對(duì)鋁元素的分析方法是GB/T3654.4-2008《硼鐵鋁含量的測(cè)定而實(shí)際生產(chǎn)中低鋁硼鐵很普遍，是非晶態(tài)合金的主要原材料，對(duì)于鋁含量小于1.00%的硼鐵，缺少合適的標(biāo)準(zhǔn)分析方法。分光光度法是對(duì)冶金產(chǎn)品中微量元素也不能滿足GB/T1.1-2020的要求。本標(biāo)準(zhǔn)是對(duì)GB/T3654.4-2008進(jìn)——增加了“試樣分析結(jié)果接受程序流程圖”。本標(biāo)準(zhǔn)規(guī)定了采用EDTA滴定法、鉻天青S分光光度法和電感耦合等離子體發(fā)射光譜法測(cè)定硼鐵中鋁的含量。本標(biāo)準(zhǔn)適用于硼鐵中鋁含量的測(cè)定，EDTA滴選擇硼鐵6#（由0.1000g硼鐵標(biāo)樣（GSB03-2599-表5-1精密度和準(zhǔn)確度試驗(yàn)編號(hào)標(biāo)準(zhǔn)值/%測(cè)定值（9次）/%平均值/%極差/%標(biāo)準(zhǔn)偏差/%相對(duì)標(biāo)準(zhǔn)偏差/%GSB03-2599-20100.990.9880.9971.0210.9930.9691.0100.9860.9740.9840.9910.0520.016以硼鐵6#樣品（GSB03-2599-2010，Al量為0.99mg）作為基體，加入不同量的鋁標(biāo)準(zhǔn)溶液，按試驗(yàn)方法操作，進(jìn)行回表5-2回收率試驗(yàn)加入Al量(mg)2.003.00樣品中Al量（mg）2.993.99測(cè)得Al量(mg)回收率(%)1.98,1.97,2.0099.0，98.0，101.03.00,3.02,3.03100.5，101.5，102.04.00,3.99,4.03100.3，100.0，101.3適量氫氟酸加熱溶解，待劇烈反應(yīng)停止后，冒高氯酸煙，繼續(xù)加熱冒煙至濕鹽狀，取下稍冷，加少量水和定最合適的檢測(cè)波長(zhǎng)，現(xiàn)以一定濃度的鋁標(biāo)準(zhǔn)溶液在450nm圖5-1波長(zhǎng)與吸光度關(guān)系圖移取在一組50mL容量瓶中分別分取0mL、0.50mL、1.00mL、2.00mL、3.00mL、4.00mL鋁標(biāo)準(zhǔn)溶液（5μg/mL），按顯色液操作，以不加鋁的空白試表5-3校準(zhǔn)曲線試驗(yàn)鋁標(biāo)液加入量（mL）00.502.003.004.00吸光度（A）0.0020.0680.1330.2650.4010.522圖5-2吸光度和鋁的加入量關(guān)系圖由測(cè)得吸光度表明，顯色溶液中鋁含量在（0~20）μg符合比爾定律，校準(zhǔn)稱取0.1000g硼鐵4#樣品，分別改變顯色過(guò)程中六次甲基四胺的加入量、表5-4六次甲基四胺加入量試驗(yàn)六次甲基四胺加入量（mL）0.52.02.5吸光度（A）0.3120.3180.3220.3200.322表5-5鉻天青S加入量試驗(yàn)鉻天青S加入量（mL）0.52.02.53.0吸光度（A）0.3030.3100.3200.3220.3230.322上，所以本方法選擇混勻后放置20min進(jìn)行測(cè)量。顯色溫度試驗(yàn)結(jié)果表明在以硼鐵4#樣品作為基體，加入不同的鋁標(biāo)準(zhǔn)溶液后按試驗(yàn)方法操作，進(jìn)行表5-6回收率試驗(yàn)加入鋁量(μg)5.0010.0015.00測(cè)得鋁量(μg)回收率(%)4.955.015.0399.0100.2100.610.0510.089.93100.5100.899.315.0715.1514.95100.5101.099.7），表5-7精密度和準(zhǔn)確度試驗(yàn)編號(hào)標(biāo)準(zhǔn)值/%測(cè)量值（9次）/%平均值/%極差/%標(biāo)準(zhǔn)偏差/%相對(duì)標(biāo)準(zhǔn)偏差/%YSBC28633-20110.0360.03630.03700.03580.03620.03550.03650.03610.03680.03630.1830.1860.1880.03630.00150.0005YSBC28634-20110.1850.1850.1860.1840.1890.1900.1820.5830.5890.5860.1860.0080.0027合成樣0.5880.5920.5860.5850.5830.5850.5840.5860.0090.00290.50取1#～6#硼鐵樣品，將試樣置于聚四氟乙烯燒杯中，加入5mL硝酸，2mL在少量不溶物，所以本試驗(yàn)選擇酸溶后如有殘?jiān)?-8回收率試驗(yàn)加入鋁量(mg)2.003.00測(cè)得鋁量(mg)回收率(%)1.020.991.01102.099.0101.02.031.982.01101.599.0100.53.023.012.97100.7100.399.0），表5-9精密度和準(zhǔn)確度試驗(yàn)編號(hào)標(biāo)準(zhǔn)值/%測(cè)定值（9次）/%平均值/%極差/%標(biāo)準(zhǔn)偏差/%相對(duì)標(biāo)準(zhǔn)偏差/%YSBC28633-20110.0360.03620.03630.03650.03610.03640.03620.03580.03600.03590.1870.1860.1890.03620.00070.00020.64YSBC28634-20110.1850.1880.1870.1880.1900.1860.1870.5860.5890.5880.1880.0080.00130.71合成樣0.5880.5910.5920.5900.5890.5900.5880.5890.0060.00180.30量方法與結(jié)果的準(zhǔn)確度（正確度與精密度）第2度）的一致性，隨后用Grubbs法檢驗(yàn)實(shí)驗(yàn)室單元平均值的一致性，確定是否有表6-2精密度原始數(shù)據(jù)實(shí)驗(yàn)室（質(zhì)量分?jǐn)?shù)）/%P-10.01620.03670.08520.1890.5860.9910.01640.03620.08520.1920.5840.9900.01560.03570.08610.1870.5860.992P-20.01600.03200.08100.1730.6020.01500.03300.08300.1750.6150.01700.03300.07960.1800.6130.996P-30.01840.03600.08270.1850.5860.9970.01810.03610.08260.1860.5870.9920.01810.03580.08310.1850.5880.987P-40.01590.04070.08420.2000.6070.01780.04270.08360.2050.5930.01630.04150.08190.1950.6080.986P-50.01750.03440.08290.1910.5750.01700.03520.08360.1880.5800.01820.03390.08490.1960.5680.982P-60.01860.04270.08140.2040.6080.02070.04370.08420.1970.6240.9960.01980.04320.08190.2000.610P-70.01750.03550.08150.1800.5800.9820.01700.03500.08110.1820.5830.9880.01830.03620.08250.1810.5880.993P-80.01920.03780.08410.1920.5930.9990.01950.03830.08450.1900.5950.02010.03890.08390.1860.600表6-3單元平均值實(shí)驗(yàn)室（質(zhì)量分?jǐn)?shù)）/%P-10.01610.03620.08550.18930.58530.9910P-20.01600.03270.08120.17600.61001.0253P-30.01820.03600.08280.18530.58700.9920P-40.01670.04160.08320.20000.60271.0130P-50.01760.03450.08380.19170.57431.0103P-60.01970.04320.08250.20030.61401.0130P-70.01760.03560.08170.18100.58370.9877P-70.01960.03830.08420.18930.59601.0047P-80.00210.00170.00290.00910.01620.0510表6-4曼德爾h統(tǒng)計(jì)量實(shí)驗(yàn)室P-1-1.117-0.2950.025-0.632-1.026P-2-1.163-1.281-1.381-1.548P-30.365-0.360-0.226-0.447-0.513-0.951P-4-0.7000.0870.6140.631P-5-0.075-0.7700.4960.300-1.4240.430P-6-0.4420.631P-7-0.052-0.472-1.020-0.958-0.752-1.277P-80.3000.7610.0250.1350.003圖6-1曼德爾h統(tǒng)計(jì)量表6-5單元標(biāo)準(zhǔn)差實(shí)驗(yàn)室（質(zhì)量分?jǐn)?shù)）/%P-10.000420.000500.000520.002520.001150.00100P-20.001000.000580.001710.003610.007000.02730P-30.000170.000150.000260.000580.001000.00500P-40.001000.001010.001190.005000.008390.02862P-50.000600.000660.001010.004040.006030.02710P-60.001050.000500.001490.003510.008720.01480P-70.000660.000600.000720.001000.004040.00551P-80.000460.000550.000310.003060.003610.00551表6-6曼德爾k統(tǒng)計(jì)量實(shí)驗(yàn)室P-10.5670.8210.5020.7780.2010.055P-20.948P-30.2360.2510.2560.1790.1740.277P-4P-50.8200.981P-60.8210.820P-70.8920.9900.6970.3090.7040.305P-80.6240.9040.2950.9450.6280.305圖6-2曼德爾k統(tǒng)計(jì)量表6-7單元方差和柯克倫檢驗(yàn)實(shí)驗(yàn)室P-11.73E-072.50E-072.70E-076.33E-061.33E-061.00E-06P-21.00E-063.33E-072.92E-061.30E-054.90E-057.45E-04P-33.00E-082.33E-087.00E-083.33E-071.00E-062.50E-05P-41.00E-061.01E-061.42E-062.50E-057.03E-05P-53.63E-074.30E-071.03E-061.63E-053.63E-057.34E-04P-62.50E-072.23E-061.23E-057.60E-052.19E-04P-74.30E-073.63E-075.20E-071.00E-061.63E-053.03E-05P-82.10E-073.03E-079.33E-089.33E-061.30E-053.03E-05C0.2570.3420.3410.2990.2890.314p=8，n=3時(shí)，柯克倫檢驗(yàn)1%顯著水平臨界值為0.615，5%顯著水平臨界值表6-8格拉布斯檢驗(yàn)水平單個(gè)高值單個(gè)低值0.862兩個(gè)高值0.2470.1690.3950.3660.2670.517兩個(gè)低值0.4780.5150.2740.3310.4830.420表6-9精密度mrR圖6-3精密度函數(shù)關(guān)系圖6-4精密度函數(shù)關(guān)系表6-10精密度原始數(shù)據(jù)實(shí)驗(yàn)室（質(zhì)量分?jǐn)?shù)）/%P-10.01660.03800.08460.1940.5850.9800.01720.03750.08520.1920.5850.9790.01690.03820.08560.1900.5860.982P-20.01730.03450.08600.1940.5780.9630.01750.03500.08600.1960.5740.9650.01800.03500.08700.1920.5720.961P-30.01810.03650.08320.1840.5870.9950.01810.03620.08370.1850.5880.9920.01800.03630.08290.1860.5890.992P-40.01670.03560.08470.1860.5800.9750.01660.03590.08490.1870.5830.9780.01720.03600.08500.1880.5850.979P-50.01810.03620.08440.1840.5870.9930.01810.03610.08400.1860.5880.9920.01800.03630.08520.1860.5870.992P-60.01780.03850.08510.1860.5950.01810.03820.08550.1920.5910.01790.03900.08620.1870.596P-70.01750.03530.08220.1820.5780.9850.01760.03550.08190.1810.5820.9860.01740.03520.08250.1860.5750.980P-80.01830.03580.08360.1890.5900.9900.01850.03650.08410.1840.5880.9960.01860.03620.08330.1900.5870.994表6-11單元平均值實(shí)驗(yàn)室（質(zhì)量分?jǐn)?shù)）/%P-10.01690.03790.08510.19200.58530.9803P-20.01760.03480.08630.19400.57470.9630P-30.01810.03630.08330.18500.58800.9930P-40.01680.03580.08490.18700.58270.9773P-50.01810.03620.08450.18530.58730.9923P-60.01790.03860.08560.18830.59401.0080P-70.01750.03530.08220.18300.57830.9837P-80.01850.03620.08370.18770.58830.9933表6-12曼德爾h統(tǒng)計(jì)量實(shí)驗(yàn)室P-1-1.3320.5090.082-0.449P-2-1.249-1.658-1.737P-30.684-0.050-0.882-0.7620.5170.492P-4-1.447-0.4500.311-0.216-0.353-0.672P-50.684-0.1570.062-0.6710.4080.443P-60.4530.8570.148P-7-0.295-0.849-1.677-1.308-1.060-0.201P-8-0.183-0.584-0.0340.5710.517圖6-5曼德爾h統(tǒng)計(jì)量表6-13單元標(biāo)準(zhǔn)差實(shí)驗(yàn)室（質(zhì)量分?jǐn)?shù)）/%P-10.000300.000360.000500.002000.000580.00153P-20.000360.000290.000580.002000.003060.00200P-30.000060.000150.000400.001000.001000.00173P-40.000320.000210.000150.001000.002520.00208P-50.000060.000100.000610.001150.000580.00058P-60.000150.000400.000560.003210.002650.00265P-70.000100.000150.000300.002650.003510.00321P-80.000150.000350.000400.003210.001530.00306表6-14曼德爾k統(tǒng)計(jì)量實(shí)驗(yàn)室P-10.9060.2610.678P-20.9060.887P-30.2630.5580.8740.4530.4530.768P-40.7600.3300.4530.923P-50.2630.3650.5230.2610.256P-60.695P-70.4550.5580.649P-80.6950.8740.692圖6-6曼德爾k統(tǒng)計(jì)量表6-15單元方差和柯克倫檢驗(yàn)實(shí)驗(yàn)室P-19.00E-081.30E-072.53E-074.00E-063.33E-072.33E-06P-21.30E-078.33E-083.33E-074.00E-069.33E-064.00E-06P-33.33E-092.33E-081.63E-071.00E-061.00E-063.00E-06P-41.03E-074.33E-082.33E-081.00E-066.33E-064.33E-06P-53.33E-091.00E-083.73E-071.33E-063.33E-073.33E-07P-62.33E-081.63E-073.10E-071.03E-057.00E-067.00E-