《銀粉中鐵、鈣、鎂、鋁、銅、錳、鈦、鋯、硼、磷、硅、鉍、鉛、鋅、鉀和鈉含量的測定電感耦合等離子體發(fā)射光譜法》編制說明1工作簡況1.1任務(wù)來源根據(jù)2024年5月寧夏材料研究學(xué)會下發(fā)的寧材學(xué)字[2024]8號“關(guān)于2024年第一批《鈹鋁鑄件工業(yè)計算機(jī)層析成像（CT）檢測方法》等8項(xiàng)團(tuán)體標(biāo)準(zhǔn)立項(xiàng)的通知”要求，團(tuán)體標(biāo)準(zhǔn)《銀粉中鐵、鈣、鎂、鋁、銅、錳、鈦、鋯、硼、磷、硅、鉍、鉛、鋅、鉀和鈉含量的測定電感耦合等離子體發(fā)射光譜法》由寧夏材料研究學(xué)會歸口，計劃編號為：T/NXCL2024003。主要起草單位為：西北稀有金屬材料研究院寧夏有限公司、寧夏中色新材料有限公司、寧夏東方鉭業(yè)股份有限公司。1.2項(xiàng)目背景銀粉是一種由銀或銀合金制成的顆粒狀功能性粉末材料，以優(yōu)良的導(dǎo)熱導(dǎo)電性能，在電氣和電子工業(yè)領(lǐng)域有著非常廣泛的應(yīng)用，是電接觸、電阻、耐溫等材料不可缺少的部分。同時以其抑菌性和光學(xué)性能，在能源、醫(yī)療等方面都特別的應(yīng)用價值。在銀粉的化學(xué)分析檢測要求中，一般情況下較多關(guān)注的是銀粉的純度，以控制制備工藝鐵、鈣、鎂、鋁、銅、錳等雜質(zhì)元素帶來的后續(xù)產(chǎn)品性能影響，以及工藝改進(jìn)等。隨著太陽能產(chǎn)業(yè)的興起，銀粉作為太陽能電池正極導(dǎo)電銀漿最關(guān)鍵材料，經(jīng)常需要混合玻璃粉，組成較復(fù)雜的鉛、鉍、鋅等金屬氧化物以及硼、硅等非金屬氧化物體系，以滿足質(zhì)量導(dǎo)體的最終性能體現(xiàn)。產(chǎn)品多元化需求造成各添加元素量的不確定性，對銀粉的分析檢測能力與工作效率，以及質(zhì)量控制體系整體提升帶來迫切要求。因此，開發(fā)一種準(zhǔn)確、簡便的測定方法，實(shí)現(xiàn)銀粉中各元素快速定量分析非常必要。目前國內(nèi)尚無銀粉中鐵、鈣、鎂、鋁、銅、錳、鈦、鋯、硼、磷、硅、鉍、鉛、鋅、鉀和鈉量的化學(xué)分析方法標(biāo)準(zhǔn)。本文件建立電感耦合等離子體發(fā)射光譜法直接測定銀粉中鐵、鈣、鎂、鋁、銅、錳、鈦、鋯、硼、磷、硅、鉍、鉛、鋅、鉀和鈉含量的分析方法，綜合生產(chǎn)需求與檢測效率因素，保障銀粉成分分析數(shù)據(jù)有效性，為產(chǎn)品質(zhì)量控制、性能改進(jìn)以及新品研發(fā)提供有力支撐。本文件包含方法原理、所用試劑、儀器設(shè)備、試驗(yàn)步驟、試驗(yàn)數(shù)據(jù)處理和精密度要求等。1.3主要參加單位和工作成員及其所做的工作本標(biāo)準(zhǔn)起草單位為：西北稀有金屬材料研究院寧夏有限公司、寧夏中色新材料有限公司、寧夏東方鉭業(yè)股份有限公司。其中，西北稀有金屬材料研究院寧夏有限公司主要負(fù)責(zé)試驗(yàn)方案制定，試驗(yàn)樣品收集和分發(fā)，分析方法研究，試驗(yàn)結(jié)果處理，標(biāo)準(zhǔn)文本、試驗(yàn)報告和編制說明撰寫等工作；寧夏中色新材料有限公司為一驗(yàn)單位，主要負(fù)責(zé)對試驗(yàn)方案中的條件實(shí)驗(yàn)進(jìn)行驗(yàn)證，提供精密度和準(zhǔn)確度測試數(shù)據(jù)，以及對方法提出建議；寧夏東方鉭業(yè)股份有限公司為二驗(yàn)單位，主要負(fù)責(zé)提供精密度試驗(yàn)數(shù)據(jù)，并對標(biāo)準(zhǔn)文本提出修改意見和建議。標(biāo)準(zhǔn)牽頭單位西北稀有金屬材料研究院寧夏有限公司是國內(nèi)唯一的鈹材研究和生產(chǎn)基地，國家高新技術(shù)企業(yè)，建有稀有金屬特種材料國家重點(diǎn)實(shí)驗(yàn)室。公司分析檢測所主持及參與多項(xiàng)鈹、鈹鋁合金、銅鈹合金、銻鈹芯塊等國家軍用標(biāo)準(zhǔn)和行業(yè)標(biāo)準(zhǔn)制修訂工作。寧夏中色新材料有限公司是一家從事稀有稀土金屬壓延加工、有色金屬壓延加工、有色金屬合金制造等業(yè)務(wù)的公司，公司經(jīng)營范圍還包括有色金屬合金銷售、高性能有色金屬及合金材料銷售、有色金屬鑄造、新材料技術(shù)研發(fā)、電子專用材料研發(fā)、金屬切削加工服務(wù)、金屬制品修理等。在本次修訂中，反饋產(chǎn)品使用情況及方法檢測需求信息，同時作為第一驗(yàn)證單位，提供實(shí)驗(yàn)樣本的準(zhǔn)確度驗(yàn)證及精密度數(shù)據(jù)。寧夏東方鉭業(yè)股份有限公司是中色（寧夏）東方集團(tuán)有限公司下屬控股子公司，是中國有色礦業(yè)集團(tuán)有限公司成員單位。公司主要從事稀有金屬鉭、鈮、鈦及其合金等高技術(shù)產(chǎn)品的研發(fā)、生產(chǎn)、銷售和進(jìn)出口業(yè)務(wù)，產(chǎn)品廣泛應(yīng)用于電子、通訊、航空、航天、冶金、石油、化工、體育、醫(yī)療、原子能、太陽能等領(lǐng)域。在本次修訂過程中，提供實(shí)驗(yàn)樣本的精密度數(shù)據(jù)，并對標(biāo)準(zhǔn)文件等提出了相應(yīng)的修改意見。本文件主要起草人：白英麗、李暉、王巧、張健康、馬肖、王佳麗、張靜、殷藝丹、秦雅男、李娜。各起草人在本文件編制過程中的工作職責(zé)見表1。表1工作成員及所做工作起草人所做工作白英麗、李暉、王巧、王佳麗、殷藝丹、秦雅男、李娜負(fù)責(zé)樣品搜集、試驗(yàn)方案的確定、條件試驗(yàn)實(shí)施、樣品測試、方法驗(yàn)證，標(biāo)準(zhǔn)文件和編制說明編寫等。張健康標(biāo)準(zhǔn)修訂工作的整體統(tǒng)籌及指導(dǎo)，技術(shù)性修改建議、標(biāo)準(zhǔn)技術(shù)內(nèi)容審核、試驗(yàn)進(jìn)度組織協(xié)調(diào)等。馬肖、張靜標(biāo)準(zhǔn)文件和編制說明修改建議、方法試驗(yàn)驗(yàn)證等。1.4主要工作過程西北稀有金屬材料研究院寧夏有限公司在現(xiàn)有設(shè)備、人員、技術(shù)的基礎(chǔ)上，加上對客戶需求的了解，成立了團(tuán)體標(biāo)準(zhǔn)編制組，召開了標(biāo)準(zhǔn)項(xiàng)目編制啟動會議，對標(biāo)準(zhǔn)編寫工作進(jìn)行了部署和分工，主要工作過程經(jīng)歷了以下幾個階段。1.4.1立項(xiàng)階段2024年4月，西北稀有金屬材料研究院寧夏有限公司向?qū)幭牟牧涎芯繉W(xué)會提交了《銀粉中鐵、鈣、鎂、鋁、銅、錳、鈦、鋯、硼、磷、硅、鉍、鉛、鋅、鉀和鈉含量的測定電感耦合等離子體發(fā)射光譜法》團(tuán)體標(biāo)準(zhǔn)制訂的項(xiàng)目建議書、標(biāo)準(zhǔn)草案等材料。寧夏材料研究學(xué)會組織專家根據(jù)寧材學(xué)字[2024]04號《2024年度團(tuán)體標(biāo)準(zhǔn)立項(xiàng)征集的公告》材料申報要求進(jìn)行評審立項(xiàng)。2024年5月16日，寧夏材料研究學(xué)會發(fā)布了《關(guān)于2024年第一批《鈹鋁鑄件工業(yè)計算機(jī)層析成像（CT）檢測方法》等8項(xiàng)團(tuán)體標(biāo)準(zhǔn)立項(xiàng)的通知》（寧材學(xué)字[2024]8號），正式下達(dá)該團(tuán)體標(biāo)準(zhǔn)的制訂任務(wù)，標(biāo)準(zhǔn)名稱為《銀粉中鐵、鈣、鎂、鋁、銅、錳、鈦、鋯、硼、磷、硅、鉍、鉛、鋅、鉀和鈉含量的測定電感耦合等離子體發(fā)射光譜法》，項(xiàng)目計劃編號為T/NXCL2024003，完成年限為2024年12月，技術(shù)歸口單位為寧夏材料研究學(xué)會。1.4.2起草階段1）2024年5月中旬，成立了《銀粉中鐵、鈣、鎂、鋁、銅、錳、鈦、鋯、硼、磷、硅、鉍、鉛、鋅、鉀和鈉含量的測定電感耦合等離子體發(fā)射光譜法》標(biāo)準(zhǔn)編制組，確定了各成員的工作職能和任務(wù)，制定了工作計劃和進(jìn)度安排。2）2024年5月下旬，調(diào)研客戶提出的銀粉中鐵、鈣、鎂、鋁、銅、錳、鈦、鋯、硼、磷、硅、鉍、鉛、鋅、鉀和鈉含量檢測需求，并收集涉及銀粉中鐵、鈣、鎂、鋁、銅、錳、鈦、鋯、硼、磷、硅、鉍、鉛、鋅、鉀和鈉含量的檢測標(biāo)準(zhǔn)，分析不能滿足生產(chǎn)、使用需求的具體點(diǎn)。3）2024年6月上旬，編制組完成銀粉中鐵、鈣、鎂、鋁、銅、錳、鈦、鋯、硼、磷、硅、鉍、鉛、鋅、鉀和鈉含量的各項(xiàng)檢測試驗(yàn)，提交了團(tuán)體標(biāo)準(zhǔn)《銀粉中鐵、鈣、鎂、鋁、銅、錳、鈦、鋯、硼、磷、硅、鉍、鉛、鋅、鉀和鈉含量的測定電感耦合等離子體發(fā)射光譜法》。驗(yàn)證樣品及驗(yàn)證報告交寧夏中色新材料有限公司、寧夏東方鉭業(yè)股份有限公司進(jìn)行驗(yàn)證。1.4.3征求意見階段2025年4月下旬，就《銀粉中鐵、鈣、鎂、鋁、銅、錳、鈦、鋯、硼、磷、硅、鉍、鉛、鋅、鉀和鈉含量的測定電感耦合等離子體發(fā)射光譜法》團(tuán)體標(biāo)準(zhǔn)的標(biāo)準(zhǔn)文本和編制說明，征求寧夏參進(jìn)寧宇達(dá)冶金有限公司、中色（寧夏）東方有限公司特種材料分公司、寧夏大地循環(huán)發(fā)展股份有限公司、?？咸妓兀ㄖ袊┯邢薰镜葐挝坏囊庖姟Ｕ骷浇ㄗh或意見的共25條，詳見標(biāo)準(zhǔn)征求意見稿意見匯總處理表。2025年5月，編制組對征求意見進(jìn)行試驗(yàn)、討論，采納其中20條建議，并補(bǔ)充相應(yīng)的數(shù)據(jù)內(nèi)容，形成了《銀粉中鐵、鈣、鎂、鋁、銅、錳、鈦、鋯、硼、磷、硅、鉍、鉛、鋅、鉀和鈉含量的測定電感耦合等離子體發(fā)射光譜法》送審稿。2標(biāo)準(zhǔn)的編制原則2.1符合性：標(biāo)準(zhǔn)格式嚴(yán)格按照GB/T1.1-2020《標(biāo)準(zhǔn)化工作導(dǎo)則第1部分：標(biāo)準(zhǔn)化文件的結(jié)構(gòu)和起草規(guī)則》、GB/T20001.4-2015《標(biāo)準(zhǔn)編寫規(guī)則第4部分：試驗(yàn)方法標(biāo)準(zhǔn)》等文件的要求編寫，并按照GB/T6379.2-2004《測量方法與結(jié)果的準(zhǔn)確度（正確度與精密度）第2部分：確定標(biāo)準(zhǔn)測試方法重復(fù)性與再現(xiàn)性的基本方法》的要求進(jìn)行試驗(yàn)數(shù)據(jù)的統(tǒng)計及重復(fù)性限和再現(xiàn)性限的計算。2.2合理性：滿足國內(nèi)金屬銀粉中鐵、鈣、鎂、鋁、銅、錳、鈦、鋯、硼、磷、硅、鉍、鉛、鋅、鉀和鈉含量的檢測需要為原則，提高標(biāo)準(zhǔn)的適用性；以與實(shí)際相結(jié)合為原則，提高標(biāo)準(zhǔn)的可操作性；充分考慮國家法律、安全、衛(wèi)生、環(huán)保法規(guī)的要求。2.3先進(jìn)性：本方法操作方便規(guī)范，定義科學(xué)，以實(shí)測為主，準(zhǔn)確度和精密度滿足分析檢測要求，具有先進(jìn)性、可操作性和廣泛的適用性。3標(biāo)準(zhǔn)主要內(nèi)容的確定依據(jù)及主要試驗(yàn)和驗(yàn)證情況分析3.1測定方法的選擇電感耦合等離子體原子發(fā)射光譜法（ICP-AES法）具有分析線性范圍寬、低的檢出限、元素間干擾小、精密度好、儀器操作簡便和分析速度快等優(yōu)點(diǎn)，目前已在分析檢測領(lǐng)域廣泛應(yīng)用。因此本文件采用電感耦合等離子體原子發(fā)射光譜儀測定銀粉中鐵、鈣、鎂、鋁、銅、錳、鈦、鋯、硼、磷、硅、鉍、鉛、鋅、鉀和鈉含量。3.2測定范圍的修訂在制定銀粉中鋁、鉍、鈣、銅、鐵、鎂、錳、鉛、鈦、鋅、鋯、鉀、鈉、硼、磷和硅含量測定范圍時，根據(jù)產(chǎn)品客戶的反饋要求，結(jié)合日常檢測樣品實(shí)際情況，對銀粉中雜質(zhì)元素及添加元素含量測定范圍作了拓展，最終確定出本文件銀粉中鋁、鉍、鈣、銅、鐵、鎂、錳、鉛、鈦、鋅、鋯、鉀、鈉、硼、磷和硅等元素的測定范圍，見表2。表2方法測定范圍測定元素測定范圍％測定元素測定元素％Al0.0010～0.10Fe0.0010～0.10Bi0.0010～5.00Mg0.0010～0.10Ca0.0010～0.10Mn0.0010～0.10Cu0.0010～0.10Pb0.0010～5.00Ti0.0010～0.10Na0.010～0.10Zn0.0010～5.00B0.010～0.10Zr0.0010～0.10P0.010～0.10K0.010～0.10Si0.010～0.103.3樣品預(yù)處理銀粉容易溶于稀或濃硝酸中，本實(shí)驗(yàn)采用濃硝酸溶解后低溫回流除氮，然后稀釋十倍，.樣品在用硝酸溶解時，為保持合適的溶液酸度，對硝酸介質(zhì)體積分?jǐn)?shù)進(jìn)行了試驗(yàn)。配制系列待測元素的混合標(biāo)準(zhǔn)工作溶液，其中鋁、鉍、鈣、銅、鐵、鎂、錳、鉛、鈦、鋅、鋯、鉀、鈉、硼、磷和硅的質(zhì)量濃度均為1.0μg/mL。鉍、鉛、鋅的質(zhì)量濃度均為10.0μg/mL。硝酸介質(zhì)體積分?jǐn)?shù)分別為1%、5%、10%。測定上述溶液，結(jié)果見表3。表3酸度對測定結(jié)果的影響元素理論值μg/mL測定值，μg/mLφ(HNO3)=1%φ(HNO3)=2%φ(HNO3)=3%Al1.001.011.031.04Bi10.0010.0010.0010.00Ca1.001.011.051.1Cu1.000.991.021.03Fe1.001.001.001.00Mg1.001.021.041.02Mn1.001.021.011.04Pb10.0010.009.9810.1Ti1.000.981.010.97Zn10.0010.009.989.99Zr1.000.970.980.96K1.001.001.011.01Na1.001.001.001.02B1.001.000.991.00P1.001.001.000.99Si1.001.001.011.02通過實(shí)驗(yàn)，硝酸介質(zhì)體積分?jǐn)?shù)分別為1%、2%、3%時，對各元素的測定結(jié)果基本無影響，本著節(jié)約和環(huán)保要求，因此本法確定硝酸介質(zhì)體積分?jǐn)?shù)為1%。該酸度對被測元素譜線測定值基本無影響，因此，基體無需酸匹配。3.4分析譜線的選擇按照實(shí)驗(yàn)方法，于電感耦合等離子體原子發(fā)射光譜法對標(biāo)準(zhǔn)溶液系列、各單元素標(biāo)準(zhǔn)溶液（1.0μg/mL）和樣品試液進(jìn)行譜圖掃描，分別選擇待測元素鋁、鉍、鈣、銅、鐵、鎂、錳、鉛、鈦、鋅、鋯、鉀、鈉、硼、磷和硅的2～3條譜線，觀察譜線疊加時的譜圖形狀、峰強(qiáng)度及元素間的干擾，剔除元素之間有相互干擾的譜線，從中選擇靈敏度高，干擾小、信背比大的待測元素分析譜線。根據(jù)上述原則選擇表4中譜線作為待測元素譜線。表4各元素分析譜線元素分析線波長nm元素分析線波長nmAl396.152Ti323.452Bi222.821/223.061Zn202.548/206.200Ca317.993Zr327.307/343.823Cu324.754/327.396K589.592Fe238.204/259.940Na766.49Mg279.553/285.213B249.678Mn257.610/259.372P178.284Pb220.353Si288.1583.5基體效應(yīng)的影響繪制在0.1μg/mL的Fe、Ca、Mg、Al、Cu、Mn、Ti、Zr、B、P、Si、Bi、Pb、Zn、K、Na試驗(yàn)溶液中，分別加入的Ag基體濃度（1.0mg/mL）（保證酸匹配），分別測定其譜線凈峰值及不加基體溶液時譜線凈峰值，以其比值考察基體濃度對待測元素的測定影響，結(jié)果見表5。表5銀基體效應(yīng)的影響元素質(zhì)量濃度（μg/mL）Ag基體（mg/mL）實(shí)測值（μg/mL）回收率（%）Al0.101.00.09999.0Bi0.101.00.09898.0Ca0.101.00.09999.0Cu0.101.00.09999.0Fe0.101.00.09999.0Mg0.101.00.09999.0Mn0.101.00.09999.0Pb0.101.00.09999.0Ti0.101.00.09898.0Zn0.101.00.09898.0Zr0.101.00.09999.0K0.101.00.09797.0Na0.101.00.103103.0B0.101.00.09999.0P0.101.00.102102.0Si0.101.00.09999.0基體匹配的譜線凈峰值及不加基體的譜線凈峰值比值越接近1時，表明基體對待測元素的測定無顯著影響。由上表數(shù)據(jù)看出,Ag基體濃度小于1.0mg/mL時，在安捷倫5110全譜直讀等離子體發(fā)射光譜儀上對Fe、Ca、Mg、Al、Cu、Mn、Ti、Zr、B、P、Si、Bi、Pb、Zn、K、Na測定無顯著影響。3.6共存元素干擾試驗(yàn)銀粉中大部分雜質(zhì)元素含量較低，共存干擾也很小，基本可以忽略，但是Bi、Pb、Zn三種元素對Si的干擾比較嚴(yán)重。在不同試驗(yàn)溶液中，分別加入不同量的共存元素,分別測定加入共存元素后,譜線凈峰值及不加入共存元素時的譜線凈峰值，以其比值考察不同量共存元素的測定影響，結(jié)果見表6。表6共存元素干擾試驗(yàn)干擾元素加入量（ug/mL）PbBiZnSiPb0.50-1.001.000.9810.00-1.001.001．0820.00-1.000.991.1550.00-0.981.001.30Bi0.500.99-1.001.1010.001.00-1.001.2020.001.01-1.001.5050.001.01-1.002.50Zn0.501.001.00-1.0310.001.011.00-1.0820.001.001.00-1.2050.001.001.00-1.50Si0.500.991.011.00-1.001.001.011.00-5.001.001.011.00-10.01.011.021.00-由表6數(shù)據(jù)看出，Bi、Pb、Zn雖然含量較高，但共存干擾較小，但是對Si的干擾很大。由于銀樣品中Bi、Pb、Zn的含量為0.0010～50.0ug/mL之間且不固定，因此無法進(jìn)行基體匹配，銀中測定Si的時候只能選擇標(biāo)準(zhǔn)加入校正法，以消除Bi、Pb、Zn的共存干擾。3.7工作曲線與線性回歸按照儀器設(shè)定的工作條件對標(biāo)準(zhǔn)溶液系列進(jìn)行測定，以待測元素質(zhì)量濃度為橫坐標(biāo)，發(fā)射強(qiáng)度為縱坐標(biāo)，繪制工作曲線。工作曲線的線性方程、相關(guān)系數(shù)見表7。表7校準(zhǔn)曲線的線性范圍、線性回歸方程和相關(guān)系數(shù)元素波長/nm線性范圍w/%線性方程相關(guān)系數(shù)Al396.1520.0010%～0.10%y=57025.78x+32.960.99989Bi182.2050.0010%～5.0%y=5268.31*x+28.410.99990Ca317.9330.0010%～0.10%y=43883.83x+127.280.99992Cu327.3960.0010%～0.10%y=72441.64x+570.110.99990Fe259.9400.0010%～0.10%y=37558.59x+17.810.99989Mg279.5020.0010%～0.10%y=59290.22x+18.840.99990Mn257.6100.0010%～0.10%y=324236.61x+7.960.99996Pb223.0610.0010%～5.0%y=4128.04*x+53.750.99995Ti323.6580.0010%～0.10%y=34849.73x+9.440.99996Zn206.2000.0010%～5.0%y=110415.50x+1921.980.99994Zr343.8230.0010%～0.10%y=1586140.67x+44.220.99994K766.4900.010%～0.10%y=8304.78x+30.440.99990Na589.5920.010%～0.10%y==46832.26x+92.7180.99997B249.6070.010%～0.10%y=38368.43x+139.520.99997P178.2840.010%～0.10%y=1120.01x+6.860.99995Si185.0670.010%～0.10%y=12521.17x+49.150.999913.8元素檢出限和定量下限的確定按照儀器設(shè)定的工作條件對標(biāo)準(zhǔn)溶液系列進(jìn)行測定，以待測元素質(zhì)量濃度為橫坐標(biāo)，發(fā)射強(qiáng)度為縱坐標(biāo)，繪制校準(zhǔn)曲線。對空白溶液連續(xù)測定11次，以測定結(jié)果標(biāo)準(zhǔn)偏差的3倍計算各元素的檢出限；以測定結(jié)果標(biāo)準(zhǔn)偏差的10倍計算各元素的測定下限。校準(zhǔn)曲線的線性方程、相關(guān)系數(shù)、檢出限和測定下限見表8。表8起草單位檢出限和測定下限元素測定值％平均值％標(biāo)準(zhǔn)偏差檢出限％測定下限％Al0.0016，0.0016，0.0015，0.0016，0.0015，0.0013，0.0016，0.0016，0.0014，0.0014，0.00140.00150.000110.00030.001Bi0.00019，0.00022，0.00020，0.00023，0.00022，0.00017，0.00022，0.00020，0.00023，0.00022，0.000180.00020.000020.00010.00019Ca0.0015，0.0012，0.0014，0.0012，0.0014，0.0013，0.0014，0.0015，0.0014，0.0014，0.00130.00140.000110.00030.001Cu0.0016,0.0015,0.0017,0.0016，0.0017,0.0014，0.0015，0.0017，0.0015,0.0017,0.00140.00160.000090.00030.00093Fe0.0002，0.0003，0.0002，0.0003，0.0003，0.0004，0.0003，0.0002，0.0003，0.0004，0.0003，0.00030.000070.00020.00066Mg0.0002，0.0002，0.0002，0.0003，0.0002，0.0002，0.0001，0.0003，0.0002，0.0003，0.0002，0.00020.000050.00020.00054Mn0.00019，0.00017，0.00020，0.00019，0.00022，0.00039，0.00013，0.00011，0.00041，0.00021，0.000190.00020.000090.00030.00095Pb0.0002，0.0003，0.0001，0.0002，0.0004，0.0002，0.0003，0.0002，0.0004，0.0002，0.00010.00020.000090.00030.00092Ti0.00015，0.00016，0.00018，0.00024，0.00019，0.00017，0.00019，0.00026，0.00016，0.00028，0.000150.00020.000050.00010.00046Zn0.00017，0.00021，0.00022，0.00019，0.00025，0.00019，0.00018，0.00020，0.00029，0.00018，0.000240.00020.000040.00010.00036Zr0.00022，0.00041，0.00020，0.00021，0.00020，0.00043，0.00021，0.00020，0.00028，0.00020，0.000210.00030.000090.00030.00086K0.0011，0.0012，0.0021，0.0012，0.0018，0.0016，0.0011，0.0012，0.0011，0.0012，0.00190.00140.000370.00110.0037Na0.0018，0.0011，0.0009，0.0011，0.0020，0.0010，0.0011，0.0013，0.0012，0.0011，0.00100.00120.000350.0010.0035B0.0017，0.0009，0.0009，0.0009，0.0014，0.0009，0.0012，0.0010，0.0009，0.0009，0.00100.00110.000260.00080.0026P0.0009，0.0011，0.0008，0.0008，0.0015，0.0008，0.0008，0.0013，0.0008，0.0008，0.00120.0010.000250.00080.0026Si0.0012，0.0008，0.0009，0.0001，0.0009，0.0009，0.0010，0.0009，0.0010，0.0014，0.00090.00090.000310.00090.0031表8結(jié)果表明，該方法的測定下限滿足測定范圍要求。第一驗(yàn)證單位（寧夏中色新材料有限公司）的方法測定下限見表9。表9一驗(yàn)（寧夏中色新材料有限公司）檢出限和測定下限元素測定值％平均值％標(biāo)準(zhǔn)偏差檢出限％測定下限％Al0.0018，0.0016，0.0015，0.0017，0.0014，0.0015，0.0017，0.0016，0.0014，0.0015，0.00160.00160.00010.00030.001Bi0.00020，0.00024，0.00020，0.00023，0.00022，0.00023，0.00022，0.00026，0.00023，0.00019，0.000280.000230.000030.00010.00026Ca0.0017，0.0014，0.0014，0.0016，0.0014，0.0013，0.0014，0.0018，0.0014，0.0014，0.00130.00140.00010.00030.0010Cu0.0017，0.0016，0.0018，0.0017，0.0018，0.0015，0.0015，0.0018，0.0015，0.0018，0.00150.00160.00010.00030.0010Fe0.00050，0.00027，0.00030，0.00040，0.00027，0.00040，0.00027，0.00040，0.00025，0.00050，0.000260.000350.00010.00030.00095Mg0.00016，0.00019，0.00020，0.00030，0.00024，0.00020，0.00013，0.00030，0.00021，0.00030，0.000200.000220.000060.00020.00057Mn0.00019，0.00017，0.00020，0.00019，0.00022，0.00039，0.00013，0.00011，0.00290，0.00021，0.000190.000210.000080.00020.00076Pb0.00028，0.00019，0.00022，0.00023，0.00040，0.00023，0.00030，0.00028，0.00040，0.00020，0.000240.000270.000070.00020.00072Ti0.00018，0.00020，0.00018，0.00024，0.00019，0.00017，0.00029，0.00026，0.00016，0.00028，0.000150.000210.000050.00020.0005Zn0.00027，0.00021，0.00022，0.00019，0.00025，0.00019，0.00018，0.00026，0.00029，0.00018，0.000240.000230.000040.00010.00038Zr0.00040，0.00032，0.00020，0.00021，0.00020，0.00023，0.00021，0.00020，0.00028，0.00019，0.000210.000240.000070.00020.00066K0.0010，0.0012，0.0021，0.0013，0.0018，0.0016，0.0022，0.0012，0.0009，0.0012，0.00170.00120.000440.00130.0044Na0.0012，0.0010，0.0010，0.0012，0.0021，0.0010，0.0012，0.0013，0.0011，0.0012，0.00110.00120.000310.00090.0031B0.0016，0.0010，0.0009，0.0010，0.0013，0.0012，0.0015，0.0010，0.0009，0.0011，0.00100.00110.000240.000710.0024P0.0010，0.0012，0.0008，0.0009，0.0015，0.0009，0.0008，0.0012，0.0008，0.0008，0.00120.0010.000240.00070.0024Si0.0011，0.0009，0.0010，0.0013，0.0009，0.0011，0.0014，0.0020，0.0011，0.0014，0.00090.00120.000320.0010.0032表9結(jié)果表明，該方法的測定下限滿足測定范圍要求，與起草單位一致。3.9準(zhǔn)確度試驗(yàn)3.9.1起草單位加標(biāo)回收試驗(yàn)于兩個銀粉樣品中加入不同量的各元素標(biāo)準(zhǔn)溶液，按實(shí)驗(yàn)方法進(jìn)行加標(biāo)回收試驗(yàn)，結(jié)果見表10。表10起草單位加標(biāo)回收試驗(yàn)樣品編號元素樣品值/%加入量/%測得值/%回收率/%Ag-1#Al0.00180.00400.0058100.0Bi0.00210.00400.006097.5Ca0.00170.00400.005697.5Cu0.00160.00400.005597.5Fe0.00260.00400.0066100.0Mg0.00210.00400.006097.5Mn0.00200.00400.005997.5Pb0.00230.00400.0064102.5Ti0.00160.00400.005495.0Zn0.00180.00400.0058100.0Zr0.00210.00400.0061100.0K0.01160.0200.0321102.5Na0.01070.0200.0307100.0B0.00910.0200.028798.0P0.00810.0200.0283101.0Si0.00870.0200.028599.0Ag-2#Al0.03640.0400.075898.5Bi0.03610.0400.0769102.0Ca0.02490.0400.063396.0Cu0.03720.0400.076197.3Fe0.03650.0400.0782104.3Mg0.03670.0400.0771101.0Mn0.03640.0400.0779103.8Pb0.03650.0400.0768100.8Ti0.03750.0400.075795.5Zn0.03560.0400.0768103.0Zr0.04290.0400.0835101.5K0.03510.0400.074297.8Na0.04270.0400.0837102.5B0.04290.0400.0829100.0P0.04120.0400.079696.0Si0.05040.0400.0920104.0由表10數(shù)據(jù)可知，銀粉樣品中加標(biāo)回收率在95.0%～104.3%之間，證明方法準(zhǔn)確度滿足實(shí)驗(yàn)要求。3.9.2一驗(yàn)加標(biāo)回收試驗(yàn)第一驗(yàn)證單位(寧夏中色新材料有限公司)的加標(biāo)回收試驗(yàn)結(jié)果見表11。表11一驗(yàn)加標(biāo)回收試驗(yàn)樣品編號元素樣品值/%加入量/%測得值/%回收率/%Ag-1#Al0.00190.00400.005897.5Bi0.00210.00400.005995.0Ca0.00200.00400.0061102.5Cu0.00100.00400.0051102.5Fe0.00260.00400.006597.5Mg0.00220.00400.006197.5Mn0.00210.00400.006097.5Pb0.00220.00400.0063102.3Ti0.00180.00400.005798.2Zn0.00180.00400.0059102.5Zr0.00200.00400.005998.2K0.01170.0200.0321101.9Na0.01100.0200.030798.5B0.00930.0200.028696.5P0.00820.0200.0283100.5Si0.00870.0200.028699.5Ag-2#Al0.03580.0400.0761100.8Bi0.03660.0400.0774102.0Ca0.02560.0400.063795.3Cu0.03670.0400.076198.5Fe0.03620.0400.0777103.8Mg0.03690.0400.076799.5Mn0.03600.0400.0776104.0Pb0.03590.0400.0773103.5Ti0.03790.0400.076095.3Zn0.03630.0400.0770101.8Zr0.04300.0400.0830100.0K0.03530.0400.074297.3Na0.04270.0400.080895.3B0.04300.0400.082799.3P0.04160.0400.080497.0Si0.05210.0400.0933103.0表11結(jié)果表明，該方法準(zhǔn)確度滿足分析要求，與起草單位一致。3.10精密度試驗(yàn)對3個不同元素含量的銀粉樣品，采用本方法分別獨(dú)立地進(jìn)行11次測定，測定結(jié)果見表12。表12起草單位樣品測定結(jié)果樣品元素測定結(jié)果/％（n=11）平均值/％sRSD/％Ag-1#Al0.0016，0.0018，0.0019，0.0018，0.0016，0.0020，0.0018，0.0020，0.0017，0.0016，0.00190.00180.00028.47Bi0.0019，0.0022，0.0020，0.0023，0.0022，0.0017，0.0022，0.0020，0.0023，0.0022，0.00180.00210.00029.07Ca0.0018，0.0019，0.0015，0.0016，0.0017，0.0018，0.0018，0.0015，0.0016，0.0015，0.00170.00170.00017.85Cu0.0018，0.0015，0.0017，0.0016，0.0017，0.0014，0.0015，0.0017，0.0015，0.0017，0.00140.00160.00017.20Fe0.0027，0.0027，0.0025，0.0025，0.0027，0.0026，0.0027，0.0025，0.0025，0.0029，0.00260.00260.00014.99Mg0.0022，0.0019，0.0020，0.0021，0.0024，0.0020，0.0019，0.0020，0.0021，0.0020，0.00200.00210.00016.66Mn0.0019，0.0021，0.0019，0.0020，0.0023，0.0019，0.0022，0.0018，0.0020，0.0020，0.00190.00200.00017.07Pb0.0024，0.0026，0.0022，0.0023，0.0020，0.0023，0.0026，0.0021，0.0023，0.0020，0.00230.00230.00029.36Ti0.0015，0.0016，0.0018，0.0014，0.0016，0.0017，0.0019，0.0015，0.0016，0.0016，0.00150.00160.00019.16Zn0.0019，0.0020，0.0017，0.0017，0.0019，0.0017，0.0020，0.0017，0.0016，0.0021，0.00170.00180.00018.19Zr0.0022，0.0021，0.0020，0.0021，0.0020，0.0021，0.0021，0.0020，0.0021，0.0020，0.00210.00210.00012.56K0.0109，0.0121，0.0113，0.0118，0.0117，0.0119，0.0109，0.0121，0.0113，0.0118，0.01170.01160.00043.45Na0.0109，0.0107，0.0108，0.0106，0.0104，0.0104，0.0109，0.0107，0.0108，0.0106，0.01040.01070.00021.63B0.0086，0.0091，0.0093，0.0090，0.0091，0.0092，0.0089，0.0097，0.0095，0.0091，0.00890.00910.00033.27P0.0085，0.0087，0.0080，0.0080，0.0084，0.0083，0.0075，0.0079，0.0082，0.0079，0.00780.00810.00034.22Si0.0086，0.0084，0.0087，0.0083，0.0089，0.0086，0.0088，0.0085，0.0090，0.0093，0.00840.00870.00033.56Ag-2#Al0.0370，0.0368，0.0373，0.0378，0.0374，0.0376，0.0375，0.0348，0.0349，0.0345，0.03430.03640.00143.84Bi0.0369，0.0363，0.0371，0.0359，0.0351，0.0347，0.0349，0.0354，0.0386，0.0340，0.03860.03610.00154.24Ca0.0269，0.0253，0.0255，0.0256，0.0254，0.0253，0.0234，0.0229，0.0251，0.0239，0.02490.02490.00114.52Cu0.0380，0.0378，0.0375，0.0385，0.0380，0.0376，0.0357，0.0352，0.0363，0.0398，0.03440.03720.00164.29Fe0.0367，0.0366，0.0368，0.0351，0.0359，0.0369，0.0383，0.0356，0.0370，0.0371，0.03530.03650.00092.57Mg0.0369，0.0371，0.0374，0.0381，0.0375，0.0373，0.0357，0.0349，0.0363，0.0350，0.03730.03670.00102.86Mn0.0376，0.0350，0.0363，0.0365，0.0364，0.0362，0.0358，0.0346，0.0365，0.0370，0.03850.03640.00113.00Pb0.0356，0.0373，0.0377，0.0363，0.0357，0.0363，0.0378，0.0369，0.0363，0.0352，0.03610.03650.00092.37Ti0.0383，0.0386，0.0376，0.0384，0.0365，0.0385，0.0375，0.0385，0.0364，0.0361，0.03620.03750.00102.73Zn0.0357，0.0363，0.0358，0.0367，0.0365，0.0357，0.0353，0.0349，0.0341，0.0362，0.03490.03560.00082.21Zr0.0428，0.0435，0.0431，0.0432，0.0424，0.0428，0.0425，0.0421，0.0432，0.0433，0.04280.04290.00041.00K0.0366，0.0348，0.0348，0.0352，0.0356，0.0343，0.0356，0.0342，0.0343，0.0354，0.03580.03510.00082.15Na0.0430，0.0425，0.0431，0.0430，0.0421，0.0422，0.0430，0.0426，0.0432，0.0427，0.04240.04270.00040.85B0.0438，0.0439，0.0438，0.0439，0.0437，0.0440，0.0418，0.0417，0.0418，0.0416，0.04190.04290.00112.54P0.0392，0.0438，0.0408，0.0416，0.0420，0.0382，0.0441，0.0408，0.0416，0.0420，0.03880.04120.00194.60Si0.0509，0.0513，0.0506，0.0508，0.0488，0.0507，0.0501，0.0490，0.0517，0.0497，0.04990.05020.00102.07Ag-3#Al0.0900,0.0861,0.0873,0.0856,0.0867,0.0850,0.0861,0.0890,0.0840,0.0867,0.08800.08680.00172.00Bi4.28,4.20,4.36,4.22,4.21,4.27,4.19,4.18,4.22,4.31,4.234.240.0561.32Ca0.0813,0.0790,0.0722,0.0678,0.0761,0.0736,0.0856,0.0760,0.0783,0.0750,0.07400.07630.00486.23Cu0.0990，0.108，0.112，0.108，0.107，0.107，0.113，0.108，0.098，0.108，0.1050.1070.00454.24Fe0.0970,0.0941,0.0968,0.0980,0.0984,0.0964,0.0941,0.0947,0.0957,0.0980,0.09450.09620.00161.69Mg0.0960,0.0943,0.0930,0.0947,0.0910,0.0944,0.0930,0.0900,0.0947,0.0960,0.09440.09380.00192.02Mn0.0940,0.0910,0.0922,0.0950,0.0931,0.0960,0.0950,0.0932,0.0941,0.0920,0.09410.09360.00151.61Pb4.40，4.41，4.39，4.40，4.38，4.40，4.41，4.38，4.40，4.38，4.404.400.0240.54Ti0.0973,0.0960,0.101,0.0990,0.0972,0.0980,0.0951,0.0960,0.0991,0.0970,0.1030.09810.00242.40Zn4.70，4.60，4.75，4.72，4.62，4.72，4.61，4.74，4.72，4.71，4.734.690.05511.17Zr0.0990,0.112,0.108,0.0980,0.107,0.108,0.107,0.108,0.111,0.0980,0.1080.1060.00514.79K0.0938，0.0988，0.0984，0.0936，0.0980，0.0988，0.0938，0.0979，0.0981，0.0938，0.09730.0970.00232.35Na0.107，0.108,0.105，0.105，0.105，0.107，0.107，0.106，0.105，0.105，0.1050.1050.00232.23B0.0989，0.0995，0.1010，0.0994，0.1040，0.0991，0.0981，0.1050，0.0981，0.0977，0.09600.1000.00272.69P0.0982，0.1021，0.0982，0.0951，0.0902，0.1002，0.0972，0.0935，0.0906，0.0902，0.09540.0960.00414.28Si0.106，0.107，0.107，0.107，0.107，0.0994，0.0997，0.100，0.0991，0.0999，0.09940.1030.00363.54由表12結(jié)果可知，本法的RSD％在0.20%～9.36%之間，精密度能滿足分析要求。第一驗(yàn)證單位（寧夏中色新材料有限公司）的精密度試驗(yàn)結(jié)果見表13。表13一驗(yàn)（寧夏中色新材料有限公司）精密度實(shí)驗(yàn)樣品元素測定結(jié)果/％（n=11）平均值/％sRSD/％Ag-1#Al0.0019，0.0017，0.0019，0.0018，0.0021，0.0020，0.0018，0.0021，0.0017，0.0016，0.00190.00190.00028.53Bi0.0024，0.0020，0.0021，0.0023，0.0022，0.0018，0.0022，0.0020，0.0021，0.0022，0.00170.00210.00029.53Ca0.0020，0.0023，0.0018，0.0020，0.0018，0.0019，0.0021，0.0022，0.0018，0.0019，0.00220.00200.00028.94Cu0.0009，0.0010，0.0011，0.0010，0.0010，0.0012，0.0011，0.0009，0.0010，0.0011，0.00120.00100.00019.91Fe0.0027，0.0025，0.0026，0.0028，0.0027，0.0026，0.0027，0.0026，0.0025，0.0028，0.00270.00270.00013.73Mg0.0021，0.0022，0.0024，0.0021，0.0023，0.0021，0.0019，0.0020，0.0021，0.0024，0.00200.00220.00026.96Mn0.0019，0.0021，0.0020，0.0018，0.0022，0.0019，0.0023，0.0022，0.0019，0.0023，0.00190.00210.00028.48Pb0.0023，0.0022，0.0020，0.0024，0.0020，0.0023，0.0026，0.0021，0.0023，0.0019，0.00240.00220.00029.50Ti0.0017，0.0016，0.0020，0.0015，0.0016，0.0017，0.0020，0.0018，0.0016，0.0017，0.00180.00170.00029.42Zn0.0019，0.0020，0.0017，0.0016，0.0019，0.0017，0.0020，0.0015，0.0016，0.0017，0.00160.00170.00029.27Zr0.0020，0.0019，0.0020，0.0021，0.0020，0.0019，0.0019，0.0020，0.0021，0.0020，0.00190.00200.00014.08K0.0112，0.0122，0.0112，0.0118，0.0117，0.0119，0.0113，0.0121，0.0113，0.0118，0.01210.01170.00043.24Na0.0110，0.0106，0.0117，0.0106，0.0124，0.0104，0.0111，0.0103，0.0120，0.0106，0.01040.01100.00076.50B0.0084，0.0091，0.0093，0.0095，0.0098，0.0092，0.0089，0.0100，0.0095，0.0100，0.00840.00930.00066.02P0.0086，0.0089，0.0079，0.0094，0.0084，0.0083，0.0074，0.0080，0.0082，0.0076，0.00730.00820.00067.77Si0.0078，0.0087，0.0087，0.0083，0.0087，0.0078，0.0082，0.0087，0.0087，0.0093，0.00970.00860.00066.59Ag-2#Al0.0362，0.0357，0.0374，0.0374，0.0371，0.0363，0.0378，0.0335，0.0349，0.0342，0.03390.03590.00154.27Bi0.0371，0.0369，0.0354，0.0385，0.0375，0.0348，0.0363，0.0354，0.0344，0.0385，0.03810.03660.00154.02Ca0.0264，0.0253，0.0251，0.0255，0.0280，0.0253，0.0242，0.0247，0.0251，0.0276，0.02460.02560.00124.75Cu0.0386，0.0370，0.0352，0.0387，0.0373，0.0380，0.0359，0.0354，0.0353，0.0372，0.03580.03680.00133.60Fe0.0357，0.0364，0.0354，0.0351，0.0350，0.0369，0.0383，0.0356，0.0370，0.0382，0.03530.03630.00123.30Mg0.0390，0.0371，0.0374，0.0381，0.0375，0.0373，0.0357，0.0358，0.0363，0.0349，0.03730.03690.00123.18Mn0.0369，0.0360，0.0354，0.0342，0.0371，0.0361，0.0352，0.0382，0.0364，0.0369，0.03390.03600.00133.57Pb0.0361，0.0373，0.0348，0.0350，0.0352，0.0363，0.0379，0.0359，0.0363，0.0352，0.03510.03590.00102.79Ti0.0389，0.0386，0.0391，0.0384，0.0365，0.0385，0.0375，0.0385，0.0364，0.0381，0.03720.03800.00092.47Zn0.0371，0.0364，0.0351，0.0364，0.0358，0.0372，0.0364，0.0365，0.0364，0.0358，0.03620.03610.00082.19Zr0.0428，0.0436，0.0445，0.0437，0.0415，0.0426，0.0443，0.0431，0.0416，0.0435，0.04260.04310.00102.27K0.0366，0.0360，0.0348，0.0352，0.0356，0.0338，0.0356，0.0336，0.0343，0.0354，0.03750.03530.00123.32Na0.0430，0.0425，0.0431，0.0416，0.0421，0.0422，0.0430，0.0426，0.0442，0.0437，0.04240.04270.00092.04B0.0442，0.0439，0.0435，0.0450，0.0437，0.0440，0.0418，0.0417，0.0418，0.0423，0.04150.04300.00122.87P0.0392，0.0448，0.0408，0.0416，0.0420，0.0406，0.0454，0.0408，0.0416，0.0420，0.03980.04170.00194.54Si0.0514，0.0520，0.0518，0.0518，0.0506，0.0517，0.0529，0.0501，0.0195，0.0525，0.05260.05150.00112.06Ag-3#Al0.0898，0.0861，0.0838，0.0852，0.0867，0.0841，0.0866，0.0867，0.0838，0.0867，0.08390.08580.00182.14Bi4.25，4.30，4.33，4.22，4.34，4.27，4.19，4.22，4.26，4.31，4.324.270.05041.18Ca0.0795，0.0790，0.0735，0.0698，0.0761，0.0736，0.0820，0.0760，0.0783，0.0750，0.07890.07650.00354.51Cu0.110，0.113，0.112，0.108，0.107，0.106，0.111，0.108，0.099，0.108，0.1010.1070.00434.02Fe0.0980，0.0960，0.0968，0.0980，0.1080，0.0964，0.0970，0.1070，0.0957，0.0980，0.09600.09880.00444.43Mg0.0970，0.0943，0.0960，0.0947，0.0910，0.0944，0.0930，0.0910，0.0980，0.0970，0.09440.09460.00232.45Mn0.0990,0.0931,0.0935,0.0933,0.0970,0.0937，0.0931,0.0980,0.0950,0.0933,0.09200.09470.00232.43Pb4.45,4.48,4.39,4.40,4.38,4.40,4.41,4.31,4.28,4.38,4.404.390.05541.26Ti0.100,0.101,0.0978,0.102,0.0991,0.0982,0.106,0.0990,0.104,0.105,0.09940.1010.00292.85Zn4.76,4.80,4.89,4.82,4.84,4.76,4.90,4.87,4.79,4.77,4.904.830.05571.15Zr0.113,0.107,0.108,0.107,0.110,0.113,0.107,0.097,0.107,0.098,0.1090.1070.00524.85K0.0941,0.0987,0.0985,0.0946,0.0980,0.0986,0.0951,0.0976,0.0981,0.0938,0.09720.09680.00192.00Na0.113,0.106,0.115,0.109,0.113,0.107,0.107,0.106,0.105,0.115,0.1200.1110.00494.42B0.0982,0.0999,0.0981,0.0994,0.1040,0.0991,0.0981,0.1050,0.0981,0.0977,0.09600.09940.00272.73P0.0976,0.104,0.0990,0.0940,0.0922,0.100,0.0974,0.0935,0.0929,0.0924,0.09540.09620.00383.92Si0.114,0.106,0.104,0.108,0.110,0.109,0.0998,0.110,0.0996,0.0992,0.1080.1060.00494.64第二驗(yàn)證單位（寧夏東方鉭業(yè)股份有限公司）的精密度試驗(yàn)結(jié)果見表14。表14二驗(yàn)（寧夏東方鉭業(yè)股份有限公司）精密度實(shí)驗(yàn)樣品元素測定結(jié)果/％（n=11）平均值/％sRSD/％Ag-1#Al0.0023,0.0021,0.0020,0.0018,0.0020,0.0019,0.0018,0.0020,0.0018,0.0022,0.00230.00200.00029.31Bi0.0024,0.0022,0.0024,0.0023,0.0020,0.0019,0.0022,0.0020,0.0023,0.0022,0.00260.00220.00029.11Ca0.0013,0.0016,0.0015,0.0017,0.0016,0.0018,0.0017,0.0015,0.0019,0.0015,0.00170.00160.00029.94Cu0.0018,0.0015,0.0019,0.0016,0.0017,0.0015,0.0016,0.0017,0.0018,0.0017,0.00200.00170.00029.31Fe0.0026,0.0028,0.0025,0.0024,0.0027,0.0026,0.0027,0.0024,0.0026,0.0028,0.00260.00260.00015.47Mg0.0024,0.0020,0.0021,0.0022,0.0023,0.0022,0.0025,0.0021,0.0021,0.0020,0.00230.00220.00027.08Mn0.0022,0.0020,0.0019,0.0021,0.0020,0.0019,0.0020,0.0020,0.0018,0.0020,0.00190.00200.00015.18Pb0.0023,0.0025,0.0021,0.0023,0.0020,0.0024,0.0025,0.0020,0.0022,0.0021,0.00230.00220.00028.06Ti0.0017,0.0018,0.0019,0.0016,0.0017,0.0018,0.0019,0.0016,0.0017,0.0020,0.00160.00180.00017.80Zn0.0020,0.0019,0.0018,0.0019,0.0018,0.0019,0.0018,0.0017,0.0019,0.0018,0.00190.00190.00014.79Zr0.0023,0.0022,0.0020,0.0022,0.0021,0.0022,0.0023,0.0020,0.0021,0.0022,0.00210.00220.00014.80K0.0110,0.0111,0.0113,0.0118,0.0120,0.0119,0.0109,0.0121,0.0113,0.0118,0.01170.01150.00043.57Na0.0115,0.0112,0.0113,0.0105,0.0104,0.0114,0.0109,0.0107,0.0108,0.0106,0.01050.01090.00043.56B0.0096,0.0092,0.0093,0.0094,0.0091,0.0092,0.0090,0.0097,0.0095,0.0091,0.00930.00930.00022.40P0.0083,0.0088,0.0080,0.0081,0.0082,0.0083,0.0083,0.0086,0.0082,0.0079,0.008230.00830.00022.99Si0.0088,0.0083,0.0087,0.0088,0.0091,0.0093,0.0098,0.0093,0.0097,0.0097,0.00900.00920.00055.29Ag-2#Al0.0370,0.0368,0.0373,0.0378,0.0374,0.0376,0.0379,0.0362,0.0349,0.0339,0.03520.03650.00133.62Bi0.0369,0.0363,0.0371,0.0359,0.0351,0.0339,0.0341,0.0354,0.0376,0.0340,0.03800.03580.00154.11Ca0.0240,0.0252,0.0256,0.0257,0.0254,0.0233,0.0254,0.0230,0.0251,0.0238,0.02490.02470.00103.92Cu0.0379,0.0378,0.0378,0.0385,0.0380,0.0376,0.0367,0.0362,0.0363,0.0398,0.03590.03750.00113.06Fe0.0357,0.0367,0.0368,0.0351,0.0359,0.0369,0.0383,0.0356,0.0350,0.0361,0.03530.03610.00102.73Mg0.0379,0.0360,0.0373,0.0382,0.0375,0.0376,0.0357,0.0359,0.0374,0.0353,0.03820.03700.00112.87Mn0.0374,0.0352,0.0364,0.0365,0.0366,0.0362,0.0358,0.0366,0.0365,0.0372,0.03840.03660.00082.29Pb0.0358,0.0349,0.0378,0.0361,0.0357,0.0364,0.0379,0.0369,0.0363,0.0352,0.03590.03630.00102.63Ti0.0369,0.0366,0.0377,0.0364,0.0365,0.0375,0.0375,0.0377,0.0364,0.0371,0.03620.03700.00061.55Zn0.0355,0.0357,0.0364,0.0357,0.0365,0.0349,0.0363,0.0367,0.0348,0.0356,0.03670.03590.00071.90Zr0.0438,0.0434,0.0439,0.0442,0.0434,0.0418,0.0425,0.0440,0.0432,0.0423,0.04380.04330.00081.80K0.0356,0.0368,0.0348,0.0352,0.0366,0.0362,0.0356,0.0356,0.0343,0.0354,0.03670.03570.00082.22Na0.0415,0.0421,0.0431,0.0430,0.0411,0.0422,0.0430,0.0406,0.0432,0.0427,0.04140.04220.00092.14B0.0437,0.0446,0.0437,0.0438,0.0443,0.0440,0.0428,0.0417,0.0433,0.0446,0.04150.04350.00112.44P0.0383,0.0443,0.0408,0.0416,0.0420,0.0379,0.0423,0.0408,0.0416,0.0420,0.03760.04080.00215.11Si0.0516,0.0529,0.0517,0.0519,0.0515,0.0516,0.0530,0.0533,0.0530,0.0533,0.05290.05240.00071.43Ag-3#Al0.0901,0.0851,0.0873,0.0856,0.0867,0.0850,0.0861,0.0880,0.0840,0.0867,0.08780.08660.00171.96Bi4.26,4.12,4.36,4.22,4.21,4.27,4.16,4.13,4.22,4.21,4.234.220.06761.60Ca0.0780,0.0710,0.0760,0.0678,0.0761,0.0736,0.0856,0.0760,0.0690,0.0650,0.07400.07380.00567.62Cu0.100,0.0980,0.102,0.108,0.0960,0.107,0.113,0.108,0.0981,0.108,0.1000.1030.00545.21Fe0.0910,0.0941,0.0968,0.0930,0.0984,0.0964,0.0900,0.0947,0.0957,0.0890，0.09100.09360.00313.29Mg0.0870,0.0943,0.0930,0.0947,0.0910,0.0944,0.0930,0.0900,0.0940,0.0960,0.08900.09240.00283.01Mn0.0960,0.0890,0.0920,0.0950,0.0930,0.0960,0.0880,0.0930,0.0940,0.0910,0.09410.09280.00262.85Pb4.42,4.35,4.39,4.49,4.38,4.33,4.41,4.31,4.29,4.25,4.304.390.06861.57Ti0.0991,0.0958,0.0982,0.104,0.0973,0.0984,0.0962,0.0976,0.0987,0.102,0.09840.09870.00242.43Zn4.73,4.64,4.76,4.67,4.70,4.69,4.67,4.68,4.69,4.59,4.704.680.04420.94Zr0.109,0.112,0.108,0.099,0.119,0.108,0.114,0.108,0.111,0.108,0.1140.1100.00514.64K0.0948,0.0988,0.0984,0.0936,0.0980,0.0988,0.0968,0.0979,0.0981,0.0938,0.09930.09710.00212.13Na0.116,0.109,0.105,0.105,0.105,0.107,0.109,0.106,0.112,0.105,0.1150.1090.00403.72B0.102，0.0995,0.101,0.0994,0.104，0.0991,0.0981,0.1050,0.0981,0.107,0.09600.1010.00333.31P0.0916,0.0992,0.0984,0.0957,0.0922,0.0987,0.0972,0.0936,0.0906,0.0912,0.09540.09490.00323.39Si0.0974,0.0997,0.104,0.0981,0.102,0.0990,0.0978,0.101,0.0996,0.0968,0.09620.09920.00242.383.11主要實(shí)驗(yàn)（或驗(yàn)證）的分析按照GB/T6379.2-2004《測量方法與結(jié)果的準(zhǔn)確度》的內(nèi)容，通過對西北稀有金屬材料研究院寧夏有限公司、寧夏中色新材料有限公司、寧夏東方鉭業(yè)股份有限公司的試驗(yàn)數(shù)據(jù)和驗(yàn)證數(shù)據(jù)分別按照重復(fù)性和允許差的公式進(jìn)行計算，得到了不同含量的重復(fù)性限和允許差。3.11.1樣品數(shù)據(jù)對比起草單位與驗(yàn)證單位的試驗(yàn)結(jié)果統(tǒng)計見表15。表15各元素的試驗(yàn)結(jié)果對比元素試驗(yàn)單位水平1水平2水平3，%s，%s，%sAl西北稀有金屬材料研究院寧夏有限公司起草0.00180.00020.03640.00140.08680.0017東方鉭業(yè)一驗(yàn)0.00190.00020.03590.00150.08580.0018中