《鈮鐵鈦含量的測(cè)定變色酸光度法和二安替比林甲烷光度法》國(guó)家標(biāo)準(zhǔn)編制說(shuō)明20226《鈮鐵鈦含量的測(cè)定變色酸光度法和二安替比林甲烷光度法》國(guó)家標(biāo)準(zhǔn)編制說(shuō)明一、任務(wù)來(lái)源1、任務(wù)來(lái)源根據(jù)國(guó)家標(biāo)準(zhǔn)化管理委員會(huì)文件國(guó)標(biāo)委發(fā)[2021]192021鐵鈦含量的測(cè)定變色酸光度法和二安替比林甲烷光度法》（2、標(biāo)準(zhǔn)編制的目的和意義生產(chǎn)和使用具有重要的意義。GB/T3654.8-2008《鈮鐵鈦含量的測(cè)定變色酸光度法》提供了變色酸光度GB/T1.1-2020GB/T3654.8進(jìn)行修訂，增加了GB/T1.1-2020要求編寫(xiě)，重新進(jìn)行操作步驟的范了鈮鐵鈦含量的測(cè)定標(biāo)準(zhǔn)，使測(cè)定結(jié)果表述更加科學(xué)、更加規(guī)范。用和貿(mào)易要求提供技術(shù)支撐。二、起草單位情況軍等。并進(jìn)行文稿編輯等工作。三、標(biāo)準(zhǔn)編制過(guò)程起草(草案、調(diào)研)階段:20217月接到標(biāo)準(zhǔn)的制訂任務(wù)，于當(dāng)月成立了標(biāo)準(zhǔn)制訂小組；20217月～9寫(xiě)工作；2021年9月：組織8家實(shí)驗(yàn)室對(duì)標(biāo)準(zhǔn)草案規(guī)定的方法進(jìn)行精密度協(xié)作試驗(yàn)；2022年1月：完成精密度數(shù)據(jù)的統(tǒng)計(jì)，并根據(jù)協(xié)作單位返回的的意見(jiàn)進(jìn)行了征求意見(jiàn)稿的編寫(xiě)。征求意見(jiàn)階段:2022年4月-5月，發(fā)出征求意見(jiàn)稿單位數(shù)25個(gè)，另發(fā)送全國(guó)生鐵和鐵合金標(biāo)準(zhǔn)化技術(shù)委員會(huì)全體委員,并在中國(guó)鋼鐵標(biāo)準(zhǔn)網(wǎng)公開(kāi)征求意見(jiàn)。2022年6月，標(biāo)委會(huì)對(duì)收集到的意見(jiàn)進(jìn)行了進(jìn)一步的處理，并形成標(biāo)準(zhǔn)送審稿，計(jì)劃召開(kāi)標(biāo)準(zhǔn)評(píng)審會(huì)。四、標(biāo)準(zhǔn)編制原則GB/T1.1-20201部分：GB/T（正確度與精密度1GB/T6379.2-2004《測(cè)量方法與（正確度與精密度2的基本方法》，以及國(guó)內(nèi)有關(guān)部門(mén)專(zhuān)家的意見(jiàn)，進(jìn)行認(rèn)真編制。編制原則：⑴注重檢測(cè)手段的先進(jìn)性和主流發(fā)展趨勢(shì)，參考國(guó)內(nèi)外先進(jìn)標(biāo)準(zhǔn)。⑵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)性能指標(biāo)適度超前現(xiàn)有產(chǎn)品標(biāo)準(zhǔn)原則。⑶充分考慮了滿(mǎn)足國(guó)家法律法規(guī)、安全衛(wèi)生以及環(huán)保法規(guī)的要求。五、標(biāo)準(zhǔn)修訂的主要內(nèi)容GB/T3654.8－2008GB/T3654.8－2008修改了“本標(biāo)準(zhǔn)”為“本文件”（見(jiàn)1范圍）；修改了“規(guī)范性引用文件”的引導(dǎo)語(yǔ)（見(jiàn)2規(guī)范性引用文件）；增加了“術(shù)語(yǔ)和定義”（見(jiàn)3術(shù)語(yǔ)和定義）；修改了“儀器”為“儀器和設(shè)備”（見(jiàn)4.3儀器和設(shè)備）；增加了“測(cè)定次數(shù)”內(nèi)容（見(jiàn)4.5.1測(cè)定次數(shù)）；修改了試料量，鈦含量為﹥0.50%～1.00%時(shí)分取量由10.00mL，改為20.00mL（見(jiàn)4.5.2）；修改了“空白試驗(yàn)”為“空白試驗(yàn)和驗(yàn)證試驗(yàn)”（見(jiàn)4.5.3）100mL5mL20mL100mL100mL5mL”（4.5.4.1）；修改了顯色溶液：“向一份試液和隨同試料的空白溶液中加入10mL草酸溶液”改為“向一份試液和隨同試料的空白溶液中補(bǔ)加草酸溶液（4.2.6）至30mL”（見(jiàn)4.5.4.5）；修改了參比溶液：“向另一份試液和隨同試料的空白溶液中加入10mL草酸溶液”改為“向另一份試液和隨同試料的空白溶液中補(bǔ)加草酸溶液（4.2.6）至30mL”（見(jiàn)4.5.4.6）；修改了校準(zhǔn)曲線(xiàn)的繪制，移取鈦標(biāo)準(zhǔn)溶液及體積（4.5.52）；修改了“分析結(jié)果的計(jì)算”為“分析結(jié)果的計(jì)算和表示”（修改了“允許差”為“精密度”，增加內(nèi)容（4.7精密度）；增加了“方法二 二安替比林甲烷光度法”（見(jiàn)5方法二二安替比甲烷光度法）；增加了規(guī)范性附錄“試樣分析值接受程序流程圖”(見(jiàn)附錄A）。六、試驗(yàn)?zāi)芰︱?yàn)證本標(biāo)準(zhǔn)規(guī)定了采用變色酸光度法和二安替比林甲烷光度法測(cè)定鈮鐵中鈦的含量，測(cè)定范圍（質(zhì)量分?jǐn)?shù)）：0.010%～2.50%。試驗(yàn)條件的選擇變色酸光度法光吸收曲線(xiàn)1475nm475nm圖1光吸收曲線(xiàn)試驗(yàn)圖（變色酸光度法）樣品溶解過(guò)程中硫酸量的選擇稱(chēng)取0.2000g10mL～20mL結(jié)果基本沒(méi)有影響，又進(jìn)行了加標(biāo)試驗(yàn)（加入2mL含鈦量為200.0μg/mL標(biāo)液得到同樣的結(jié)論，本方法選擇加入硫酸15mL。樣品溶解方法試驗(yàn)0.2000g（GSB03-2202-2008）1：將試料100mL5mL，20mL2：100mL5mL100mL5mL100mL100mL20mL1作。表1 溶解試驗(yàn)結(jié)果樣品溶解方法方法1方法2方法3標(biāo)樣鈦含量（%）0.490.490.49測(cè)得鈦含量（%）0.4850.4910.486顯色條件試驗(yàn)0.2000g1#樣品，分別改變顯色過(guò)程中草酸的加入量、變色酸加2、3表2 草酸加入量試驗(yàn)草酸加入量（mL）05101520吸光度（A）0.4120.4180.4220.4200.422表3變色酸加入量試驗(yàn)變色酸加入量（mL） 3 4 5 6 7 8吸光度（A） 0.353 0.370 0.420 0.422 0.42 0.422由上表結(jié)果可以看出，草酸加入量為5mL以上時(shí)，吸光度值基本趨于穩(wěn)定，本試驗(yàn)選擇加入10mL只要保證在繪制工作曲線(xiàn)和樣品分析時(shí)溫度保持一致即可。二安替比林甲烷光度法光吸收曲線(xiàn)取一鈮鐵樣品，于不同波長(zhǎng)處進(jìn)行比色，繪制吸收曲線(xiàn)，如圖2?？梢钥闯觯诓ㄩL(zhǎng)390nm處出現(xiàn)了最高峰，所以本試驗(yàn)選擇390nm為測(cè)定波長(zhǎng)。圖2光吸收曲線(xiàn)試驗(yàn)圖（二安替比林甲烷光度法）顯色條件試驗(yàn)4～618℃～30℃，溫度對(duì)結(jié)果基本沒(méi)有影響。因此，本試驗(yàn)選擇加入5mL15mL30min表4 鹽酸加入量試驗(yàn)鹽酸加入量（mL）2345810吸光度0.3800.3950.4050.4100.4090.410表5 二安替比林甲烷加入量試驗(yàn)二安替比林甲烷加入量（mL）1012 14 151618吸光度0.3610.390 0.408 0.4100.4100.410表6顯色時(shí)間試驗(yàn)顯色時(shí)間（min） 01025 304050吸光度 0.2840.3610.404 0.4100.4100.4002.回收率變色酸光度法（97TR43024）7。表7 回收率試驗(yàn)加入鈦量(μg)80120200測(cè)得鈦量(μg)77,78,82117,116,119196,197,202回收率(%)96.25、97.50、102.5097.50，96.67，99.1798.00，98.50，101.00由表7可以看出，本方法的回收率在96.25%～102.50%之間，回收率良好。二安替比林甲烷光度法（97TR43024）8。表8 回收率試驗(yàn)加入鈦量(μg)80120200測(cè)得鈦量(μg)78,79,81116,118,120195,198,198回收率(%)97.50%，98.75,101.25%96.67,98.33%，100.00%97.50%，99.00%，99.00%896.67%～101.250%3.精密度和準(zhǔn)確度試驗(yàn)變色酸光度法31（0.2000g（40.0μg/mL3mL99?？梢钥闯霰痉椒ǖ木芏群蜏?zhǔn)確度均較好。表9 精密度和準(zhǔn)確度試驗(yàn)（變色酸光度法）編號(hào) 標(biāo)準(zhǔn)值/% 測(cè)定值（9次）/% 平均值/% 極差

/%

相對(duì)標(biāo)準(zhǔn)偏差/%0.1820.1810.18297TR430240.1850.1850.1830.1830.1840.0050.0020.990.1840.1860.1860.4900.4950.486GSB03-2202-20080.490.4910.4910.4920.4900.0100.0040.720.4950.4850.4881.301.331.3221NR430031.321.331.291.301.3080.0400.0161.201.291.311.302.512.502.56鈮鐵-10#2.522.492.492.552.5120.0700.0261.032.512.492.511#試樣

0.518 0.518 0.510 0.520 0.520 0.510

0.513 0.015 0.006 1.08二安替比林甲烷光度法31（0.2000g（40.0μg/mL3mL1910。可以看出本方法的精密度和準(zhǔn)確度均較好。表10 精密度和準(zhǔn)確度試驗(yàn)（二安替比林甲烷光度法）編號(hào) 標(biāo)準(zhǔn)值/% 測(cè)定值（9次）/% 平均值/% 極差

/%0.494/%0.4940.4820.480GSB03-2202-20080.490.4950.4950.4920.4890.0150.0061.110.4880.4880.4880.8750.8700.880GBW(E)0104140.870.8900.8900.8680.8760.0220.0091.010.8700.8680.8721.331.311.3121NR430031.321.291.291.311.310.0400.0120.941.311.311.302.522.562.50鈮鐵-10#2.522.492.492.552.520.0700.0250.982.512.522.530.5120.5060.5201#試樣―0.5160.5120.5100.5130.0140.0040.830.5100.5160.516

相對(duì)標(biāo)準(zhǔn)偏差七、方法精密度的制定鋼鐵集團(tuán)有限責(zé)任公司、中信錦州金屬股份有限公司等88GB/T6379.1（草案位或4位有效數(shù)字。精密度試驗(yàn)的統(tǒng)計(jì)計(jì)算按GB/T6379.2－2004（ISO5725－2:1994）《測(cè)量（正確度與精密度2再現(xiàn)性的基本方法》推薦的統(tǒng)計(jì)方法進(jìn)行。Cochran（精度）Grubbs法檢驗(yàn)實(shí)驗(yàn)室單元平均值的一致性，確定是否有rr，R12～19。表11實(shí)驗(yàn)室名稱(chēng)及編號(hào)實(shí)驗(yàn)室編號(hào) 實(shí)驗(yàn)室名稱(chēng)武鋼集團(tuán)昆明鋼鐵股份有限公司柳州鋼鐵股份有限公司酒泉鋼鐵集團(tuán)有限責(zé)任公司本溪鋼鐵（集團(tuán)）有限責(zé)任公司技術(shù)中心理化檢測(cè)所三明鋼鐵中信錦州金屬股份有限公司包頭稀土研究院北京科大分析檢驗(yàn)中心有限公司原始數(shù)據(jù)鈦測(cè)定原始數(shù)據(jù)見(jiàn)表12、表13，含量以質(zhì)量分?jǐn)?shù)（w/%）表示。變色酸光度法123123456780.1821.310.5600.2940.8800.7790.5190.47810.1791.300.5680.2910.8780.7670.5260.4830.1861.330.5710.2890.8710.7710.5130.4920.1821.3040.5450.2860.8830.7950.5140.49120.1831.3180.5480.3040.8860.7900.5170.4990.1811.3080.5580.2920.8890.7810.5220.5040.1901.260.5570.2950.8750.8050.5280.47330.1821.290.5390.2840.8960.7930.5350.4740.1871.300.5470.2960.9050.8120.5130.46240.1821.290.5500.2880.8700.7980.5220.4880.1811.320.5480.2870.8710.7800.5240.486

表12原始數(shù)據(jù)：鈮鐵中鈦的含量（變色酸光度法）水平j(luò)0.1801.290.5500.2880.8680.7820.5240.4860.1841.330.5600.2960.8750.7860.5130.48350.1841.310.5620.2980.8660.7900.5230.4910.1851.330.5760.2850.8790.7750.5170.4980.1741.300.5460.2980.8730.7810.5270.50060.1761.290.5430.2880.8650.7820.5150.5040.1771.300.5500.2860.8620.7790.5170.4910.1771.3510.5500.2930.8610.7500.5020.47670.1751.3530.5290.2980.8740.7570.5210.4720.1721.3410.5300.3040.8550.7670.5130.4820.1851.280.560.2990.8600.7690.5280.47580.1851.270.5880.2950.8720.7720.5270.4790.1831.290.5850.3000.8660.7750.5250.482二安替比林甲烷光度法表13原始數(shù)據(jù)：鈮鐵中鈦的含量（二安替比林甲烷光度法）實(shí)驗(yàn)室ji123456780.1811.320.5610.2870.8730.7740.5240.48810.1851.310.5650.2910.8760.7690.5300.4890.1811.320.5590.2850.8730.7780.5220.4880.1881.3450.5620.2750.9040.7950.5140.47320.1881.3280.5560.2880.8840.7980.5280.5060.1901.3310.5700.2850.8960.7910.5080.4850.1751.300.5380.2780.9020.7850.5320.49230.1761.340.5540.2890.8780.8090.5360.4820.1811.320.5490.2850.8720.7980.5220.4900.1821.340.5380.2890.8900.7800.5000.49140.1811.300.5400.2890.8830.7910.5200.4650.1831.330.5420.2880.8610.7800.5200.4850.1841.310.5590.2970.8660.7690.5220.48550.1841.330.5650.2950.8730.7810.5160.4880.1851.310.5740.2880.8780.7860.5270.4960.1801.290.5400.2830.8740.7740.5140.48160.1791.290.5410.2850.8640.7780.5250.4800.1811.300.5500.2890.8690.7770.5140.4860.1861.3350.5590.2980.8690.7790.5310.49270.1861.3370.5440.3080.8840.7800.5360.4980.1901.3320.5430.2990.8750.7840.5230.5000.1831.320.5630.2950.8740.7790.5270.50380.1841.310.5550.2980.8750.7770.5170.4970.1831.350.5620.2960.8620.7770.5170.500CochranSr1415。變色酸光度法表14鈦單元方差檢驗(yàn)和r值計(jì)算（變色酸光度法）水平j(luò)實(shí)驗(yàn)室i1234567810.0040.0150.0060.0030.0050.0060.0070.00720.0010.0070.0070.0090.0030.0070.0040.00730.0040.0210.0090.0070.0150.0100.0110.00740.0010.0170.0010.0010.0020.0100.0010.00150.0010.0120.0090.0070.0070.0080.0050.00860.0020.0060.0040.0060.0060.0020.0060.00770.0030.0060.0120.0060.0100.0090.0100.00580.0010.0100.0150.0030.0060.0030.0020.004平方和0.0000410.0013270.0006260.0002630.0004780.0004220.0003460.000277均方0.0000050.0001660.0000780.0000330.0000600.0000530.0000430.000035MAX0.0040.0210.0150.0090.0150.0100.0110.008柯克倫統(tǒng)計(jì)量C0.3980.3270.3770.3200.4960.2310.3650.203Sr0.00230.01290.00880.00570.00770.00730.00660.0059r0.00640.03640.02500.01620.02190.02050.01860.0167當(dāng)n=3,P=8時(shí)，柯克倫檢驗(yàn)5%臨界值為0.516；1%臨界值為0.615。二安替比林甲烷光度法表15鈦單元方差檢驗(yàn)和r值計(jì)算（二安替比林甲烷光度法）水平j(luò)實(shí)驗(yàn)室i1234567810.0020.0060.0030.0030.0020.0050.0040.00120.0010.0090.0070.0070.0100.0040.0100.01730.0030.0200.0080.0060.0160.0120.0070.00540.0010.0210.0020.0010.0150.0060.0120.01450.0010.0120.0080.0050.0060.0090.0060.00660.0010.0060.0060.0030.0050.0020.0060.00370.0020.0030.0090.0060.0080.0030.0070.00480.0010.0210.0040.0020.0070.0010.0060.003平方和 0.000025 0.0015550.0003160.0001510.0007560.0003060.0004550.000562均方 0.000003 0.0001940.0000400.0000190.0000950.0000380.0000570.000070MAX0.0030.0210.0090.0070.0160.0120.0120.017柯克倫統(tǒng)計(jì)量C0.4130.2790.2540.3060.3330.4710.2930.497Sr0.00180.01390.00630.00430.00970.00620.00750.0084r0.00500.03940.01780.01230.02750.01750.02130.0237當(dāng)n=3,P=8時(shí)，柯克倫檢驗(yàn)5%臨界值為0.516；1%臨界值為0.615。GrubbsSR1617。變色酸光度法1231234567810.1821.3130.5660.2910.8760.7720.5190.48420.1821.3100.5500.2940.8860.7890.5180.49830.1861.2830.5480.2920.8920.8030.5250.47040.1811.3000.5490.2880.8700.7870.5230.48750.1841.3230.5660.2930.8730.7840.5180.49160.1761.2970.5460.2910.8670.7810.5200.49870.1751.3480.5360.2980.8630.7580.5120.47780.1841.2800.5780.2980.8660.7720.5270.479總體均值m0.1811.3070.5550.2930.8740.7810.5200.485實(shí)驗(yàn)室間標(biāo)準(zhǔn)差s0.004160.022260.013600.003640.010170.013530.004770.01018Gmax（單個(gè)）1.201.861.671.441.751.681.351.27Gmin（單個(gè)）1.601.211.371.491.071.681.721.54Gmax（兩個(gè)）0.63120.26530.35500.25710.16470.42670.43220.3986Gmin（兩個(gè)）0.15860.50990.57660.55870.66270.41260.41480.4185SL21.559E-054.403E-041.588E-042.317E-068.353E-051.654E-048.298E-069.211E-05SR0.00460.02460.01540.00590.01200.01480.00720.0113R0.01290.06960.04350.01680.03380.04180.02030.0318

表16 鈦平均值一致性檢驗(yàn)和R值計(jì)算（變色酸光度法）水平j(luò)格拉布斯檢驗(yàn)臨界值：P=81%點(diǎn)：2.2745%點(diǎn)：2.126。P=81%點(diǎn)：0.05635%點(diǎn)：0.1101。二安替比林甲烷光度法

17R（二安替比林甲烷光度法）水平j(luò)1 2 3 4 5 6 7 810.1821.3170.5620.2880.8740.7740.5250.48820.1891.3350.5630.2830.8950.7950.5170.48830.1771.3200.5470.2840.8840.7970.5300.48840.1821.3230.5400.2890.8780.7840.5130.48050.1841.3170.5660.2930.8720.7790.5220.49060.1801.2930.5440.2860.8690.7760.5180.48270.1871.3350.5490.3020.8760.7810.5300.49780.1831.3270.5600.2960.8700.7780.5200.500總體均值m0.1831.3210.5540.2900.8770.7830.5220.489實(shí)驗(yàn)室間標(biāo)準(zhǔn)差s0.003690.013170.009950.006580.008470.008660.006140.00657Gmax（單個(gè)）1.491.061.231.772.051.671.321.65Gmin（單個(gè)）1.582.081.381.110.981.061.391.34Gmax（兩個(gè)）0.33570.57480.55790.24050.11580.11760.33370.2396Gmin（兩個(gè)）0.39490.27330.44800.60610.68920.67800.50190.