《銅鈹合金化學(xué)分析方法 第1部分 鈹、鈷、鎳、鈦、鐵、鋁、硅、鉛、鎂、磷含量的測定 電感耦合等離子原子發(fā)射光譜法》 送審稿編制說明

一、工作簡況（一）任務(wù)來源根據(jù)2022年4月29日工業(yè)和信息化部發(fā)布的《工業(yè)和信息化部辦公廳關(guān)于印發(fā)2022年第一批行業(yè)標(biāo)準(zhǔn)制修訂和外文版項目計劃的通知》（工信廳科函[2022]94號）的要求，有色金屬行業(yè)標(biāo)準(zhǔn)《銅鈹合金化學(xué)分析方法第1部分：鈹、鈷、鎳、鈦、鐵、鋁、硅、鉛、鎂、磷含量的測定電感耦合等離子體原子發(fā)射光譜法》修訂項目由全國有色金屬標(biāo)準(zhǔn)化技術(shù)委員會負(fù)責(zé)歸口，由西北稀有金屬材料研究院寧夏有限公司負(fù)責(zé)起草，該項目計劃編號：2022-0224T-YS，項目周期為18個月，完成年限為2023年10月。（二）項目背景銅鈹合金作為高級精密的彈性元件材料，廣泛應(yīng)用于航空航天、電子通訊、自動化等領(lǐng)域，產(chǎn)品種類較多，根據(jù)鈹含量分類主要有C17300（含鈹量為1.80%～2.10%)，C17500（含鈹量為0.40%～0.70%)，及原料銅鈹中間合金錠（含鈹量為3.50%～4.10%）等。其中鈹、鈷、鎳、鈦為其產(chǎn)品添加元素，鐵、鋁、硅、鉛、鎂、磷為產(chǎn)品雜質(zhì)元素，均為影響合金質(zhì)量的重要指標(biāo)。精準(zhǔn)控制添加元素含量范圍，降低雜質(zhì)元素含量是保障合金產(chǎn)品性能的基本前提，因此精確檢測銅鈹合金中各元素含量具有重要意義。目前，銅鈹合金相關(guān)檢測標(biāo)準(zhǔn)主要有GB/T5121.27-2008（鈹測定范圍為0.010%~3.00%）、YS/T470.1-2004（鈹測定范圍為0.10%～3.00%）、YS/T470.2-2004（鈹測定范圍為3.00%～6.00%）、YS/T470.3-2004（磷測定范圍為0.0010%～0.12%），其中YS/T470.2-2004及YS/T470.3-2004分別采用滴定法及分光光度法，操作相對繁瑣，分析效率較低，難以滿足目前快速發(fā)展的生產(chǎn)需求。本次對于YS/T470.1-2004的修訂，充分考慮到標(biāo)準(zhǔn)的適應(yīng)性，于電感耦合等離子體原子發(fā)射光譜法增加磷量的測定，同時根據(jù)實際檢測需求拓寬部分元素的檢測上限及測定下限：鈹為0.0106.00鈷、鎳為0.0103.00鈦為0.0100.50鐵、鋁、硅、鎂為0.0100.30磷為0.00500.20鉛為0.00200.060％。修訂后方法涵蓋YS/T470.1-2004、流程復(fù)雜的YS/T470.2-2004及YS/T470.3-2004，提高工作效率，利于促進銅鈹合金產(chǎn)業(yè)的高速發(fā)展。（三）主要參加單位和工作成員及其所做的工作1.本標(biāo)準(zhǔn)起草單位及其分工本標(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、五礦鈹業(yè)股份有限公司、新疆有色金屬研究所、富蘊恒盛鈹業(yè)有限責(zé)任公司、上海有色金屬工業(yè)技術(shù)監(jiān)測中心有限公司。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)試驗方案制定，試驗樣品收集和分發(fā)，分析方法研究，試驗結(jié)果處理，標(biāo)準(zhǔn)文本、試驗報告和編制說明撰寫等工作；五礦鈹業(yè)股份有限公司、新疆有色金屬研究所為一驗單位，主要負(fù)責(zé)對試驗方案中的條件實驗進行驗證，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；富蘊恒盛鈹業(yè)有限責(zé)任公司、上海有色金屬工業(yè)技術(shù)監(jiān)測中心有限公司為二驗單位，主要負(fù)責(zé)提供精密度試驗數(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實驗室。公司分析檢測所主持及參與多項鈹、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。五礦鈹業(yè)股份有限公司系全球從礦石中提煉金屬鈹及其化合物的三家企業(yè)之一，是國內(nèi)唯一的金屬鈹和高純氧化鈹生產(chǎn)企業(yè)。公司主要從事鈹原料的資源控制，鈹、鋯等系列產(chǎn)品的冶煉、加工及相關(guān)材料的研發(fā)、制造和銷售等。在本次修訂中，反饋產(chǎn)品使用情況及方法檢測需求信息，同時作為第一驗證單位，提供實驗樣本的準(zhǔn)確度驗證及精密度數(shù)據(jù)。新疆有色金屬研究所是國內(nèi)唯一從事輕稀有金屬鋰銣銫冶煉、分析、新材料開發(fā)和推廣應(yīng)用的專業(yè)科研生產(chǎn)單位，是新疆維吾爾自治區(qū)重點科研院所之一。在本次修訂過程中，作為第一驗證單位，驗證試驗條件以及方法的定量下限，提供實驗樣本的準(zhǔn)確度驗證及精密度數(shù)據(jù)。富蘊恒盛鈹業(yè)有限責(zé)任公司，主要經(jīng)營鈹及鈹合金產(chǎn)品的加工、銷售，礦產(chǎn)品收購、加工、銷售，采礦選礦設(shè)備的加工，采選礦工藝設(shè)計技術(shù)咨詢，對外貿(mào)易等。在本次修訂過程中，提供實驗樣本的精密度數(shù)據(jù)。上海有色金屬工業(yè)技術(shù)監(jiān)測中心有限公司主體業(yè)務(wù)涉及第三方檢測服務(wù)(含金屬材料化學(xué)成分檢測、性能檢測、環(huán)保監(jiān)測、無損檢測等)、設(shè)備檢定、檢測培訓(xùn)等方面，是國家質(zhì)量監(jiān)督檢驗檢疫總局全國工業(yè)產(chǎn)品生產(chǎn)許可證辦公室審查部授權(quán)的檢測機構(gòu)。在本次修訂過程中，提供實驗樣本的精密度數(shù)據(jù)，并對標(biāo)準(zhǔn)文稿等提出了相應(yīng)的修改意見。2.本標(biāo)準(zhǔn)起草人員及其工作職責(zé)本標(biāo)準(zhǔn)主要起草人：李暉、王巧、馬肖、孫洪濤、溫亞勇、王永生、黃華新、朱云、張健康、張新輝、謝奕斌、莫蓉、殷藝丹、李娜、關(guān)黎曉、朱新明、郝晶晶。各起草人在本標(biāo)準(zhǔn)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標(biāo)準(zhǔn)技術(shù)內(nèi)容審核、試驗進度組織協(xié)調(diào)、標(biāo)準(zhǔn)文件（四）主要工作過程西北稀有金屬材料研究院寧夏有限公司在接到標(biāo)準(zhǔn)修訂任務(wù)后，成立了標(biāo)準(zhǔn)編制組，召開了標(biāo)準(zhǔn)項目編制啟動會議，對標(biāo)準(zhǔn)編寫工作進行了部署和分工，主要工作過程經(jīng)歷了以下幾個階段。1.立項階段2020年11月，西北稀有金屬材料研究院寧夏有限公司向全國有色金屬標(biāo)準(zhǔn)化技術(shù)委員會重金屬分標(biāo)委提交了YS/T470.1-2004《銅鈹合金化學(xué)分析方法第1部分：電感耦合等離子體原子發(fā)射光譜法測定鈹、鈷、鎳、鈦、鐵、鋁、硅、鉛、鎂量》標(biāo)準(zhǔn)修訂的項目建議書、標(biāo)準(zhǔn)草案和立項報告等材料，經(jīng)全體委員論證同意立項。隨后由秘書處組織全體委員網(wǎng)絡(luò)投票，投票通過后轉(zhuǎn)報給工業(yè)和信息化部科技司，并掛網(wǎng)向社會公開征求意見。2022年4月29日，工業(yè)和信息化部發(fā)布了《關(guān)于印發(fā)2022年第一批行業(yè)標(biāo)準(zhǔn)制修訂和外文版項目計劃的通知》（工信廳科函[2022]94號），正式下達(dá)該標(biāo)準(zhǔn)的修訂任務(wù)，標(biāo)準(zhǔn)名稱為《銅鈹合金化學(xué)分析方法第1部分：鈹、鈷、鎳、鈦、鐵、鋁、硅、鉛、鎂、磷含量的測定電感耦合等離子體原子發(fā)射光譜法》，項目計劃編號為2022-0224T-YS，項目周期為18個月，完成年限為2023年10月，技術(shù)歸口單位為全國有色金屬標(biāo)準(zhǔn)化技術(shù)委員會。2.起草階段2.1任務(wù)落實2022年9月15日至16日，全國有色金屬標(biāo)準(zhǔn)化技術(shù)委員會重金屬分標(biāo)委在江蘇省揚州市召開，并同步召開網(wǎng)絡(luò)會議。組織召開了《銅鈹合金化學(xué)分析方法》修訂任務(wù)落實會。會上確定了由西北稀有金屬材料研究院寧夏有限公司牽頭負(fù)責(zé)《銅鈹合金化學(xué)分析方法第1部分：鈹、鈷、鎳、鈦、鐵、鋁、硅、鉛、鎂、磷含量的測定電感耦合等離子體原子發(fā)射光譜法》的起草工作，由五礦鈹業(yè)股份有限公司、新疆有色金屬研究所、富蘊恒盛鈹業(yè)有限責(zé)任公司、上海有色金屬工業(yè)技術(shù)監(jiān)測中心有限公司四家單位協(xié)助起草；明確了所采用的分析方法及其測定范圍；同時確定了樣品制備單位、進度安排等事項。2.2樣品收集及試驗研究2022年9月~2022年11月編制組委托五礦鈹業(yè)股份有限公司、新疆有色金屬研究所、富蘊恒盛鈹業(yè)有限責(zé)任公司根據(jù)市場上銅鈹合金產(chǎn)品的生產(chǎn)和應(yīng)用情況，結(jié)合西北稀有金屬材料研究院寧夏有限公司生產(chǎn)及研究情況，開展試驗樣品的成分設(shè)計、選材和制備，充分考慮到試驗樣品的代表性，共制備了BeCu-1#（含量近似于C17500,TBe0.5-2.5）、BeCu-2#（含量近似于C17720,TBe2）、BeCu-3#（含量近似于銅鈹中間合金錠）三種牌號的銅鈹合金樣品為本標(biāo)準(zhǔn)統(tǒng)一的試驗樣品，相關(guān)信息見表2所示。表2本標(biāo)準(zhǔn)試驗樣品的基本信息序號水平/%水平/%平/%的含量水平/%平/%1BeCu-1#狀2BeCu-2#狀3BeCu-3#狀2022年12月~2023年5月編制組開展大量試驗研究工作，形成了標(biāo)準(zhǔn)文本和編制說明。試驗內(nèi)容主要包含樣分析譜線選擇、基體效應(yīng)的消除等方法影響因素討論，以及方法相關(guān)精密度和準(zhǔn)確度驗證。3.征求意見階段編制組通過發(fā)函，全國有色金屬標(biāo)準(zhǔn)化技術(shù)委員會將《銅鈹合金化學(xué)分析方法第1部分：鈹、鈷、鎳、鈦、鐵、鋁、硅、鉛、鎂、磷含量的測定電感耦合等離子體原子發(fā)射光譜法》征求意見資料在中國有色金屬標(biāo)準(zhǔn)質(zhì)量信息網(wǎng)（）上掛網(wǎng)，向社會公開征求意見。征求意見的單位包括主要生產(chǎn)、經(jīng)銷、使用、科研、第三方檢驗機構(gòu)等單位及大專院校，征求意見單位廣泛且具有代表性。編制組根據(jù)匯總意見，采納專家意見，對標(biāo)準(zhǔn)討論稿進行修改和完善，形成預(yù)審稿。2023年7月25日～26日由全國有色金屬標(biāo)準(zhǔn)化技術(shù)委員會主持，在浙江省寧波市召開標(biāo)準(zhǔn)討論會，來自中鋁洛陽銅加工有限公司、金川集團股份有限公司、國標(biāo)（北京）檢驗認(rèn)證有限公司、廣東省科學(xué)院工業(yè)分析檢測中心、五礦鈹業(yè)股份有限公司等單位的五十多名專家代表參會，對本文件的預(yù)審稿、編制說明進行了充分、細(xì)致的討論，并提出修改意見。會后，編制組共發(fā)送《征求意見稿》的單位數(shù)22個，收到《征求意見稿》后，回函的單位數(shù)22個，收到《征求意見稿》后，回函并有建議或意見的單位數(shù)10個，詳見標(biāo)準(zhǔn)征求意見稿意見匯總處理表。征求意見范圍廣泛且具代表性，編制組根據(jù)匯總意見，采納以上專家意見，對標(biāo)準(zhǔn)預(yù)審稿進行修改和完善，形成送審稿。二、標(biāo)準(zhǔn)的編制原則（一）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》的要求進行試驗數(shù)據(jù)的統(tǒng)計及重復(fù)性限和再現(xiàn)性限的計算。（二）適用性和先進性本標(biāo)準(zhǔn)是對YS/T470.1-2004《銅鈹合金化學(xué)分析方法第1部分：電感耦合等離子體發(fā)射光譜法測定鈹、鈷、鎳、鈦、鐵、鋁、硅、鉛、鎂量》的修訂起草。在充分調(diào)研國內(nèi)外銅鈹合金相關(guān)產(chǎn)品標(biāo)準(zhǔn)及行業(yè)內(nèi)銅鈹合金分析檢測實際需求的基礎(chǔ)上，對原標(biāo)準(zhǔn)的測定范圍、測定方法、試驗操作的技術(shù)細(xì)節(jié)、精密度數(shù)據(jù)進行修改或補充，進一步規(guī)范了銅鈹合金中鈹、鈷、鎳、鈦、鐵、鋁、硅、鉛、鎂、磷含量的分析方法，同時又體現(xiàn)了行業(yè)內(nèi)對銅鈹合金化學(xué)成分分析的技術(shù)水平，具有先進性、可操作性和廣泛的適用性。主要修訂內(nèi)容如下：1）增加了電感耦合等離子體原子發(fā)射光譜法測定磷量，測定范圍：0.0050％～0.20％。2）更改了部分元素測定范圍，鈹測定范圍由0.10％～3.00％更改為0.010％～6.00%,鈷測定范圍由0.103.00％更改為0.0103.00鎳測定范圍由0.0503.00％更改為0.0103.00鈦測定范圍由0.100.50％更改為0.0100.50鉛測定范圍由0.00500.060％更改為0.00200.060％。3）補充精密度數(shù)據(jù)，提高了標(biāo)準(zhǔn)的可參照性。三、標(biāo)準(zhǔn)主要內(nèi)容的確定依據(jù)及主要試驗和驗證情況分析（一）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，適用于銅鈹合金中多元素含量的分析。因此本標(biāo)準(zhǔn)采用電感耦合等離子體原子發(fā)射光譜儀測定銅鈹合金中鈹、鈷、鎳、鈦、鐵、鋁、硅、鉛、鎂、磷的含量。（二）測定范圍的修訂在制定銅鈹合金中鈹、鈷、鎳、鈦、鐵、鋁、硅、鉛、鎂、磷元素測定范圍時，根據(jù)YS-T334-1995《鈹青銅棒》，YS/T260-2016《銅鈹中間合金錠》，GB24459-2009《鈹銅合金防爆工具》，GB/T26313-2010《鈹青銅無縫管》等標(biāo)準(zhǔn)文件，以及產(chǎn)品客戶的反饋要求，結(jié)合日常檢測樣品實際情況，對產(chǎn)品鈹、鈷、鎳、鈦、鐵、鋁、硅、鉛、鎂、磷元素范圍作了拓展，最終確定出本文件鈹、鈷、鎳、鈦、鐵、鋁、硅、鉛、鎂、磷元素的測定范圍數(shù)值，見表3。表3產(chǎn)品要求各元素范圍與本標(biāo)準(zhǔn)各元素的測定范圍的比較P（三）樣品預(yù)處理銅基合金易溶于硝酸，但合金中硅量較高的話，僅采用硝酸溶解，溶液渾濁，樣品溶解不完全，故需加入一定量的氫氟酸或鹽酸助溶。試驗對不同硅量的銅鈹合金，分別采用硝酸、硝酸-氫氟酸、硝酸-鹽酸溶解，于氫氟酸系統(tǒng)進樣，測定結(jié)果見表4。表4高硅銅鈹合金溶解方法測試對比表4可知，在銅鈹合金中硅量小于或近似于0.20%時，不同溶解方法數(shù)據(jù)差距很小，其測定影響可以忽略，即采用5mL濃硝酸即可滿足分析要求。當(dāng)銅鈹合金中硅量大于0.20%時，采用5mL濃硝酸溶解所得數(shù)據(jù)偏低，而硝酸-氫氟酸、硝酸-鹽酸溶解數(shù)據(jù)更高且比較接近。實際操作中，“硝酸-鹽酸”溶解比“硝酸-氫氟酸”更簡便且易控制，因此，對于高硅銅鈹合金（硅的質(zhì)量分?jǐn)?shù)大于0.20%）樣品，采用加入少量鹽酸助溶處理。（四）分析譜線的選擇按照實驗方法，對標(biāo)準(zhǔn)系列溶液、各單元素標(biāo)準(zhǔn)溶液（1.0μg/mL）和樣品試液進行譜圖掃描分析，分別選擇待測元素各2～3條譜線。觀察待測元素譜線疊加時的譜圖形狀、峰強度及元素間的干擾，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，見表5。表5各元素推薦的分析線波長P（五）基體效應(yīng)和干擾試驗實驗對比了基體匹配和無基體時的各元素的工作曲線，結(jié)果見表6和圖1。由表5結(jié)果及圖1對比工作曲線可以看出，銅基體在本實驗選定的樣品溶液濃度下，對鈹、鎳、鈦的測定譜線強度基本無顯著性影響，但對鈷、鐵、鋁、硅、鉛、鎂、磷的測定譜線強度有一定影響。為保證各元素測定的準(zhǔn)確性，對各元素標(biāo)準(zhǔn)系列溶液進行基體匹配，以消除干擾。表6基體影響實驗P圖1各元素的工作曲線對比（六）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)溶液系列進行測定，以待測元素質(zhì)量濃度為橫坐標(biāo)，發(fā)射強度為縱坐標(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工作曲線與線性回歸P（七）元素檢出限和定量下限的確定按實驗方法分別對11份空白溶液進行測定，以3倍的空白溶液標(biāo)準(zhǔn)偏差計算元素的檢出限（3s）。以10倍的空白溶液標(biāo)準(zhǔn)偏差對應(yīng)的元素質(zhì)量濃度值計算分析方法測定下限，見表8。表8元素檢出限及測定下限%%%%0.0019,0.0019,0.0015,0.0017,0.00130.0019,0.0015,0.0017,0.000.0003,0.0012,0.0010,0.0008,0.00090.0012,0.0010,0.0008,0.000.0009,0.0011,0.0005,0.0001,0.00020.0007,0.0006,0.0006,0.0006,0.00070.0007,0.0006,0.0006,0.000.0001,0.0001,0.0001,0.0002,0.00010.0001,0.0001,0.0001,0.000.0003,0.0004,0.0004,0.0003,0.00040.0004,0.0004,0.0003,0.000.0005,0.0005,0.0004,0.0004,0.00040.0005,0.0005,0.0004,0.000.0005,0.0004,0.0004,0.0005,0.00060.0006,0.0002,0.0004,0.000.0001,0.0001,0.0002,0.0001,0.00010.0002,0.0001,0.0002,0.00P0.0001,0.0012,0.0005,0.0001,0.00030.0011,0.0005,0.0001,0.00表8結(jié)果表明，該方法的測定下限滿足測定范圍要求。第一驗證單位（新疆有色金屬研究所）的方法測定下限見表9。表9一驗（新疆有色金屬研究所）的方法測定下限%%%%0.0014，0.0011，0.0010，0.000.0009，0.0015，0.0010，0.000.0002，0.0021，0.0011，0.000.0007，0.0010，0.0007，0.000.0006，0.0003，0.0004，0.000.0004，0.0003，0.0005，0.000.0004，0.0005，0.0006，0.000.0005，0.0007，0.0004，0.000.0009，0.0005，0.0010，0.00P0.001，0.0011，0.0012，0.001由表9可知，該方法滿足測定范圍要求，與起草單位結(jié)論一致。（八）準(zhǔn)確度試驗1.起草單位加標(biāo)回收試驗在兩個銅鈹合金樣品中加入不同量的各元素標(biāo)準(zhǔn)溶液，按實驗方法進行加標(biāo)回收試驗，結(jié)果見表10。表10起草單位加標(biāo)回收試驗結(jié)果PP由表10數(shù)據(jù)可知，銅鈹合金樣品中各元素的加標(biāo)回收率在97.0％～104.0％之間，方法測定結(jié)果準(zhǔn)確度滿足銅鈹合金中各元素含量的分析方法要求。第一驗證單位（新疆有色金屬研究所）的加標(biāo)回收試驗結(jié)果見表11。表11一驗（新疆有色金屬研究所）加標(biāo)回收試驗結(jié)果PP由表11可知，各元素的加標(biāo)回收率均在96.2％～104.9％之間，說明該方法測定結(jié)果準(zhǔn)確可靠，與起草單位結(jié)論一致。第一驗證單位（五礦鈹業(yè)股份有限公司）的加標(biāo)回收試驗結(jié)果見表12。表12一驗（五礦鈹業(yè)股份有限公司）加標(biāo)回收試驗結(jié)果PP由表12可知，各元素的加標(biāo)回收率均在96.7％～104.6％之間，說明該方法測定結(jié)果準(zhǔn)確可靠，與起草單位結(jié)論一致。2.標(biāo)樣測定以本法測定牌號為99M301（美國加聯(lián)公司）、DM8089（美國加聯(lián)公司）銅鈹合金標(biāo)準(zhǔn)樣品，檢驗方法準(zhǔn)確度，結(jié)果見表13。表13標(biāo)樣測定結(jié)果標(biāo)準(zhǔn)值/%不確定度/%測定值/%是是是是是是是是是是是是是是是是P是由表13數(shù)據(jù)可知，本法測定兩種銅鈹合金標(biāo)準(zhǔn)樣品與標(biāo)準(zhǔn)值吻合，方法測定結(jié)果準(zhǔn)確度滿足銅鈹合金中各元素含量的分析方法要求。（九）精密度試驗對3個不同鈹、鈷、鎳、鈦、鐵、鋁、硅、鉛、鎂、磷含量的銅鈹合金樣品，采用本方法對鈹、鈷、鎳、鈦、鐵、鋁、硅、鉛、鎂、磷含量分別獨立地進行11次測定，測定結(jié)果表14起草單位精密度實驗％（平均值/%sRSD/%0.476,0.495,0.492,0.469,0.493486,0.472,0.489,0.473,0.0378,0.0394,0.0398,0.0384,0.380,0.0394,0.0394,0.0401,0.0.0818,0.0826,0.0828,0.0815,0820,0.0826,0.0826,0.0828,0.0810.313,0.316,0.316,0.315,0.314,0.0248,0.0255,0.0270,0.0262,0250,0.0255,0.0257,0.0271,0.020.0206,0.0201,0.0203,0.0202,0211,0.0201,0.0201,0.0203,0.0200.0218,0.0220,0.0218,0.0218,0220,0.0220,0.0220,0.0218,0.020.0168,0.0185,0.0172,0.0188,0170,0.0185,0.0182,00.0211,0.0202,0.0201,0.0201,0210,0.0202,0.0202,0.0203,0.02P0.0386,0.0397,0.0406,0.0407,0.390,0.0397,0.0395,0.0406,0.02.467,2.471,2.452,2.428,2.463,428,2.466,2.473,2.462,0.306,0.301,0.304,0.305,0.3090.405,0.406,0.405,0.406,0.404,402,0.407,0.406,0.400.120,0.119,0.121,0.121,0.122,0.118,0.117,0.117,0.118,0.118,0.104,0.101,0.102,0.103,0.103,0.111,0.108,0.109,0.109,0.1090.0101,0.0102,0.0096,0.0096,0101,0.0096,0.0099,00.0995,0.0997,0.0991,0.1000,0995,0.0997,0.0991,0.1000,0.099P0.141,0.140,0.142,0.141,0.142,3.908,3.829,3.832,3.877,3.8922,3.834,3.834,3.82.794,2.767,2.792,2.766,2.7952.824,2.789,2.821,2.789,2.8160.0319,0.0311,0.0311,0.0312,0.319,0.0311,0.0314,0.0312,0.0.265,0.262,0.263,0.261,0.2630.261,0.254,0.253,0.253,0.258254,0.258,0.253,0.20.0629,0.0622,0.0581,0.0606,0.621,0.0617,0.0599,0.0606,0.050.0489,0.0463,0.0482,0.0487,0.489,0.0463,0.0481,0.0487,0.04870.264,0.252,0.256,0.254,0.254251,0.256,0.254,0.2P0.0161,0.0165,0.0157,0.0172,0.由表14結(jié)果可知，本法的RSD％在0.30％～4.05％之間，精密度較好，能滿足方法分析要求。第一驗證單位（五礦鈹業(yè)股份有限公司）的精密度試驗結(jié)果見表15。表15一驗（五礦鈹業(yè)股份有限公司）精密度實驗％（/%sRSD/%0.462,0.466,0.484,0.462,0.482,0.40.0366,0.0377,0.0365,0.0355,0.03760.0366,0.0375,0.0364,0.030.0757,0.0776,0.0785,0.0777,0.07650.0774,0.0767,0.0766,0.070.318,0.314,0.319,0.315,0.313,0.30.0231,0.0247,0.0241,0.0247,0.0240.0236,0.0233,0.0247,0.020.0213,0.0212,0.0215,0.0222,0.02210.0224,0.0211,0.0212,0.020.0197,0.0194,0.0193,0.0192,0.01970.0195,0.0193,0.0184,0.010.0161,0.0159,0.0165,0.0171,0.01550.0163,0.0169,0.0176,0.010.0203,0.0187,0.0173,0.0198,0.01860.0183,0.0183,0.0196,0.01P0.0375,0.0384,0.0392,0.0377,0.03760.0377,0.0395,0.0394,0.032.407,2.401,2.428,2.407,2.433,2.0.318,0.314,0.309,0.305,0.313,0.30.396,0.399,0.395,0.392,0.396,0.30.117,0.124,0.123,0.122,0.123,0.10.111,0.114,0.113,0.110,0.111,0.10.107,0.106,0.103,0.108,0.117,0.10.103,0.103,0.102,0.103,0.0.0992,0.102,0.0997,0.0.0101,0.0114,0.0103,0.0112,0.01000.0113,0.0103,0.0104,0.010.0964,0.0962,0.0979,0.0965,0.0980.0961,0.0962,0.0965,0.09P0.138,0.134,0.139,0.135,0.134,0.13.821,3.817,3.866,3.824,3.874,32.753,2.741,2.752,2.749,2.759,2.742.773,2.771,2.768,2.779,2.789,2.70.0319,0.0311,0.0311,0.0312,0.0310.0311,0.0314,0.0312,0.030.257,0.258,0.254,0.256,0.252,0.250.255,0.257,0.259,0.251,0.254,0.20.0579,0.0593,0.0585,0.0598,0.0590.0587,0.0603,0.0587,0.050.0457,0.0428,0.0444,0.0437,0.04530.0448,0.0432,0.0459,0.040.256,0.255,0.254,0.249,0.261,0.2P0.0153,0.0147,0.0155,0.0161,0.01650.0149,0.0162,0.0158,0.01由表15可知，樣品中各元素的相對標(biāo)準(zhǔn)偏差在0.27％～4.86％之間，說明該方法的精密度良好，與起草單位結(jié)論一致。第一驗證單位（新疆有色金屬研究所）的精密度試驗結(jié)果見表16。表16一驗（新疆有色金屬研究所）精密度實驗％（/%sRSD/%0.466,0.469,0.459,0.471,0.0.468,0.471,0.463,00.0376,0.0398,0.0380,0.0390,0.03890.0378,0.0378,0.0371,0.030.0805,0.0799,0.0792,0.0820,0.0810.0802,0.0795,0.0812,0.080.306,0.312,0.310,0.310,0.308,0.30.0249，0.0250，0.0247，0.020.0200，0.0213，0.0219，0.020.0209,0.0211,0.0208,0.0208,0.02020.0202,0.0213,0.0208,0.020.0171,0.0167,0.0174,0.0171,0.0170.0169,0.0173,0.0168,0.010.0203,0.0198,0.0196,0.0200,0.0190.0200,0.0202,0.0196,0.020P0.0393,0.0396,0.0390,0.0387,0.0390.0396,0.0395,0.0395,0.032.411,2.428,2.417,2.431,2.433,2.40.299,0.302,0.300,0.299,0.297,0.30.397,0.398,0.400,0.399,0.403,0.40.123,0.123,0.120,0.120,0.120,0.10.112,0.113,0.112,0.113,0.113,0.110.110,0.109,0.111,0.109,0.111,0.10.106,0.105,0.104,0.104,0.104,0.10.0103,0.0102,0.0101,0.0096,0.01050.0100,0.0102,0.0104,0.000.0963,0.0938,0.0947,0.0939,0.0960.0950,0.0957,0.0940,0.09P0.135,0.140,0.139,0.138,0.140,0.133.789,3.811,3.812,3.835,3.811,32.751,2.756,2.728,2.746,2.736,2.72.813,2.787,2.797,2.780,2.807,2.70.0314,0.0326,0.0302,0.0316,0.0290.0308,0.0320,0.0302,0.020.267,0.265,0.263,0.264,0.262,0.260.257,0.260,0.262,0.258,0.259,0.260.0593,0.0590,0.0591,0.0597,0.05950.0599,0.0595,0.0592,0.060.0437,0.0441,0.0434,0.0450,0.0440.0466,0.0447,0.0442,0.040.244,0.248,0.242,0.247,0.245,0.24P0.0169,0.0170,0.0172,0.0175,0.01680.0169,0.0167,0.0166,0.016由表16結(jié)果可知，本法的RSD％在0.40％～3.25％之間，說明該方法的精密度良好，與起草單位結(jié)論一致。第二驗證單位（富蘊恒盛鈹業(yè)有限責(zé)任公司）的精密度試驗結(jié)果見表17。表17二驗（富蘊恒盛鈹業(yè)有限責(zé)任公司）精密度實驗％（平均值/%sRSD/%0.473,0.466,0.473,0.455,0.468,0.40.0377,0.0379,0.0395,0.0377,0.0390.0393,0.0385,0.0378,0.030.0801,0.0810,0.0811,0.0813,0.0810.0778,0.0791,0.0786,0.080.306,0.305,0.303,0.308,0.309,0.30.0265,0.0262,0.0261,0.0264,0.0260.0260,0.0260,0.0259,0.0260.0212,0.0209,0.0213,0.0214,0.0200.0210,0.0204,0.0206,0.020.0220,0.0216,0.0215,0.0199,0.0200.0219,0.0205,0.0202,0.020.0171,0.0168,0.0168,0.0173,0.0160.0170,0.0173,0.0165,0.010.0199,0.0198,0.0195,0.0195,0.0190.0196,0.0198,0.0198,0.01P0.0401,0.0398,0.0389,0.0391,0.0390.0395,0.0395,0.0386,0.032.423,2.437,2.424,2.455,20.300,0.296,0.294,0.301,0.301,0.30.407,0.396,0.399,0.394,0.397,0.30.117,0.117,0.117,0.120,0.118,0.10.114,0.109,0.109,0.114,0.113,0.10.108,0.106,0.107,0.107,0.107,0.10.104,0.103,0.104,0.107,0.107,0.10.0097,0.0097,0.0092,0.0086,0.0080.0091,0.0093,0.0097,0.000.0958,0.0961,0.0977,0.0967,0.0960.0964，0.0977,0.0967,0.09P0.139,0.139,0.140,0.139,0.137,0.13.893,3.833,3.855,3.911,3.877,3.2.776,2.804,2.776,2.770,2.802,2.2.792,2.784,2.786,2.813,2.817,2.80.0289,0.0316,0.0298,0.0312,0.0310.0294,0.0291,0.0315,0.020.255,0.256,0.253,0.251,0.255,0.20.250,0.246,0.249,0.249,0.255,0.20.0591,0.0584,0.0593,0.0585,0.05880.0604,0.0594,0.0595,0.0610.0457,0.0469,0.0470,0.0470,0.0470.0479,0.0491,0.0477,0.040.253,0.254,0.253,0.254,0.254,0.2P0.0162,0.0156,0.0161,0.0161,0.0150.0164,0.0157,0.0160,0.01由表17結(jié)果可知，本法的RSD％在0.26％～5.03％之間，精密度較好，能滿足方法分析要求。與起草單位結(jié)論一致。第二驗證單位（上海有色金屬工業(yè)技術(shù)監(jiān)測中心有限公司）的精密度試驗結(jié)果見表18。表18二驗（上海有色金屬工業(yè)技術(shù)監(jiān)測中心有限公司）精密度實驗％（/%s%0.489/0.485/0.487/0.485/0.481/0.40.0385/0.0387/0.0388/0.0384/0.0380.0385/0.0390/0.0385/0.030.0839/0.0856/0.0877/0.0855/0.0860.0820/0.0826/0.0818/0.080.314/0.304/0.324/0.320/0.329/0.30.0251/0.0254/0.0250/0.0254/0.0250.0266/0.0259/0.0264/0.020.0198/0.0205/0.0203/0.0198/0.0190.0210/0.0199/0.0208/0.020.0203/0.0205/0.0220/0.0204/0.0190.0211/0.0207/0.0203/0.020.0176/0.0172/0.0171/0.0174/0.0160.0179/0.0169/0.0173/0.010.0207/0.0202/0.0192/0.0186/0.0180.0206/0.0194/0.0206/0.01P0.0380/0.0385/0.0388/0.0389/0.0390.0396/0.0393/0.0387/0.032.437/2.429/2.418/2.417/2.431/2.0.293/0.294/0.297/0.290/0.299/0.30.403/0.403/0.404/0.405/0.402/0.40.121/0.119/0.118/0.120/0.121/0.10.114/0.115/0.113/0.113/0.112/0.10.102/0.102/0.103/0.103/0.103/0.10.110/0.111/0.109/0.108/0.108/0.10.0093/0.0097/0.0094/0.0095/0.0090.0089/0.0093/0.0094/0.000.0993/0.0998/0.0996/0.0987/0.0990.0997/0.0989/0.0984/0.09P0.139/0.138/0.138/0.136/0.139/0.13.815/3.813/3.824/3.831/3.814/32.795/2.779/2.786/2.794/2.797/2.2.818/2.818/2.824/2.819/2.835/2.0.0311/0.0289/0.0304/0.0310/0.0310.0304/0.0311/0.0319/0.020.255/0.254/0.256/0.254/0.260/0.20.257/0.251/0.254/0.256/0.259/0.20.0602/0.0595/0.0611/0.0598/0.0600.0612/0.0597/0.0607/0.060.0440/0.0422/0.0485/0.0436/0.0470.0459/0.0431/0.0436/0.040.249/0.244/0.245/0.250/0.251/0.2P0.0169/0.0163/0.0161/0.0165/0.0150.0164/0.0159/0.0168/0.01由表18結(jié)果可知，本法的RSD％在0.15％～4.90％之間，精密度較好，能滿足方法分析要求。與起草單位結(jié)論一致。（十）主要實驗（或驗證）的分析按照GB/T6379.2-2004《測量方法與結(jié)果的準(zhǔn)確度》，通過對西北稀有金屬材料研究院寧夏有限公司、五礦鈹業(yè)股份有限公司、新疆有色金屬研究所、富蘊恒盛鈹業(yè)有限責(zé)任公司、上海有色金屬工業(yè)技術(shù)監(jiān)測中心有限公司五家單位的試驗數(shù)據(jù)和驗證數(shù)據(jù)分別按照重復(fù)性和再現(xiàn)性的公式進行計算，得到了不同含量的重復(fù)性限和再現(xiàn)性限。1.樣品數(shù)據(jù)對比起草單位與驗證單位的試驗結(jié)果統(tǒng)計對比見表19～表28。表19鈹?shù)脑囼灲Y(jié)果對比X,%sX,%sX,%s西北稀有金屬材料研究院寧夏有上海有色金屬工業(yè)技術(shù)監(jiān)測中心表20鈷的試驗結(jié)果對比X,%sX,%sX,%s西北稀有金屬材料研究院寧夏有上海有色金屬工業(yè)技術(shù)監(jiān)測中心表21鎳的試驗結(jié)果對比X,%sX,%sX,%s西北稀有金屬材料研究院寧夏有上海有色金屬工業(yè)技術(shù)監(jiān)測中心表22鈦的試驗結(jié)果對比X,%sX,%sX,%s西北稀有金屬材料研究院寧夏有上海有色金屬工業(yè)技術(shù)監(jiān)測中心表23鐵的試驗結(jié)果對比X,%sX,%sX,%s西北稀有金屬材料研究院寧夏有上海有色金屬工業(yè)技術(shù)監(jiān)測中心表24鋁的試驗結(jié)果對比X,%sX,%sX,%s西北稀有金屬材料研究院寧夏有上海有色金屬工業(yè)技術(shù)監(jiān)測中心表25硅的試驗結(jié)果對比X,%sX,%sX,%s西北稀有金屬材料研究院寧夏有上海有色金屬工業(yè)技術(shù)監(jiān)測中心表26鉛的試驗結(jié)果對比X,%sX,%sX,%s西北稀有金屬材料研究院寧夏有上海有色金屬工業(yè)技術(shù)監(jiān)測中心表27鎂的試驗結(jié)果對比X,%sX,%sX,%s西北稀有金屬材料研究院寧夏有上海有色金屬工業(yè)技術(shù)監(jiān)測中心表28磷的試驗結(jié)果對比X,%sX,%sX,%s西北稀有金屬材料研究院寧夏有上海有色金屬工業(yè)技術(shù)監(jiān)測中心采用格拉布斯檢驗方法，分別對五家單位中鈹、鈷、鎳、鈦、鐵、鋁、硅、鉛、鎂、磷含量的檢測數(shù)據(jù)進行異常值情況分析，結(jié)果見表29～表78。111 1 Snn nS表29不同鈹含量水平樣品分析結(jié)果異常值分析（西材院） X/%sG/%G/%表30不同鈷含量水平樣品分析結(jié)果異常值分析（西材院） X/%sG/%G/%表31不同鎳含量水平樣品分析結(jié)果異常值分析（西材院） X/%sG/%G/%表32不同鈦含量水平樣品分析結(jié)果異常值分析（西材院） X/%sG/%G/%表33不同鐵含量水平樣品分析結(jié)果異常值分析（西材院） X/%sG/%G/%表34不同鋁含量水平樣品分析結(jié)果異常值分析（西材院） X/%sG/%G/%表35不同硅含量水平樣品分析結(jié)果異常值分析（西材院） X/%sG/%G/%表36不同鉛含量水平樣品分析結(jié)果異常值分析（西材院） X/%sG/%G/%表37不同鎂含量水平樣品分析結(jié)果異常值分析（西材院） X/%sG/%G/%表38不同磷含量水平樣品分析結(jié)果異常值分析（西材院） X/%sG/%G/%表39不同鈹含量水平樣品分析結(jié)果異常值分析（五礦鈹業(yè)） X/%sG/%G/%表40不同鈷含量水平樣品分析結(jié)果異常值分析（五礦鈹業(yè)） X/%sG/%G/%表41不同鎳含量水平樣品分析結(jié)果異常值分析（五礦鈹業(yè)） X/%sG/%G/%表42不同鈦含量水平樣品分析結(jié)果異常值分析（五礦鈹業(yè)） X/%sG/%G/%表43不同鐵含量水平樣品分析結(jié)果異常值分析（五礦鈹業(yè)） X/%sG/%G/%表44不同鋁含量水平樣品分析結(jié)果異常值分析（五礦鈹業(yè)） X/%sG/%G/%表45不同硅含量水平樣品分析結(jié)果異常值分析（五礦鈹業(yè)） X/%sG/%G/%表46不同鉛含量水平樣品分析結(jié)果異常值分析（五礦鈹業(yè)） X/%sG/%G/%表47不同鎂含量水平樣品分析結(jié)果異常值分析（五礦鈹業(yè)） X/%sG/%G/%表48不同磷含量水平樣品分析結(jié)果異常值分析（五礦鈹業(yè)） X/%sG/%G/%表49不同鈹含量水平樣品分析結(jié)果異常值分析（新疆有色） X/%sG/%G/%表50不同鈷含量水平樣品分析結(jié)果異常值分析（新疆有色） X/%sG/%G/%表51不同鎳含量水平樣品分析結(jié)果異常值分析（新疆有色） X/%sG/%G/%表52不同鈦含量水平樣品分析結(jié)果異常值分析（新疆有色） X/%sG/%G/%表53不同鐵含量水平樣品分析結(jié)果異常值分析（新疆有色） X/%sG/%G/%表54不同鋁含量水平樣品分析結(jié)果異常值分析（新疆有色） X/%sG/%G/%表55不同硅含量水平樣品分析結(jié)果異常值分析（新疆有色） X/%sG/%G/%表56不同鉛含量水平樣品分析結(jié)果異常值分析（新疆有色） X/%sG/%G/%表57不同鎂含量水平樣品分析結(jié)果異常值分析（新疆有色） X/%sG/%G/%表58不同磷含量水平樣品分析結(jié)果異常值分析（新疆有色） X/%sG/%G/%表59不同鈹含量水平樣品分析結(jié)果異常值分析（富蘊恒盛） X/%sG/%G/%表60不同鈷含量水平樣品分析結(jié)果異常值分析（富蘊恒盛） X/%sG/%G/%表61不同鎳含量水平樣品分析結(jié)果異常值分析（富蘊恒盛） X/%sG/%G/%表62不同鈦含量水平樣品分析結(jié)果異常值分析（富蘊恒盛） X/%sG/%G/%表63不同鐵含量水平樣品分析結(jié)果異常值分析（富蘊恒盛） X/%sG/%G/%表64不同鋁含量水平樣品分析結(jié)果異常值分析（富蘊恒盛） X/%sG/%G/%表65不同硅含量水平樣品分析結(jié)果異常值分析（富蘊恒盛） X/%sG/%G/%表66不同鉛含量水平樣品分析結(jié)果異常值分析（富蘊恒盛） X/%sG/%G/%表67不同鎂含量水平樣品分析結(jié)果異常值分析（富蘊恒盛） X/%sG/%G/%表68不同磷含量水平樣品分析結(jié)果異常值分析（富蘊恒盛） X/%sG/%G/%表69不同鈹含量水平樣品分析結(jié)果異常值分析（上海監(jiān)測） X/%sG/%G/%表70不同鈷含量水平樣品分析結(jié)果異常值分析（上海監(jiān)測） X/%sG/%G/%表71不同鎳含量水平樣品分析結(jié)果異常值分析（上海監(jiān)測） X/%sG/%G/%表72不同鈦含量水平樣品分析結(jié)果異常值分析（上海監(jiān)測） X/%sG/%G/%表73不同鐵含量水平樣品分析結(jié)果異常值分析（上海監(jiān)測） X/%sG/%G/%表74不同鋁含量水平樣品分析結(jié)果異常值分析（上海監(jiān)測） X/%sG/%G/%表75不同硅含量水平樣品分析結(jié)果異常值分析（上海監(jiān)測） X/%sG/%G/%表76不同鉛含量水平樣品分析結(jié)果異常值分析（上海監(jiān)測） X/%sG/%G/%表77不同鎂含量水平樣品分析結(jié)果異常值分析（上海監(jiān)測） X/%sG/%G/%表78不同磷含量水平樣品分析結(jié)果異常值分析（上海監(jiān)測） X/%sG/%G/%根據(jù)格拉布斯檢驗方法，查表得：n=11,a=0.05時，舍棄界限值為2.234。表29～表78數(shù)據(jù)結(jié)果顯示鈹、鈷、鎳、鈦、鐵、鋁、硅、鉛、鎂、磷不同含量樣品的各單位11次測定數(shù)據(jù)均無異常值。2.方法的重復(fù)性限和再現(xiàn)性限1.重復(fù)性在重復(fù)性條件下獲得的兩次獨立測試結(jié)果的測定值，在表79給出的平均值范圍內(nèi)，這兩個測試結(jié)果的絕對差值不超過重復(fù)性限（r超過重復(fù)性限（r）情況不超過5％。重復(fù)性限（r）按表79數(shù)據(jù)采用線性內(nèi)插法或外延法求得。精密度試驗原始數(shù)據(jù)見附錄A。表79重復(fù)性限w/%r/%w/%r/%w/%r/%w/%r/%w/%r/%w/%r/%w/%r/%w/%r/%w/%r/%w/%r/%2.再現(xiàn)性在再現(xiàn)性條件下獲得的兩次獨立測試結(jié)果的測定值，在表80給出的平均值范圍內(nèi)，兩個測試結(jié)果的絕對差值不應(yīng)超過再現(xiàn)性限（R超過再現(xiàn)性限（R）的情況不超過5%，再現(xiàn)性限（R）按表80數(shù)據(jù)采用線性內(nèi)插法或外延法求得。