1鈮礦石鉭礦石化學(xué)分析方法體光譜法(報(bào)批稿)編制說明標(biāo)準(zhǔn)起草單位：國家地質(zhì)實(shí)驗(yàn)測試中心二〇二二年九月2目錄第一章工作簡況 1 第二章標(biāo)準(zhǔn)編制原則和確定標(biāo)準(zhǔn)主要內(nèi)容的依據(jù) 7 第三章主要試驗(yàn)的分析綜述報(bào)告及技術(shù)經(jīng)濟(jì)論證 10 1第一章工作簡況節(jié)任務(wù)來源第二節(jié)編制過程檢測相關(guān)的標(biāo)準(zhǔn)和文獻(xiàn)資料，明確了本標(biāo)準(zhǔn)制定的主要問題、2氧化鈣、氧化鎂、氧化鉀、氧化鈉、二氧化鈦、氧化錳、3。進(jìn)行方法精密度協(xié)作試驗(yàn)。求意見稿。段4修改完善。4.審查階段術(shù)委員會(huì)勘查技術(shù)與實(shí)驗(yàn)測試分技術(shù)委員會(huì)組織實(shí)驗(yàn)測試技術(shù)專家上報(bào)。5三節(jié)主要編制人員號(hào)準(zhǔn)的具體貢獻(xiàn)1的2協(xié)助實(shí)驗(yàn)研究，有關(guān)標(biāo)3475標(biāo)準(zhǔn)溶液、監(jiān)控溶液的6789計(jì)書，標(biāo)準(zhǔn)文寫和修改數(shù)據(jù)統(tǒng)計(jì)6第四節(jié)參加方法精密度協(xié)作試驗(yàn)單位參加方法精密度協(xié)作試驗(yàn)的有10家單位(見表2)，代表著均測試水平1234所5試應(yīng)用研究所6789產(chǎn)研究所查研究院7第二章標(biāo)準(zhǔn)編制原則和確定標(biāo)準(zhǔn)主要內(nèi)容的依據(jù)第一節(jié)標(biāo)準(zhǔn)編制的主要原則則。第二節(jié)確定標(biāo)準(zhǔn)主要內(nèi)容的依據(jù)標(biāo)準(zhǔn)方法的整體結(jié)構(gòu)和內(nèi)容編寫方法國家標(biāo)準(zhǔn)有統(tǒng)一要求和規(guī)T標(biāo)準(zhǔn)》等國家標(biāo)準(zhǔn)進(jìn)行編寫，盡量做到編寫的標(biāo)準(zhǔn)合乎規(guī)范。關(guān)的條件試驗(yàn)來確定的。本標(biāo)準(zhǔn)的主要技術(shù)指標(biāo)包括方法檢出限、測定范圍(方法定量限~方法測定上限)、精密度、正確度等。1、方法檢出限應(yīng)該是指特定分析方法中，分析物能夠被識(shí)別和82、方法定量限(測定范圍下限)是指特定分析方法中，分析物3、方法測定范圍上限一般是通過用相當(dāng)于樣品溶液中分析物濃規(guī)含量確定的?？倓t與定義》的要求，含量水平m之間的函數(shù)關(guān)系式。正確度是依據(jù)GB/T6379.4—20049算出測量方法的偏倚δ。第三章主要試驗(yàn)(或驗(yàn)證試驗(yàn))的分析綜述報(bào)告及技術(shù)經(jīng)濟(jì)論證第一節(jié)概述鉭鈮屬難熔稀有金屬,它們的物理化學(xué)性質(zhì)很相似,在自然界中能力強(qiáng)，具有超導(dǎo)性能等一系列特性。至是環(huán)境污染(如放射性元素鈾)。而具有靈敏度高、精密度好、具ESMS在已經(jīng)成為比較成熟的測試方法。所以建立鈮鉭礦多金屬礦的ICP-AES/ICP-MS分析技術(shù)方法一方面加快鉭鈮礦石的分析速度，從而縮而提高鉭鈮礦石的經(jīng)濟(jì)利用價(jià)值。目前，對(duì)鈮鉭礦石分析通常采用傳統(tǒng)化學(xué)分析方法，如GB/TT (鈮0.0010%~1.0％；鉭0.0050％~1.0％)。鈮鉭礦分析中，由于Nb2O5+14HF?2[NbF7]2-+5H2O+4H+2[Nb(OH)7]2-+4H+2[NbF7]2-+5H2O??[Nb(OH)7]2-+H++F-耦合等離子體光譜法，適合高低不同品位鈮鉭礦(0.0xx%~xx%)第二節(jié)樣品前處理?xiàng)l件實(shí)驗(yàn)2酸用量實(shí)驗(yàn) GBW07185樣品5.0mL氫氟酸+1.0mL硝酸2.0mL氫氟酸+1.0mL硝酸1.5mL氫氟酸+1.0mL硝酸NbTaNbTaNbTa3次分次測定值379285963733831337338513(μg/g)353988033767851837678518370187343665853536658563測定平均值(μg/g)367787113722845537228531標(biāo)準(zhǔn)值(μg/g)3635±708353±1643635±708353±1643635±708353±164RSD(%)3.480.32相對(duì)誤差(%)4.292.382.382.133稱樣量的影響(mg)Nb2OTa2O5(μg/g)(μg/g)(μg/g)(μg/g)00第三節(jié)樣品測定條件實(shí)驗(yàn)儀器及主要工作參數(shù)Optima8300電感耦合等離子體發(fā)射光譜儀(美國PerkinElmer公司)，采用同心霧化器及旋流霧室，耐氫氟酸系統(tǒng)。儀器工作參數(shù)2標(biāo)準(zhǔn)溶液和主要試劑氟酸介質(zhì))單元素標(biāo)準(zhǔn)儲(chǔ)備溶液(中國計(jì)量科學(xué)研究院)。蒸餾水：經(jīng)Mili-Q離子交換純化系統(tǒng)純化，電阻率達(dá)到硝酸(1.42g/mL)，氫氟酸(1.16g/mL)。3光譜干擾、背景影響及扣除選擇ICPAES基體效應(yīng)。第四節(jié)方法檢出限和測定范圍L質(zhì))配制濃度為0~100μg/mL的鈮鉭混合校準(zhǔn)溶液。根據(jù)測定樣品含W(mg/L)Nb(mg/L)1酸溶液2酸溶液300酸溶液4酸溶液50.0酸溶液6.0酸溶液7酸溶液2方法檢出限269.706292.781309.418Ta233.198Ta240.063W224.876W239.708BK11.6041.4761.3646.5061.3540.182BK21.026-0.1881.1226.2140.192.636-0.328BK3-0.190.2621.958-0.1-0.956BK41.5260.794-0.1765.092-0.2562.142BK50.3460.872-0.822-0.174-0.1062.104-0.596BK60.8220.866-0.552.70.3061.314BK70.0560.8042.8860.106-0.064-0.478BK80.9740.338-0.0140.038-0.2840.9560.32BK90.4680.690.5540.2621.602-0.756BK100.590.8561.892-0.7661.122BK110.5480.3540.4244.0661.3160.526SD0.40.70.82.40.80.83*SD2.22.47.12.44.32.410*SD成分方法檢出限μg/g測定范圍%鈮230.008~5.0鉭440.015~10.0鎢0.004~1.0方法檢出限是用該方法分解11份GBW07155鉭礦石標(biāo)準(zhǔn)物質(zhì)溶液測定結(jié)果的3倍標(biāo)準(zhǔn)偏倍數(shù)條件下的計(jì)算求得，測定下限是用該方法分解11份GBW07155鉭礦石標(biāo)準(zhǔn)物質(zhì)溶液測定結(jié)果的10倍標(biāo)準(zhǔn)偏差，在1000稀釋倍數(shù)條件下的計(jì)算求得是第五節(jié)方法精密度和準(zhǔn)確度269.706292.781309.418Ta233.198Ta240.063W224.876W239.708GBW07155-1337.0330.9333.9561.1581.6193.5202.6GBW07155-2325.5318.7337.5578.3578.3190.4206.5GBW07155-3318.4310.8327553.8559.8192.1204.3GBW07155-4311.5303.6317.3544.9550195.3198.8GBW07155-5327.6319.6329.9564.5571.2196.9200.9GBW07155-6328.1320.6338.4576.6585193.7209GBW07155-7317.0313.0331.2566.4557.6190.5198.2GBW07155-8304.3299.9315.5542.8539.3187.2197.8GBW07155-9319.5313.4326.5557.7554.2192.6193.7GBW07155-10320.6315.3336.5565.2567194.8200.7GBW07155-11313.3308.7327.4546.7549192.6200.5推薦值300.6+20.9573.0+49.1200.0+20均值319314329561564201SD9.969.687.6012.0214.802.674.293*SD29.8829.0422.836.0644.48.0112.87RSD(%)3.123.082.312.142.632.13RE(%)6.004.479.51-2.11-3.350.54Nb2O5DDGBW630±30GBW04節(jié)實(shí)際樣品的測定g融鐘，視沉淀情況補(bǔ)加硅酸鈉溶液，放置過夜。過濾溶液，bTa-1本方法平均值(%)(n=3)堿熔法的測定值(%)RSDRE.72Ta-2本方法平均值(%)(n=3)堿熔法的測定值(%)RSDRE第七節(jié)方法協(xié)作驗(yàn)證試驗(yàn)及數(shù)據(jù)統(tǒng)計(jì)1方法協(xié)作試驗(yàn)樣品的選擇在現(xiàn)有的鈮鉭礦石的國家標(biāo)準(zhǔn)物質(zhì)非常少，只有GBW07154，銅、鋅、鈮、鉭元素量的測定封閉酸溶-電感耦合等離子體質(zhì)譜。因此，精密度協(xié)作試驗(yàn)樣品的選擇，首先考慮從現(xiàn)有較高的礦石標(biāo)準(zhǔn)物質(zhì)中通過分析篩選出有一定濃度分布的標(biāo)準(zhǔn)物質(zhì)，通過分析確定了現(xiàn)有的鉭礦石標(biāo)準(zhǔn)物質(zhì)GBW07155、GBW85。從方法的使用范圍考慮，宜春鈮鉭礦區(qū)采集的鈮鉭礦NT1-2，以及鈮鉭精礦和巖石樣品標(biāo)準(zhǔn)物質(zhì)配制了2件鈮鉭礦石的混合樣品NT1-4、NT1-5。用于做測定方法精密度協(xié)作試驗(yàn)的樣品相關(guān)見表11。表11精密度協(xié)作試驗(yàn)樣品Nb、Ta、W的質(zhì)量分?jǐn)?shù)成分試驗(yàn)樣品GBW07155NT1-2GBW07185NT1-4NT1-5w(Nb)/10-21299aw(W)/10-2933694試驗(yàn)樣品均勻性檢驗(yàn)方6MS1=i=1/(10-1)MS1=i=1/(10-1)62(xij?xi)2MS2=i=1j=1/(20-10) 式中：xi—組內(nèi)平均值，x—總平均值。W2123456789(X)minmax偏差(S).39.8差(RSD%)70311F實(shí)測值F.01(v1,v2)949494F.05(v1,v2)bb07419W21650838825219390345642582924864919259099608899656188793843678929619639913399293(X)9362min33978max偏差(S)692差(RSD%)939082.9953192.09F實(shí)測值F.01(v1,v2)949494F.05(v1,v2)bb91W2123456789(X)minmax偏差(S)差1差.02差27950F實(shí)測值F.01(v1,v2)949494F.05(v1,v2)bb3方法協(xié)作試驗(yàn)數(shù)據(jù)統(tǒng)計(jì)分析按照“確定標(biāo)準(zhǔn)方法重復(fù)性與再現(xiàn)性的基本方法”標(biāo)準(zhǔn)的要求，~表17。表15鈮(Nb)精密度協(xié)作實(shí)驗(yàn)原始數(shù)據(jù)表GBW07155NT2-2GBW07185NT2-4NT2-510.0320.0740.352.953.620.0330.0730.372.943.610.0320.0730.382.993.530.0320.0710.373.003.5120.0330.0760.352.903.730.0300.0710.342.953.840.0320.0730.362.933.870.0320.0720.372.873.7530.0310.0760.373.123.810.0320.0730.383.023.800.0320.0730.363.013.760.0320.0730.363.033.7640.0330.0750.402.973.960.0330.0730.402.883.960.0340.0750.392.904.020.0330.0730.392.933.8350.0310.0680.372.963.710.0320.0680.372.973.710.0320.0700.373.013.720.0320.0720.363.083.8060.0320.0630.352.803.590.0320.0590.352.833.630.0300.0610.372.823.470.0310.0620.342.803.6870.029*0.0670.342.813.730.027*0.0680.342.833.710.029*0.0670.342.833.710.028*0.0670.352.803.6380.0300.0660.363.103.980.0300.0660.363.113.950.0300.0650.363.104.000.0310.0650.363.163.9890.0330.0740.363.023.780.0330.0740.363.023.750.0330.0740.363.023.800.0330.0740.363.063.780.0320.0720.362.973.740.0310.0720.372.973.700.0320.0730.362.983.640.0320.0710.382.963.56Nb協(xié)作試驗(yàn)數(shù)據(jù)統(tǒng)計(jì)表GBW07155NT2-2GBW07185NT2-4NT2-544444參加實(shí)驗(yàn)室數(shù)p可接受實(shí)驗(yàn)室數(shù)p總平均值(y?)60重復(fù)性變異系數(shù)(%)9410再現(xiàn)性變異系數(shù)(%)γ=SR/Sr71///A///A*SR///測量方法偏倚(δ)/////////標(biāo)準(zhǔn)值(μ)//////表16鉭(Ta)精密度協(xié)作實(shí)驗(yàn)原始數(shù)據(jù)表GBW07155NT2-2GBW07185NT2-4NT2-510.0540.1690.835.957.210.0580.1600.855.957.170.0560.1570.856.037.030.0560.1520.866.086.960.0510.1390.74**6.9420.0480.1510.72**5.307.290.0490.1560.76**5.237.010.0500.1480.79**5.166.9030.0550.1750.845.186.500.0570.1690.845.286.550.0570.1670.835.236.500.0560.1720.835.256.5340.0530.1640.835.507.400.0530.1610.845.357.430.0530.1690.835.397.520.0540.1650.845.437.4450.0560.1680.855.616.910.0590.1710.835.636.880.0580.1670.855.606.890.0550.1690.855.607.0260.0580.1760.845.817.370.0570.1780.825.627.030.0560.1760.845.797.280.0560.1800.835.757.5470.0530.1440.835.667.410.0490.1440.835.647.420.0480.1490.825.667.520.0510.1470.825.607.4380.0580.1670.886.288.040.0580.1680.866.318.060.0580.1670.876.248.070.0580.1650.886.298.0490.0510.1620.836.247.510.0510.1630.846.217.420.0510.1640.836.207.380.0510.1630.826.217.240.0560.1630.835.767.260.0600.1610.845.847.110.0580.1660.845.827.210.0580.1650.865.656.97表16-1鉭(Ta)準(zhǔn)確度協(xié)作試驗(yàn)數(shù)據(jù)統(tǒng)計(jì)表GBW07155NT2-2GBW07185NT2-4NT2-544444參加實(shí)驗(yàn)室數(shù)p可接受實(shí)驗(yàn)室數(shù)p9總平均值(y?)重復(fù)性變異系數(shù)(%)7038再現(xiàn)性變異系數(shù)(%)99γ=SR/Sr///A///A*SR///測量方法偏倚(δ)//////0///標(biāo)準(zhǔn)值(μ)//////表17鎢(W)精密度協(xié)作實(shí)驗(yàn)原始數(shù)據(jù)表GBW07155NT2-2GBW07185NT2-4NT2-5153622.429034253820.929234253322.829233352721.92993312476---298362483---296368490---297364472---299365352940.032435151741.132634651044.032037352142.0326352452737.429137651240.428538950437.028838651735.6296362553421.3**29535953324.5**28936953129.4**29837851226.9**301389648940.128436820147541.827933920448742.727532920249742.0285338755226.829035855427.229136855228.428737055627.5289367822461031.533033822661131.633134022461231.632834222660931.73283439475307370475303373475309378474301372539---311351541---298369563---293369552---301346W試驗(yàn)數(shù)據(jù)統(tǒng)計(jì)表GBW07155NT2-2GBW07185NT2-4NT2-544444參加實(shí)驗(yàn)室數(shù)p可接受實(shí)驗(yàn)室數(shù)p78.500數(shù)(%)68930.28(%)511546.4350γ=SR/Sr///A///ASR///測量方法偏倚(δ)/////////標(biāo)準(zhǔn)值(μ).0/40///.60//和格拉布斯(Grubbs)檢驗(yàn)剔除離群值，保留歧離值。再用檢驗(yàn)合格的數(shù)據(jù)計(jì)算重復(fù)性方差(Sr)和再現(xiàn)性方差(SR)，建立精密度值(重素水平范圍m鈮r＝0.0003＋0.056m鉭r＝0.002+0.032mR0.005＋