瓦里安系列瓦里安Vista扫描光谱仪

1、Varian Inc. 瓦里安公司新一代ICP介绍Vista - the new CCD Simultaneous ICP from VarianVarian 的ICP “家族”Liberty 和 VistaLiberty Series II - 世界上最好的单道扫描式 ICP-AESVista - 世界上速度最快的全谱直读式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 技术特点背景低对70 多个元素有较低的检出限为多元素分析技术极高的分析效率很宽的线性范围可分析溶液中的主量, 微量 和痕量元素干扰少主要为光谱干扰操作简单ICP 仪器组成RF 发生器计算机打印机炬管系统光学系统检测器进样泵发 射 光 谱 的 发 展 全谱直读 固体检测器(CCD) 单道扫描 PMT 多道 PMT 摄谱仪 感光板ICP-OES Basic Concepts多道光谱仪ICP-OES Basic Concepts单道扫描光谱仪多道 ICP 和单道扫描 ICP 的优缺点多道ICP单道扫描ICP优点:速

4、度快灵活 效率高易于建立方法缺点:死板速度慢, 消耗成本高扣背景不准确精度较差共同缺点:背景和信号不能同时测定, 存在时间误差扣背景速度慢Echelle optics88o19oICP-AES市场概况Varian所占市场份额(现状)ICP-AES市场概况Varian所占市场份额(预期)Vista CCD 全谱直读 ICP设计理念（一）设计制造尽可能好的最先进的全谱直读式ICP优异的性能强大的灵活性快速、节省消耗成本易于使用能够分析广泛的样品能够扩展到双向观察的动态范围高技术水平Vista CCD 全谱直读 ICP设计理念（二）什么是仪器的先进性?能够集以往仪器的优点于一身, 同时又能克服其各自

5、缺点的仪器.怎样实现?采用更新、更先进的技术Vista CCD 全谱直读 ICP设计理念（三）：技术分析当前市场状况：有两种全谱直读式ICP分段式CCD，可同时测UV、VIS，但波长不连续，覆盖6谱线，SCD饱和溢出。CID 作检测器，波长基本连续，但UV、VIS不能同时，CID 分析性能差, 需UV转换膜,寿命问题。均不能彻底实现全谱直读，速度不够快。垂直、水平、双向：均不能同时具备两者优点检测器：PMT，CID，CCD？CCD：分析性能优于光电倍增管。CID：分析性能不如光电倍增管，需要有机涂膜。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个感光元以连续倾角阵列排列波长连续测定图象匹配技术 (I-MAP)电信号处理速度提高40倍1 MHz的感光元处理速度高保真的信号再现性CCD检测器 VistaChip改进的检

8、出限和灵敏度Vista的突出特色之一 VistaChip CCD 检测器特别定做的、ICP专用的专利CCD检测器70,000个感光元保证全波长覆盖各感光元精确地与二维中阶梯光栅图象相匹配 (I-MAP技术)复式读出电路节省一半的读数时间电信号处理速度提高40倍1 MHz的感光元处理速度半导体冷却保持检测器部分-35oC恒温以降低噪声电子信号处理在CCD芯片外进行以保证高量子化效率CCD检测器工作原理（1）70,000个感光元以连续倾角排列 3 级高速寄存器 A - 集光 B - 临时储存C - 快速读出CCD检测器工作原理（2）中阶梯光栅多色仪的焦面落在检测器的感光元（A寄存器）上光敏寄存器A

9、把光信号转化为电信号每个感光元上都有溢流保护以防信号过载Vista - Anti-blooming 防止过饱和溢出0.5 mg/L Pb in 5000 mg/L AlVista谱图三维图象CCD检测器工作原理（3）经一段时间的累积，电子从寄存器A转移到临时寄存器BABCCD检测器工作原理（4）然后电子又从寄存器B转移到读出寄存器C，并以1MHz的频率顺序读出35秒检测73种元素包括25秒的进样时间！1MHz的感光元读出速度从芯片两侧读取数据的复式电路光学系统结构图 CCD检测器光栅棱镜88o光栅和棱镜的二维分光19oVista 完美的光学系统集成化、台式的中阶梯光栅光谱仪35oC恒温保证了光

10、路的稳定性 采用 94.7线/mm的中阶梯光栅的1988级衍射光CaF2 晶体棱镜做交叉色散Ar或N2 吹扫提供优异的190nm以下波长的检测 计算机控制的前置光路用于优化等离子体的视场Vista无与伦比的40MHz射频系统 集成化的内置40MHz自激式射频系统采用空气冷却且无移动部件保证了系统的高可靠性DISC - 直接耦合系统无二级匹配网络 80%的耦合效率出色的MgII/MgI比率功率输出稳定性10表明是高强度的等离子体Vista独特的轴向观察技术等离子体的结构示意图Preheating Zoneviewing height above load coilInduction ZoneIn

11、itial Radiation ZoneNormal Analytical Zone Plasma Tail Vista CCD ICP-AES Axial 轴向冷锥接口技术怎样使水平方式在改善检出限的同时，又得到垂直式的抗基体干扰能力？独特的冷锥接口专利技术轴向等离子体冷锥接口的横截面图显示“低温尾焰”已从光路中完全消除轴向尾焰消除技术Varian 特有的冷锥接口技术CCI横向“ 吹尾 ”使用剪切气对等离子体低温尾焰进行横向吹扫时， “低温尾焰”干扰不可能被完全排除（图中红色部分），并有噪声横向“ 吹尾 ” 实物照片Extraction snoutCool zone其他抽气方式Vista优越

12、的轴向检测高强度的等离子体可容许高含量的固体溶解冷锥接口技术克服了剪切气的离子化干扰无需双向检测系统全波长选择扩展了动态范围无需如双向观测系统那样两次对样品进行分析紫外短波段检测的优化设计体积极小的中阶梯光栅多色仪0.7 L/min的常规吹扫对190nm以下波段采用3.0 L/min的加压吹扫不用时加压吹扫处于关闭状态使用氮气或氩气对178nm只需30分钟的吹扫对 S (180.652, 181.960, 182.542 nm)对 P (178.192 nm)ICP的运转费用与直接用户密切相关的要因！仪器运转费用主要包括：气：使用气体的种类、纯度和用量电：一个不容忽视的因素水：我国目前严重缺水

13、！维护：尽量避免光路和电路的污染维修：故障分析及时准确零部件的价格和持续性Vista大幅度降低了运转费用预热时间短（30分钟），快速启动快速分析缩短了分析时间，极大降低了分析成本冷锥接口的轴向设计避免了大量剪切气的使用高效的吹扫系统仅须0.7或3.7 L/min的气体流量高效的射频系统消耗较少的氩气和电能优良的恒温系统大大缩短了运行时间无移动部件的射频系统和光学系统降低了维修费用方便快捷的远程诊断功能远程诊断 - Modem连接使远端的Varian技术服务部门和应用支持部门能够对仪器实现完全控制有效地降低了维护/维修费用，并减少了停机时间Vista 功能强大的高智能化软件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在线谱图库表示-图形VISTA - QCPVista 高智能分析软件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 自动最佳化分析条件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 自动最佳化Vista - 自動最佳化Ease of Use .仪器工作条件自动最佳化Vista 自动调适积分时间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 扩展工作範圍 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强大的软件功能 FACT 谱图解析软件 Fast Automated Curve -fitting Technique 快速自动匹配曲线拟合技术使用一系列的高斯曲线对分析元素的谱线和干扰元素的谱线进行精确模拟该模拟可以精确地校正极小（1/1

23、0感光元）的波长漂移干扰校正不影响分析速度,FAST!FACT 谱图解析软件的设计原理使用FACT软件的解析结果Resolved spectra using FACTVista - FACT Cd 214.438 nm interfered by Fe 214.443 实际性能测试Vista全谱直读式ICP-AES检出限ICP最基本的性能指标之一所有检出限数据的测定基于以下条件:采用轴向观察测定10秒钟的积分时间内的检出限测定3噪声对185nm以下的波段采用3 L/min的氩气对光路系统加压吹扫 没有采用内标法没有进行背景校正实际测得的检出限元素AgAlAsAuBBaBeBiCaCdCeCoC

24、rFeK波长(nm)328.068167.016188.979267.595249.773455.403234.861223.061396.847214.438418.660238.892267.716259.940766.490检出限 (g/L)0.51.05.01.40.070.040.053.00.010.32.00.50.50.40.5实际测得的检出限LiMgMnMoNaNiPPbSSeSiSrTiTlVWZnZr波长(nm)670.784279.553257.610202.030589.592231.604177.432220.353181.971196.026251.611407.

25、771334.941190.790292.402207.911213.856343.823检出限 (ug/L)0.10.010.050.80.21.37.03.09.05.01.70.010.135.00.43.00.30.3元素与其他品牌仪器的检出限对比(ppb)Vista Analytical performanceVista Measured Resolution实测的分辨率元素 波 长 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小时的稳定性实验结果4小时的稳定性优于10500010000150002000025000300000153045607590105120135150165180195210225240时间 (min)净 光 强Al 396.152As 188.979Ba 493.409Cd 214.438Cu 327.396K 766.49Mn 257.61Pb 220.353Se 196.026Zn 213.856Cu 324.754杂散光水平测试 一项重要的光学质量测试

27、样品：10,000 ppm Ca溶液测量As 193.696 nm波长处的信号该信号与基准线的偏差表明杂散光的水平Vista的杂散光水平 2 ppm As当量稳定时间测试35 minutes应 用 实 例Vista 全谱直读式 ICP-AES水和土壤样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饮用水中金属元素的分析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饮用水中主量金属元素的分析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.分析结果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基体中的检测限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 贵金属分析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铜合金的分析by Axial VistaElementMeasuredExpected (mg/L) (mg/L

36、)MicroCo4.65Cr0.170.2K1.52Si0.40.3Al4.65Na11.812MinorAs151150Ni159 150Fe19.920矿石分析 （ 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矿石分析 （ axial Vista）Reference Material GS-12ElementFoun

37、d Certified(mg/L) (mg/L)MajorsAl397399Ca125126Fe18551870K10596Mg107108Mn6063Ni16.216Pb6367S301305Geochemical地質化學分析鱼和贝类的样品分析分析条件鱼类和贝类的肉质样品使用硝酸消解最终在8% HNO3中浓缩处理标样在8% HNO3中制备仪器条件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分析结果Fish Reference MaterialsElementFoundCertified(g/L) (g/L)8G-2Se4030As37.820Cd2.012Pb20.4208G-5Se345300As224200Cd20.320Pb193.2200分析结果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