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在直讀光譜儀分析中的四類“標樣”

點擊次數:1167  更新時間:2023-02-03

1、 標(biao)(biao)(biao)(biao)(biao)準(zhun)樣(yang)(yang)(yang)品(pin)(pin)(pin)(pin)(Standard Sample):光(guang)譜(pu)定量分(fen)(fen)析(xi)(xi)是(shi)一(yi)種相對分(fen)(fen)析(xi)(xi)方法,必須使(shi)用(yong)(yong)含量經(jing)(jing)過(guo)精確(que)標(biao)(biao)(biao)(biao)(biao)定的(de)(de)(de)(de)樣(yang)(yang)(yang)品(pin)(pin)(pin)(pin)來制作(zuo)(zuo)校(xiao)準(zhun)曲線(Calibration Curve)或工(gong)(gong)作(zuo)(zuo)曲線(Work Curve),以確(que)定分(fen)(fen)析(xi)(xi)樣(yang)(yang)(yang)品(pin)(pin)(pin)(pin)(Unknown Sample)的(de)(de)(de)(de)含量,這種含量經(jing)(jing)過(guo)精確(que)標(biao)(biao)(biao)(biao)(biao)定的(de)(de)(de)(de)樣(yang)(yang)(yang)品(pin)(pin)(pin)(pin)一(yi)直被光(guang)譜(pu)分(fen)(fen)析(xi)(xi)工(gong)(gong)作(zuo)(zuo)者稱為“標(biao)(biao)(biao)(biao)(biao)準(zhun)樣(yang)(yang)(yang)品(pin)(pin)(pin)(pin)”,簡稱為“標(biao)(biao)(biao)(biao)(biao)樣(yang)(yang)(yang)”(或“標(biao)(biao)(biao)(biao)(biao)鋼”),其(qi)正規名稱是(shi) “標(biao)(biao)(biao)(biao)(biao)準(zhun)(參考)物(wu)(wu)質(zhi)”(Conference Materials),又簡稱為“標(biao)(biao)(biao)(biao)(biao)物(wu)(wu)”。光(guang)譜(pu)定量分(fen)(fen)析(xi)(xi)的(de)(de)(de)(de)標(biao)(biao)(biao)(biao)(biao)準(zhun)樣(yang)(yang)(yang)品(pin)(pin)(pin)(pin)都是(shi)成(cheng)套的(de)(de)(de)(de),用(yong)(yong)于(yu)金屬樣(yang)(yang)(yang)品(pin)(pin)(pin)(pin)光(guang)電光(guang)譜(pu)分(fen)(fen)析(xi)(xi)的(de)(de)(de)(de)標(biao)(biao)(biao)(biao)(biao)準(zhun)樣(yang)(yang)(yang)品(pin)(pin)(pin)(pin)一(yi)般是(shi)塊狀(zhuang)(zhuang)或棒(bang)狀(zhuang)(zhuang),其(qi)基本要(yao)求(qiu)是(shi):分(fen)(fen)析(xi)(xi)元素分(fen)(fen)布(bu)均(jun)勻,化(hua)學成(cheng)份可(ke)(ke)(ke)靠;組織結構、尺寸、加工(gong)(gong)方法等要(yao)與分(fen)(fen)析(xi)(xi)樣(yang)(yang)(yang)品(pin)(pin)(pin)(pin)基本一(yi)致,不能有偏析(xi)(xi)、裂紋、夾雜(za)等缺(que)陷,并經(jing)(jing)過(guo)均(jun)勻度檢查(cha)符合(he)要(yao)求(qiu);一(yi)套標(biao)(biao)(biao)(biao)(biao)準(zhun)樣(yang)(yang)(yang)品(pin)(pin)(pin)(pin)分(fen)(fen)析(xi)(xi)元素含量要(yao)有一(yi)定梯度,含量范圍比要(yao)求(qiu)分(fen)(fen)析(xi)(xi)的(de)(de)(de)(de)含量范圍稍(shao)寬。各(ge)國的(de)(de)(de)(de)“標(biao)(biao)(biao)(biao)(biao)準(zhun)物(wu)(wu)質(zhi)”的(de)(de)(de)(de)研(yan)制都是(shi)嚴格(ge)管理(li)的(de)(de)(de)(de),獲得國家部門認(ren)可(ke)(ke)(ke)的(de)(de)(de)(de)標(biao)(biao)(biao)(biao)(biao)準(zhun)物(wu)(wu)質(zhi)一(yi)般是(shi)公開銷售的(de)(de)(de)(de)。標(biao)(biao)(biao)(biao)(biao)準(zhun)物(wu)(wu)質(zhi)的(de)(de)(de)(de)詳(xiang)細知識和行(xing)情可(ke)(ke)(ke)到“中(zhong)國標(biao)(biao)(biao)(biao)(biao)準(zhun)物(wu)(wu)質(zhi)網”咨(zi)詢。為了(le)同下(xia)面要(yao)講(jiang)的(de)(de)(de)(de)幾(ji)類標(biao)(biao)(biao)(biao)(biao)樣(yang)(yang)(yang)相區別,分(fen)(fen)析(xi)(xi)工(gong)(gong)作(zuo)(zuo)者常把建立校(xiao)準(zhun)曲線的(de)(de)(de)(de)標(biao)(biao)(biao)(biao)(biao)準(zhun)樣(yang)(yang)(yang)品(pin)(pin)(pin)(pin)常稱為“校(xiao)準(zhun)標(biao)(biao)(biao)(biao)(biao)樣(yang)(yang)(yang)”(Calibration Standards or Calibration Samples)或“工(gong)(gong)作(zuo)(zuo)曲線標(biao)(biao)(biao)(biao)(biao)樣(yang)(yang)(yang)”。 


2、 標(biao)(biao)準(zhun)化(hua)(hua)(hua)樣(yang)(yang)品(pin)(Standardization Sample):用“持久曲(qu)線(xian)法(fa)”進行光譜定(ding)量(liang)分(fen)析(xi),儀器(qi)參數漂(piao)移不(bu)可(ke)避免要引起(qi)工作曲(qu)線(xian)漂(piao)移,需要通(tong)過“標(biao)(biao)準(zhun)化(hua)(hua)(hua)”(Standardization)來調整(zheng)。標(biao)(biao)準(zhun)化(hua)(hua)(hua)樣(yang)(yang)品(pin)就是標(biao)(biao)準(zhun)化(hua)(hua)(hua)操作中所用的特(te)(te)殊樣(yang)(yang)品(pin),有(you)的資料里又有(you) “校(xiao)正(zheng)標(biao)(biao)樣(yang)(yang)”(Setting-up Samples)、再校(xiao)準(zhun)標(biao)(biao)樣(yang)(yang)(Recalibration Samples)等名稱(cheng)。其基本要求(qiu)(qiu)是:組成和結構均勻穩定(ding),目標(biao)(biao)元素的含量(liang)有(you)特(te)(te)定(ding)要求(qiu)(qiu),但(dan)不(bu)必有(you)準(zhun)確的標(biao)(biao)定(ding)值。用于低端(duan)的標(biao)(biao)準(zhun)化(hua)(hua)(hua)樣(yang)(yang)品(pin)的光強值盡可(ke)能接近相應(ying)元素校(xiao)準(zhun)曲(qu)線(xian)的低端(duan)值,用于標準化樣品(pin)的光強值(zhi)盡可能(neng)在相應元素(su)校(xiao)準曲線的范圍(wei)。標(biao)準(zhun)(zhun)(zhun)(zhun)樣品(pin)(pin)(pin)(pin)可(ke)(ke)(ke)以(yi)用作(zuo)標(biao)準(zhun)(zhun)(zhun)(zhun)化樣品(pin)(pin)(pin)(pin),但要為(wei)盡(jin)可(ke)(ke)(ke)能(neng)多的(de)(de)(de)(de)(de)元素選取(qu)數目盡(jin)可(ke)(ke)(ke)能(neng)少的(de)(de)(de)(de)(de)標(biao)準(zhun)(zhun)(zhun)(zhun)化樣品(pin)(pin)(pin)(pin)是(shi)個難題。標(biao)準(zhun)(zhun)(zhun)(zhun)化樣品(pin)(pin)(pin)(pin)應該在(zai)作(zuo)校準(zhun)(zhun)(zhun)(zhun)曲線(xian)的(de)(de)(de)(de)(de)同時測光以(yi)確定(ding)初始數值,若要使用儀(yi)器(qi)“隨機”所帶的(de)(de)(de)(de)(de)校準(zhun)(zhun)(zhun)(zhun)曲線(xian),必(bi)然需要儀(yi)器(qi)商提供(gong)相應的(de)(de)(de)(de)(de)標(biao)準(zhun)(zhun)(zhun)(zhun)化樣品(pin)(pin)(pin)(pin)。標(biao)準(zhun)(zhun)(zhun)(zhun)化樣品(pin)(pin)(pin)(pin)是(shi)可(ke)(ke)(ke)以(yi)更換的(de)(de)(de)(de)(de),但必(bi)須在(zai)舊(jiu)的(de)(de)(de)(de)(de)標(biao)準(zhun)(zhun)(zhun)(zhun)化樣品(pin)(pin)(pin)(pin)用完之前試驗確定(ding)新的(de)(de)(de)(de)(de)標(biao)準(zhun)(zhun)(zhun)(zhun)化樣品(pin)(pin)(pin)(pin)的(de)(de)(de)(de)(de)測光值。


3、 監(jian)(jian)(jian)控樣(yang)(yang)(Control Sample):光譜分析(xi)的(de)(de)(de)自動化(hua)程(cheng)序中,用(yong)(yong)于(yu)監(jian)(jian)(jian)控儀器(qi)的(de)(de)(de)漂移程(cheng)度,把握恰當(dang)的(de)(de)(de)標(biao)準(zhun)(zhun)化(hua)操(cao)作(Standardization)時機,從(cong)而保持儀器(qi)正常工作狀態的(de)(de)(de)試樣(yang)(yang)。通過數理(li)統計(ji)分析(xi)確(que)定(ding)(ding)監(jian)(jian)(jian)控樣(yang)(yang)監(jian)(jian)(jian)控的(de)(de)(de)目標(biao)元素測(ce)定(ding)(ding)值的(de)(de)(de)上(shang)、下限,按設定(ding)(ding)的(de)(de)(de)時間間隔(一般(ban)比兩次標(biao)準(zhun)(zhun)化(hua)的(de)(de)(de)間隔短(duan))分析(xi)監(jian)(jian)(jian)控樣(yang)(yang),若目標(biao)元素的(de)(de)(de)測(ce)定(ding)(ding)值超出(chu)界(jie)限,則報警提示進行相應的(de)(de)(de)標(biao)準(zhun)(zhun)化(hua)操(cao)作;用(yong)(yong)新的(de)(de)(de)標(biao)準(zhun)(zhun)化(hua)系數修正產生報警的(de)(de)(de)監(jian)(jian)(jian)控樣(yang)(yang)的(de)(de)(de)測(ce)定(ding)(ding)值,若合格則標(biao)準(zhun)(zhun)化(hua)有效。用(yong)(yong)人工方式也(ye)可(ke)以使用(yong)(yong)監(jian)(jian)(jian)控樣(yang)(yang),使日(ri)常標(biao)準(zhun)(zhun)化(hua)操(cao)作更合理(li),并可(ke)減少標(biao)準(zhun)(zhun)化(hua)樣(yang)(yang)品的(de)(de)(de)日(ri)常消耗(hao)。 


4、 “內(nei)(nei)控(kong)(kong)(kong)(kong)(kong)(kong)(kong)樣(yang)”或“類標準(zhun)化(hua)樣(yang)品(pin)(pin)(pin)”(Type Standard Sample):“內(nei)(nei)控(kong)(kong)(kong)(kong)(kong)(kong)(kong)樣(yang)”源于“控(kong)(kong)(kong)(kong)(kong)(kong)(kong)制(zhi)試(shi)(shi)樣(yang)法(fa)”所用(yong)的(de)(de)(de)(de)(de)(de)“控(kong)(kong)(kong)(kong)(kong)(kong)(kong)制(zhi)試(shi)(shi)樣(yang)”。起(qi)初(chu)在攝譜(pu)法(fa)中是用(yong)一(yi)(yi)(yi)控(kong)(kong)(kong)(kong)(kong)(kong)(kong)制(zhi)樣(yang)品(pin)(pin)(pin)和分(fen)析樣(yang)品(pin)(pin)(pin)一(yi)(yi)(yi)起(qi)攝譜(pu),以(yi)確(que)(que)定工作曲(qu)(qu)線(xian)(xian)的(de)(de)(de)(de)(de)(de)移動位置(zhi);后來有人(ren)提出(chu)用(yong)簡單(dan)的(de)(de)(de)(de)(de)(de)合金或二元(yuan)(yuan)合金做出(chu)工作曲(qu)(qu)線(xian)(xian),用(yong)控(kong)(kong)(kong)(kong)(kong)(kong)(kong)制(zhi)試(shi)(shi)樣(yang)確(que)(que)定復(fu)雜合金的(de)(de)(de)(de)(de)(de)一(yi)(yi)(yi)個(ge)坐(zuo)標點(dian),通過此點(dian)平行做出(chu)復(fu)雜合金的(de)(de)(de)(de)(de)(de)工作曲(qu)(qu)線(xian)(xian),進而發展為用(yong)較(jiao)(jiao)少(shao)種類的(de)(de)(de)(de)(de)(de)標鋼(gang)作多(duo)鋼(gang)種的(de)(de)(de)(de)(de)(de)分(fen)析方法(fa)。現在光(guang)電光(guang)譜(pu)分(fen)析中的(de)(de)(de)(de)(de)(de) “內(nei)(nei)控(kong)(kong)(kong)(kong)(kong)(kong)(kong)樣(yang)”,主要用(yong)于修(xiu)正(zheng)分(fen)析樣(yang)品(pin)(pin)(pin)與“校準(zhun)標樣(yang)”之間由于組織(zhi)結(jie)構和化(hua)學(xue)組成(cheng)不(bu)(bu)一(yi)(yi)(yi)致引起(qi)的(de)(de)(de)(de)(de)(de)分(fen)析結(jie)果的(de)(de)(de)(de)(de)(de)偏差。“內(nei)(nei)控(kong)(kong)(kong)(kong)(kong)(kong)(kong)樣(yang)”是我國光(guang)譜(pu)分(fen)析人(ren)的(de)(de)(de)(de)(de)(de)習慣稱(cheng)呼(hu),國外人(ren)士(shi)稱(cheng)為Type Standard Sample,直譯過來就(jiu)是“類型(xing)標準(zhun)化(hua)樣(yang)品(pin)(pin)(pin)”,簡稱(cheng)為“類標”(Type Standard)。其基本(ben)(ben)要求(qiu)是:組織(zhi)結(jie)構和化(hua)學(xue)成(cheng)份均勻(yun)并且(qie)要與被分(fen)析的(de)(de)(de)(de)(de)(de)末知(zhi)樣(yang)品(pin)(pin)(pin)一(yi)(yi)(yi)致(若不(bu)(bu)一(yi)(yi)(yi)致就(jiu)難(nan)以(yi)達到(dao)"校正(zheng)"的(de)(de)(de)(de)(de)(de)目(mu)的(de)(de)(de)(de)(de)(de)),元(yuan)(yuan)素含量要有準(zhun)確(que)(que)的(de)(de)(de)(de)(de)(de)定值(zhi)。內(nei)(nei)控(kong)(kong)(kong)(kong)(kong)(kong)(kong)樣(yang)一(yi)(yi)(yi)般由本(ben)(ben)單(dan)位自行研制(zhi)。分(fen)析組成(cheng)復(fu)雜樣(yang)品(pin)(pin)(pin)或新鋼(gang)種又沒有合適的(de)(de)(de)(de)(de)(de)標樣(yang)作工作曲(qu)(qu)線(xian)(xian)時,內(nei)(nei)控(kong)(kong)(kong)(kong)(kong)(kong)(kong)樣(yang)修(xiu)正(zheng)法(fa)是比較(jiao)(jiao)簡捷的(de)(de)(de)(de)(de)(de)辦(ban)法(fa)。但在日常分(fen)析中長期使用(yong)內(nei)(nei)控(kong)(kong)(kong)(kong)(kong)(kong)(kong)樣(yang)又比較(jiao)(jiao)煩瑣。其實,如果消除了(le)“末知(zhi)樣(yang)”與“工作曲(qu)(qu)線(xian)(xian)標樣(yang)”之間組織(zhi)結(jie)構差異(yi)的(de)(de)(de)(de)(de)(de)影響,又正(zheng)確(que)(que)校正(zheng)了(le)共存(cun)元(yuan)(yuan)素干擾,內(nei)(nei)控(kong)(kong)(kong)(kong)(kong)(kong)(kong)樣(yang)是可以(yi)少(shao)用(yong)甚(shen)至不(bu)(bu)用(yong)的(de)(de)(de)(de)(de)(de)。


控(kong)(kong)(kong)(kong)制樣(yang)(yang)(yang)(Control Samples)要(yao)求結(jie)(jie)構、成(cheng)份均勻,如(ru)果監控(kong)(kong)(kong)(kong)某(mou)一曲(qu)線(xian)(或(huo)某(mou)一規格(ge)的(de)(de)材料(liao)),其(qi)中的(de)(de)被(bei)監控(kong)(kong)(kong)(kong)元素的(de)(de)濃(nong)度(du),對應(ying)于曲(qu)線(xian)(或(huo)該規格(ge)的(de)(de)材料(liao)含量)的(de)(de)上(shang)中段,需要(yao)濃(nong)度(du)定值,更要(yao)有根據多次測定結(jie)(jie)果經數理(li)統計處理(li)得到的(de)(de)分析(xi)值的(de)(de)允許(xu)范圍,這些測定應(ying)該在所用(yong)的(de)(de)儀(yi)器(qi)上(shang)進行。如(ru)果監控(kong)(kong)(kong)(kong)某(mou)一曲(qu)線(xian),好用(yong)標準樣(yang)(yang)(yang)品(pin)作控(kong)(kong)(kong)(kong)制樣(yang)(yang)(yang);如(ru)果是監控(kong)(kong)(kong)(kong)某(mou)一規格(ge)的(de)(de)材料(liao)(生產分析(xi)),可以用(yong)組織結(jie)(jie)構類似的(de)(de)樣(yang)(yang)(yang)品(pin)自制,降(jiang)低運行成(cheng)本。控(kong)(kong)(kong)(kong)制樣(yang)(yang)(yang)(Control Samples)更注重(zhong)的(de)(de)是允許(xu)的(de)(de)“濃(nong)度(du)范圍”。同(tong)一只控(kong)(kong)(kong)(kong)制樣(yang)(yang)(yang)(Control Samples)可用(yong)于監控(kong)(kong)(kong)(kong)幾個不同(tong)元素。

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