瓦里安系列瓦里安Vista掃描光譜儀

1、Varian Inc. 瓦里安公司新一代ICP介紹Vista - the new CCD Simultaneous ICP from VarianVarian 的ICP “家族”Liberty 和 VistaLiberty Series II - 世界上最好的單道掃描式 ICP-AESVista - 世界上速度最快的全譜直讀式ICP-AESWhat is a Plasma?A plasma is a stream of highly ionized gas containing an equal number of electrons and positive ionsA plasma is

2、electrically conductiveA plasma is affected by a magnetic fieldQuantitation in Atomic EmissionConcentration proportional to intensity emitted at the analyte wavelength.ConcentrationEmission01StandardBlanksample emissionsample concentrationAxial Channel ZonesVisual DeterminationYttrium TestAspirate 1

3、000 mg/L Y solutionBlue IonicRed AtomicICP 技術(shù)特點(diǎn)背景低對(duì)70 多個(gè)元素有較低的檢出限為多元素分析技術(shù)極高的分析效率很寬的線性范圍可分析溶液中的主量, 微量 和痕量元素干擾少主要為光譜干擾操作簡(jiǎn)單ICP 儀器組成RF 發(fā)生器計(jì)算機(jī)打印機(jī)炬管系統(tǒng)光學(xué)系統(tǒng)檢測(cè)器進(jìn)樣泵發(fā) 射 光 譜 的 發(fā) 展 全譜直讀 固體檢測(cè)器(CCD) 單道掃描 PMT 多道 PMT 攝譜儀 感光板ICP-OES Basic Concepts多道光譜儀ICP-OES Basic Concepts單道掃描光譜儀多道 ICP 和單道掃描 ICP 的優(yōu)缺點(diǎn)多道ICP單道掃描ICP優(yōu)點(diǎn):速

4、度快靈活 效率高易于建立方法缺點(diǎn):死板速度慢, 消耗成本高扣背景不準(zhǔn)確精度較差共同缺點(diǎn):背景和信號(hào)不能同時(shí)測(cè)定, 存在時(shí)間誤差扣背景速度慢Echelle optics88o19oICP-AES市場(chǎng)概況Varian所占市場(chǎng)份額(現(xiàn)狀)ICP-AES市場(chǎng)概況Varian所占市場(chǎng)份額(預(yù)期)Vista CCD 全譜直讀 ICP設(shè)計(jì)理念（一）設(shè)計(jì)制造盡可能好的最先進(jìn)的全譜直讀式ICP優(yōu)異的性能強(qiáng)大的靈活性快速、節(jié)省消耗成本易于使用能夠分析廣泛的樣品能夠擴(kuò)展到雙向觀察的動(dòng)態(tài)范圍高技術(shù)水平Vista CCD 全譜直讀 ICP設(shè)計(jì)理念（二）什么是儀器的先進(jìn)性?能夠集以往儀器的優(yōu)點(diǎn)于一身, 同時(shí)又能克服其各自

5、缺點(diǎn)的儀器.怎樣實(shí)現(xiàn)?采用更新、更先進(jìn)的技術(shù)Vista CCD 全譜直讀 ICP設(shè)計(jì)理念（三）：技術(shù)分析當(dāng)前市場(chǎng)狀況：有兩種全譜直讀式ICP分段式CCD，可同時(shí)測(cè)UV、VIS，但波長(zhǎng)不連續(xù)，覆蓋6譜線，SCD飽和溢出。CID 作檢測(cè)器，波長(zhǎng)基本連續(xù)，但UV、VIS不能同時(shí)，CID 分析性能差, 需UV轉(zhuǎn)換膜,壽命問(wèn)題。均不能徹底實(shí)現(xiàn)全譜直讀，速度不夠快。垂直、水平、雙向：均不能同時(shí)具備兩者優(yōu)點(diǎn)檢測(cè)器：PMT，CID，CCD？CCD：分析性能優(yōu)于光電倍增管。CID：分析性能不如光電倍增管，需要有機(jī)涂膜。Instrumentation for Optical Emission Spectrosco

6、pyTable 3.11 A. Comparison Between the Minimum Detectable Signals of PDA, ISPDA, CID, PMT, and CCDMinimum detectable signal(S/N=2), photon/S/detector elementaquisition PDA ISPDA CID PMT CCD _ time(s) UV VIS UV VIS UV VIS UV VIS UV VIS 10 671 363 32 53 41 32 6.3 26 3.1 1.7 100 112 62 10 17 4.2 3.3 1.

7、8 7.3 0.3 0.2Table 3.11B Parameters Used in Caculating the Minimum Detactable SignalParameter PDA ISPDA CID PMT CCDQE at 600nm73% 6% 37% 5% 84%QE at 300nm40% 10% 19% 21% 50%Dark count rate36000 4000 0.008 3 70,000個(gè)感光元以連續(xù)傾角陣列排列波長(zhǎng)連續(xù)測(cè)定圖象匹配技術(shù) (I-MAP)電信號(hào)處理速度提高40倍1 MHz的感光元處理速度高保真的信號(hào)再現(xiàn)性CCD檢測(cè)器 VistaChip改進(jìn)的檢

8、出限和靈敏度Vista的突出特色之一 VistaChip CCD 檢測(cè)器特別定做的、ICP專用的專利CCD檢測(cè)器70,000個(gè)感光元保證全波長(zhǎng)覆蓋各感光元精確地與二維中階梯光柵圖象相匹配 (I-MAP技術(shù))復(fù)式讀出電路節(jié)省一半的讀數(shù)時(shí)間電信號(hào)處理速度提高40倍1 MHz的感光元處理速度半導(dǎo)體冷卻保持檢測(cè)器部分-35oC恒溫以降低噪聲電子信號(hào)處理在CCD芯片外進(jìn)行以保證高量子化效率CCD檢測(cè)器工作原理（1）70,000個(gè)感光元以連續(xù)傾角排列 3 級(jí)高速寄存器 A - 集光 B - 臨時(shí)儲(chǔ)存C - 快速讀出CCD檢測(cè)器工作原理（2）中階梯光柵多色儀的焦面落在檢測(cè)器的感光元（A寄存器）上光敏寄存器A

9、把光信號(hào)轉(zhuǎn)化為電信號(hào)每個(gè)感光元上都有溢流保護(hù)以防信號(hào)過(guò)載Vista - Anti-blooming 防止過(guò)飽和溢出0.5 mg/L Pb in 5000 mg/L AlVista譜圖三維圖象CCD檢測(cè)器工作原理（3）經(jīng)一段時(shí)間的累積，電子從寄存器A轉(zhuǎn)移到臨時(shí)寄存器BABCCD檢測(cè)器工作原理（4）然后電子又從寄存器B轉(zhuǎn)移到讀出寄存器C，并以1MHz的頻率順序讀出35秒檢測(cè)73種元素包括25秒的進(jìn)樣時(shí)間！1MHz的感光元讀出速度從芯片兩側(cè)讀取數(shù)據(jù)的復(fù)式電路光學(xué)系統(tǒng)結(jié)構(gòu)圖 CCD檢測(cè)器光柵棱鏡88o光柵和棱鏡的二維分光19oVista 完美的光學(xué)系統(tǒng)集成化、臺(tái)式的中階梯光柵光譜儀35oC恒溫保證了光

10、路的穩(wěn)定性 采用 94.7線/mm的中階梯光柵的1988級(jí)衍射光CaF2 晶體棱鏡做交叉色散Ar或N2 吹掃提供優(yōu)異的190nm以下波長(zhǎng)的檢測(cè) 計(jì)算機(jī)控制的前置光路用于優(yōu)化等離子體的視場(chǎng)Vista無(wú)與倫比的40MHz射頻系統(tǒng) 集成化的內(nèi)置40MHz自激式射頻系統(tǒng)采用空氣冷卻且無(wú)移動(dòng)部件保證了系統(tǒng)的高可靠性DISC - 直接耦合系統(tǒng)無(wú)二級(jí)匹配網(wǎng)絡(luò) 80%的耦合效率出色的MgII/MgI比率功率輸出穩(wěn)定性10表明是高強(qiáng)度的等離子體Vista獨(dú)特的軸向觀察技術(shù)等離子體的結(jié)構(gòu)示意圖Preheating Zoneviewing height above load coilInduction ZoneIn

11、itial Radiation ZoneNormal Analytical Zone Plasma Tail Vista CCD ICP-AES Axial 軸向冷錐接口技術(shù)怎樣使水平方式在改善檢出限的同時(shí)，又得到垂直式的抗基體干擾能力？獨(dú)特的冷錐接口專利技術(shù)軸向等離子體冷錐接口的橫截面圖顯示“低溫尾焰”已從光路中完全消除軸向尾焰消除技術(shù)Varian 特有的冷錐接口技術(shù)CCI橫向“ 吹尾 ”使用剪切氣對(duì)等離子體低溫尾焰進(jìn)行橫向吹掃時(shí)， “低溫尾焰”干擾不可能被完全排除（圖中紅色部分），并有噪聲橫向“ 吹尾 ” 實(shí)物照片Extraction snoutCool zone其他抽氣方式Vista優(yōu)越

12、的軸向檢測(cè)高強(qiáng)度的等離子體可容許高含量的固體溶解冷錐接口技術(shù)克服了剪切氣的離子化干擾無(wú)需雙向檢測(cè)系統(tǒng)全波長(zhǎng)選擇擴(kuò)展了動(dòng)態(tài)范圍無(wú)需如雙向觀測(cè)系統(tǒng)那樣兩次對(duì)樣品進(jìn)行分析紫外短波段檢測(cè)的優(yōu)化設(shè)計(jì)體積極小的中階梯光柵多色儀0.7 L/min的常規(guī)吹掃對(duì)190nm以下波段采用3.0 L/min的加壓吹掃不用時(shí)加壓吹掃處于關(guān)閉狀態(tài)使用氮?dú)饣驓鍤鈱?duì)178nm只需30分鐘的吹掃對(duì) S (180.652, 181.960, 182.542 nm)對(duì) P (178.192 nm)ICP的運(yùn)轉(zhuǎn)費(fèi)用與直接用戶密切相關(guān)的要因！儀器運(yùn)轉(zhuǎn)費(fèi)用主要包括：氣：使用氣體的種類、純度和用量電：一個(gè)不容忽視的因素水：我國(guó)目前嚴(yán)重缺水

13、！維護(hù)：盡量避免光路和電路的污染維修：故障分析及時(shí)準(zhǔn)確零部件的價(jià)格和持續(xù)性Vista大幅度降低了運(yùn)轉(zhuǎn)費(fèi)用預(yù)熱時(shí)間短（30分鐘），快速啟動(dòng)快速分析縮短了分析時(shí)間，極大降低了分析成本冷錐接口的軸向設(shè)計(jì)避免了大量剪切氣的使用高效的吹掃系統(tǒng)僅須0.7或3.7 L/min的氣體流量高效的射頻系統(tǒng)消耗較少的氬氣和電能優(yōu)良的恒溫系統(tǒng)大大縮短了運(yùn)行時(shí)間無(wú)移動(dòng)部件的射頻系統(tǒng)和光學(xué)系統(tǒng)降低了維修費(fèi)用方便快捷的遠(yuǎn)程診斷功能遠(yuǎn)程診斷 - Modem連接使遠(yuǎn)端的Varian技術(shù)服務(wù)部門和應(yīng)用支持部門能夠?qū)x器實(shí)現(xiàn)完全控制有效地降低了維護(hù)/維修費(fèi)用，并減少了停機(jī)時(shí)間Vista 功能強(qiáng)大的高智能化軟件Familiar Sp

14、readsheet conceptsame look as Plasma 96Easy to useWindows 95，98 & NT 4 compatibleImproved user interface operationscut and paste, copy and pasteInter-element correctionsFACTFitted background correctionEase of Use在線譜圖庫(kù)表示-圖形VISTA - QCPVista 高智能分析軟件Adaptive Integrationautomatically sets integration tim

15、e to intensityFACT Spectral deconvolutionProgrammable QCPenhanced error actions eg recalibrate & repeatAutomaxFast auto-optimization wizardSequence WizardQuickly set up complex sequencesVista Automax 自動(dòng)最佳化分析條件Uses 3 different criteriaSignal to Background Ratio (SBR), Intensity, Signal to Root Backgr

16、ound ratio (SRBR).Optimize all or sub-set of Improves weak Iteratively optimize for non-compromised conditionsOptimizes major instrument parameters RF power, viewing height & nebulizer flowWhy Optimize?Power = 1.2kWNebulizer flow = 1.00L/minViewing height = 10mmPower = 1.5kWNebulizer flow = 1.70L/mi

17、nViewing height = 5mmAutomax 自動(dòng)最佳化Vista - 自動(dòng)最佳化Ease of Use .儀器工作條件自動(dòng)最佳化Vista 自動(dòng)調(diào)適積分時(shí)間Instrument measures sample for 0.1 secondSets read time for each according to intensityIf read time is appropriate continues to measure until replicate read timeIf too short read time increasedIf too long integratio

18、n time decreased and data from first read is not acceptedIntensity display is normalisedVista Adaptive IntegrationTo set acquisition time only need to setreplicate read timenumber of replicatesIf replicate read time = 10 secVery intense 100 x 0.1 secstrong might read 10 x 1 secweak read 1 x 10 secVi

19、sta Adaptive IntegrationAdvantages of adaptive Integrationstatistics for weak improved by long integration timeFor intense large number of readings averaged to improve resultsUnlike Optima, VistaChip is able to handle different integration times for different simultaneouslyWorks in the presence of v

20、ery intense lines because of blooming protection between pixelsVista MultiCal Extends Linear Dynamic RangeExtends linear dynamic range by calibration with lines of different sensitivity - ppb to %Easy to usesimply specify valid concentration range for each lineImproved productivity c.f. dual view as

21、 no need to re-run samplesReduces sample consumptionMay overlap for concentration ranges for improved confidenceVista - MultiCal 擴(kuò)展工作範(fàn)圍 Ca from 20 ug/L - 4000 mg/L393.366 nm - 0-2 ug/L 422.673 nm - 0-20ug/L430.253 nm - 0-4000 ug/LVista MultiCal Extended RangeMg 279.553 valid between 0 - 20 ppmMg 285

22、.213 valid between 20 - 40 ppmVista - Retrospective EditingEditReplicate resultsWeight and volumeCalibration parametersBackground correction typeBackground correction positionVista強(qiáng)大的軟件功能 FACT 譜圖解析軟件 Fast Automated Curve -fitting Technique 快速自動(dòng)匹配曲線擬合技術(shù)使用一系列的高斯曲線對(duì)分析元素的譜線和干擾元素的譜線進(jìn)行精確模擬該模擬可以精確地校正極?。?/1

23、0感光元）的波長(zhǎng)漂移干擾校正不影響分析速度,FAST!FACT 譜圖解析軟件的設(shè)計(jì)原理使用FACT軟件的解析結(jié)果Resolved spectra using FACTVista - FACT Cd 214.438 nm interfered by Fe 214.443 實(shí)際性能測(cè)試Vista全譜直讀式ICP-AES檢出限ICP最基本的性能指標(biāo)之一所有檢出限數(shù)據(jù)的測(cè)定基于以下條件:采用軸向觀察測(cè)定10秒鐘的積分時(shí)間內(nèi)的檢出限測(cè)定3噪聲對(duì)185nm以下的波段采用3 L/min的氬氣對(duì)光路系統(tǒng)加壓吹掃 沒(méi)有采用內(nèi)標(biāo)法沒(méi)有進(jìn)行背景校正實(shí)際測(cè)得的檢出限元素AgAlAsAuBBaBeBiCaCdCeCoC

24、rFeK波長(zhǎng)(nm)328.068167.016188.979267.595249.773455.403234.861223.061396.847214.438418.660238.892267.716259.940766.490檢出限 (g/L)0.51.05.01.40.070.040.053.00.010.32.00.50.50.40.5實(shí)際測(cè)得的檢出限LiMgMnMoNaNiPPbSSeSiSrTiTlVWZnZr波長(zhǎng)(nm)670.784279.553257.610202.030589.592231.604177.432220.353181.971196.026251.611407.

25、771334.941190.790292.402207.911213.856343.823檢出限 (ug/L)0.10.010.050.80.21.37.03.09.05.01.70.010.135.00.43.00.30.3元素與其他品牌儀器的檢出限對(duì)比(ppb)Vista Analytical performanceVista Measured Resolution實(shí)測(cè)的分辨率元素 波 長(zhǎng) 分辨率 (nm) (pm)As 188.979 7.5Mo 202.030 7.6Zn 213.856 8.4Pb 220.353 8.6Cr 267.716 10Cu 327.396 13Ba 614

26、.172 38Vista - 分辨率P 213.618 vs Cu 213.598 nm (0.020 nm difference) 4小時(shí)的穩(wěn)定性實(shí)驗(yàn)結(jié)果4小時(shí)的穩(wěn)定性優(yōu)于10500010000150002000025000300000153045607590105120135150165180195210225240時(shí)間 (min)凈 光 強(qiáng)Al 396.152As 188.979Ba 493.409Cd 214.438Cu 327.396K 766.49Mn 257.61Pb 220.353Se 196.026Zn 213.856Cu 324.754雜散光水平測(cè)試 一項(xiàng)重要的光學(xué)質(zhì)量測(cè)試

27、樣品：10,000 ppm Ca溶液測(cè)量As 193.696 nm波長(zhǎng)處的信號(hào)該信號(hào)與基準(zhǔn)線的偏差表明雜散光的水平Vista的雜散光水平 2 ppm As當(dāng)量穩(wěn)定時(shí)間測(cè)試35 minutes應(yīng) 用 實(shí) 例Vista 全譜直讀式 ICP-AES水和土壤樣品的分析水中成分的分析Recoveries of NIST SRM 1643 cElementMeasuredCertifiednmug/Lug/LAg328.0682.262.21+0.3As188.97983.582.1+1.2Ba233.52746.649.6+3.1Be265.04523.123.1+2.2Cd226.50212.112.

28、2+1Co228.61621.523.5+0.8Cr205.55217.419+0.6Cu324.75416.222.3+2.8Mn257.61035.735.1+2.2Mo202.030100104.3+1Ni231.60458.060.6+7.3Pb220.35332.735.3+0.9Tl190.7906.07.9V292.40228.131.4+2.8飲用水中金屬元素的分析by Axial VistaElementMeasuredCertified*nmug/Lug/LAg328.0682.222.00As188.97980.680Ba233.52749.350Cd226.5029.3

29、10Co228.61622.125Cr205.55218.320Cu324.75419.020Mn260.56942.740Ni231.60461.060Pb220.3533540Sb206.8339.110Tl190.7901410V292.4642530Zn206.20069.770VistaChip wavelength selection flexibilitychoose any no need for dual viewed opticssimultaneous analysis of trace and major elements飲用水中主量金屬元素的分析Major Eleme

30、nts by Axial VistaElementMeasuredCertified*nmmg/Lmg/LCa318.12836.535Mg279.0799.69K766.4902.12.5Na589.5926.76* High Purity Standards Co.土壤中的主量和痕量元素分析by Axial Vista after 1:10 dilutionElementMeasuredCertified*nmmg/Lmg/LAs188.9796.06.3Ba233.5276.67.0Cd214.4380.20.2Co228.6160.070.1Cu324.7543.13.0Ni231.6

31、040.100.15Sb206.8330.160.1Zn206.20068.870Fe260.709348350Al257.510649650K766.490221210Na589.592123100* High Purity Standards Co.分析結(jié)果Water SamplesGFAAS 1GFAAS 4ElementFound* CertifiedFoundCertifiedAl0.062 0.050.620.50V0.027 0.0250.270.25Cr0.010 0.010.0990.10Co0.01 0.010.100.10Cu0.011 0.010.1020.10Cd0.

32、0024 0.00250.024 0.025Se0.050 0.00250.0500.025*All results mg/LAnalysis of impurities in acidsby VistaImpurities in acids are important to semiconductor industryAcids e.g. HCl, HNO3, HF, H2O2, etcDue to the ultra trace level of impurities, acid sample is evaporated to dryness in a quartz beakerThen

33、redissolve the impurities in high purity acidsUltrasonic nebuliser is recommended USN offers generally 10 times improvement in detection limitMetallurgy 冶金分析Analysis of Palladium compounds樣品前處理Use 0.1 - 1 g sample, accurately weighedDissolve in 5 mL aqua regiaMake up to 100 mLStandards and blank pre

34、pared in 5% aqua regia基體中的檢測(cè)限5 % 王水 vs 5 g/L Pd solutionElement5% Aqua regia5g/L Pd solution(ug/L) (ug/L)Al 167.0160.360.43Au 267.5952.113.56B 182.5801.282.82Cu 224.7002.344.97P 177.4358.0116.0Pt 265.9458.9412.3Ru 240.2722.423.56Sn 189.9263.037.90Zr 343.8231.54 1.62Analysis of Palladium compoundsRep

35、eatability Test - 20 samplesPrecision ranged from 0.27 - 1.10 %RSD 貴金屬分析4 hours stability testPrecision ranged from 0.92 - 1.09 %RSD Copper alloy sample樣品前處理Use 0.1 g sample, accurately weigheddissolve in 5 mL HCl and 5 mL HNO3Make up to 100 mL銅合金的分析by Axial VistaElementMeasuredExpected (mg/L) (mg/L

36、)MicroCo4.65Cr0.170.2K1.52Si0.40.3Al4.65Na11.812MinorAs151150Ni159 150Fe19.920礦石分析 （ axial Vista）Reference Material GS-12ElementFound Certified(mg/L) (mg/L)TracesAg0.30.4As6.36.4Ba3.73.8Bi1.01.5Cr3.53.4Mo0.140.17P6.56.9Sc0.120.14Sr0.680.66V2.02.3礦石分析 （ axial Vista）Reference Material GS-12ElementFoun

37、d Certified(mg/L) (mg/L)MajorsAl397399Ca125126Fe18551870K10596Mg107108Mn6063Ni16.216Pb6367S301305Geochemical地質(zhì)化學(xué)分析魚(yú)和貝類的樣品分析分析條件魚(yú)類和貝類的肉質(zhì)樣品使用硝酸消解最終在8% HNO3中濃縮處理標(biāo)樣在8% HNO3中制備儀器條件Power1.3 kWPlasma gas15 L/minAuxiliary gas1.5 L/minNebulizer typeglass concentricNebulizer pressure215 kPaPump speed15 rpmUpt

38、ake rate1.0 mL/minIntegration time5.0 secondsReplicates3Background CorrectionOff peak and fitted分析結(jié)果Fish Reference MaterialsElementFoundCertified(g/L) (g/L)8G-2Se4030As37.820Cd2.012Pb20.4208G-5Se345300As224200Cd20.320Pb193.2200分析結(jié)果Water SamplesEPA 4EPA 12Element Found CertifiedFound Certified (mg/L)(mg/L)(mg/L) (mg/L)As 0.0400.0250.061 0.062Ba 0.1960.1650.438 0.462Cd 0.00250.00270.007