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    1. ARL QUANTRIS Top performance CCD based metals analyzer ILAP Meeting P. Dalager / E. Muller

    3. Introduction CCD based instruments appeared nearly a decade ago New technology permitted lower cost, smaller bench-top instruments and flexibility Potential to analyse all elements without any optical compromise As long as wavelengths required covered and resolution good enough Compromises were needed to integrate technology, resulted in Smaller spectrometers with limited resolution Key elements not measurable (N) High detection limits, making analysis of minor elements not possible at levels required by specifications and norms (C, P) RSD of minor elements (5-10 %) too limited to comply with norms RSD of major elements (< 2 %) too limited to optimize usage of alloying elements and save production costs Stability frequently too limited to provide accurate results day by day

    4. Introduction Thermo (formerly ARL, then Thermo ARL) Decades of experience in providing OE spectrometers Instruments with superior analytical performance, stability, reliability and lifetime ARL METALS ANALYZER, ARL 3460, ARL 4460 Thermo has experience with first generation of OE solid state detectors based instruments ONESPARK (CID) ARL EASYTEST and ARL ASSURE (CCD) Thermo took challenge to break most compromises overcome limits experienced really achieve performance of traditional PMT based instruments

    5. Market requirements Solid state detector based OES with analytical figures of merit comparable to PMT instruments Analyze CNOPS elements in steel and P in Al High reliability, stability and availability Flexible instruments with no hardware modifications required for calibration extensions at customer sites Unlimited lines selection for multi-base applications Black-box operation with easy-to-use instrument and software

    6. What is the ARL QUANTRIS ? Second generation OE-CCD spectrometer Based on up to three spectrographs and solid state detectors Utilizes high end linear CCDs Utilizes high end CCS source First CCD based instrument with analytical performance equivalent to traditional PMT based instruments able to analyse elements C, N, P, S accurately even at lowest concentrations The length of the instrument is 100 vm, its width 78 cm , its height 119 cm and its weight 330 kg.The length of the instrument is 100 vm, its width 78 cm , its height 119 cm and its weight 330 kg.

    7. Outline Introduction Market requirements What is the ARL QUANTRIS? Instrument description Choice of technical solutions Spectrometer optics Solid state imagers Excitation source Instrument stability Hardware description Analytical development Software Analytical performance Customer benefits Conclusions

    8. Choice of technical solution Spectrometer optics Three alternatives investigated Paschen-Runge with chained linear solid state detectors along Rowland circle Echelle with 2D solid-state detectors Flat-field with linear solid-state detectors From the current OE-solid state analyzers: Spectro, WAS, Metorex are Paschen-Runge for both portable and bench-top instruments Only the OneSpartk was Echelle Assure, Essytest, Metalscan are flat fieldFrom the current OE-solid state analyzers: Spectro, WAS, Metorex are Paschen-Runge for both portable and bench-top instruments Only the OneSpartk was Echelle Assure, Essytest, Metalscan are flat field

    9. Instrument description Optics: Flat field Clearly the simplest lay-out. The light goes from the primary slit to the grating where it is dispersed and then collected on the detector.Clearly the simplest lay-out. The light goes from the primary slit to the grating where it is dispersed and then collected on the detector.

    10. Instrument description Optics: Flat field Advantages Simple configuration Simple detection system Simple mapping procedure (calibration, drift correction) ? Simplicity of configuration facilitates manufacturing of stable and reliable instruments Numerous manufacturers of linear detectors Difficulties Fields not flat over long distances Linear CCDs not arbitrary long ? Compromise spectral range/ resolution ? Narrow slits for good resolution ? Reduced light flux ? Limited dynamic range High light flux for good dynamic range ? Broader slits needed ? Lower resolution Works only in 1. order of diffraction ? Resolution limited for some critical wavelengths The mapping procedure is very simple with the wavelength integration windows defined in the line database Good resolution and good dynamic range need to be found. Optimum not possible for both ? acceptable compromize needs to be found As examples of the critical wavelenghts where resolution is limited : N at 149.26 and As at 180.04 nm The mapping procedure is very simple with the wavelength integration windows defined in the line database Good resolution and good dynamic range need to be found. Optimum not possible for both ? acceptable compromize needs to be found As examples of the critical wavelenghts where resolution is limited : N at 149.26 and As at 180.04 nm

    11. Choice of technical solution Optics: ARL QUANTRIS Up to three flat field spectrographs Separation of spectral range to be analyzed within 3 modules 129-200 nm (N, C, P, S) 200-410 nm 410-780 nm (Na, Li, K ) Optimized light collection in each module through specific lenses and gratings Direct reading for all 3 modules to avoid fibre optics No aging of fibres and no replacement necessary The evaluation of all three optical architecture, including optical simulation indicated that the best choice was the flat field spectrometer. In order to improve the resolution, it was decided to split the light transmission through three spectrographs, with the better resolution being put into the 129-200 spectrograph. The pictures shows the three spectrographs embodied in a cast iron housing. The three entrance lenses can be recognized at the front: The basic 200-410 nm is at the left and horizontal The alkaline 410-780 nm is at the right and horizontal The VUV 129-200 nm is in the middle and vertical In the front, the easily removable lenses with shutting of the vacuum are visible The lenses and gratings have been specifically designed for each spectrograph to achieve optimized light collection in each case All three spectrographs are in direct reading mode, no fibre optics are used The evaluation of all three optical architecture, including optical simulation indicated that the best choice was the flat field spectrometer. In order to improve the resolution, it was decided to split the light transmission through three spectrographs, with the better resolution being put into the 129-200 spectrograph. The pictures shows the three spectrographs embodied in a cast iron housing. The three entrance lenses can be recognized at the front: The basic 200-410 nm is at the left and horizontal The alkaline 410-780 nm is at the right and horizontal The VUV 129-200 nm is in the middle and vertical In the front, the easily removable lenses with shutting of the vacuum are visible The lenses and gratings have been specifically designed for each spectrograph to achieve optimized light collection in each case All three spectrographs are in direct reading mode, no fibre optics are used

    12. Choice of technical solution Solid state imagers Multi-parameter evaluation of CMOS and CCD techniques Two sensors potentially usable Linear CCD CMOS sensor Imager basics Both sensor are pixelated metal oxide semiconductors and accumulate signal charge in each pixel proportional to local illumination intensity CCD: transfers each pixels charge packet sequentially to a common output structure, which converts charge to a voltage, buffers it and sends it off-chip CMOS: charge-to-voltage conversion takes place in each pixel The purpose here is not to go in the various details of the evaluation, but just to show that a very detailed analysis was done as on the spectrometer. Responsitivity : Amount of signal per unit of input optical energy. Gain elements easier to place on CMOS Dynamic range: Ratio of pixels saturation level to its signal threshold. CCS have significant noise advantages because of quieter sensor substrates (less on chip circuitry), common output amplifiers with transistor geometries that can be easily adapted for minimal noise. Uniformity: Consistency of response for different pixels under identical illumination conditions Shuttering: ability to start and stop exposure arbitrarily Standard for CCD, superior electronic shuttering with little fill-factor compromise. Shuttering in CMOS required number of starnsistors in each pixel, at expense of fill factor Speed : CMOS potentially faster because all camera functions can be placed on image sensor Windowing: Superior capacity of CMOS in reading out a portion of the image sensor Antiblooming: drain overexposure Natural in CMOS, requires specific engineering in CCD Integration: CMOS more integrated : timing generation, signal processing, A/D conversion, interface can all be put on chip Adaptability, flexibility:Most CMOS designed for consumer application??highly integrated and tailored for one of few applications. CCDs are more general purpose : integrator can tailor readout speed, digitizing depth, analog and digital processing Two sensors potentially usable Linear CCD CMOS sensor Imager basics Both sensor are pixelated metal oxide semiconductors and accumulate signal charge in each pixel proportional to local illumination intensity CCD: transfers each pixels charge packet sequentially to a common output structure, which converts charge to a voltage, buffers it and sends it off-chip CMOS: charge-to-voltage conversion takes place in each pixel The purpose here is not to go in the various details of the evaluation, but just to show that a very detailed analysis was done as on the spectrometer. Responsitivity : Amount of signal per unit of input optical energy. Gain elements easier to place on CMOS Dynamic range: Ratio of pixels saturation level to its signal threshold.CCS have significant noise advantages because of quieter sensor substrates (less on chip circuitry), common output amplifiers with transistor geometries that can be easily adapted for minimal noise. Uniformity: Consistency of response for different pixels under identical illumination conditions Shuttering: ability to start and stop exposure arbitrarilyStandard for CCD, superior electronic shuttering with little fill-factor compromise. Shuttering in CMOS required number of starnsistors in each pixel, at expense of fill factor Speed : CMOS potentially faster because all camera functions can be placed on image sensor Windowing: Superior capacity of CMOS in reading out a portion of the image sensor Antiblooming: drain overexposureNatural in CMOS, requires specific engineering in CCD Integration: CMOS more integrated : timing generation, signal processing, A/D conversion, interface can all be put on chip Adaptability, flexibility:Most CMOS designed for consumer application??highly integrated and tailored for one of few applications. CCDs are more general purpose : integrator can tailor readout speed, digitizing depth, analog and digital processing

    13. Choice of technical solution Detector: ARL QUANTRIS CCD Specifically designed for high end industrial, scientific or military applications Color RGB CCDs used in monochromatic mode Increases signal/noise ratio Open new possibilities for increased dynamic range Lumogen coating for CCDs used in VUV spectrograph to improve quantum efficiency Reduced quantum efficiency at lower wavelengths Coatings mandatory to increase quantum efficiency below 200 nm The CCD characteristics are: Tri-linear CCD Image Sensor high resolution with 3x8640 pixels per spectrograph Tri-linear CCD image sensor Top of the range component used in space technology Driven by micro-controller Phosphor coating on CCD for VUV spectrograph Pixels 7x9.8 m at 7 m pitch CCD temperature cooled by Peltier device to reduce dark current noise Temperature regulated via PI at 0.06C resolutionThe CCD characteristics are: Tri-linear CCD Image Sensor high resolution with 3x8640 pixels per spectrograph Tri-linear CCD image sensor Top of the range component used in space technology Driven by micro-controller Phosphor coating on CCD for VUV spectrograph Pixels 7x9.8 m at 7 m pitch CCD temperature cooled by Peltier device to reduce dark current noise Temperature regulated via PI at 0.06C resolution

    14. Choice of technical solution Source: ARL QUANTRIS Two types of sources utilized on PMT instruments HIREP on ARL METALS ANALYZER and ARL 3460 Current follows natural decay imposed by RLC circuit 8 different excitation conditions available Patented Current Controlled Source (CCS) on ARL 4460 The only servo-controlled digital source on market Solid state electronics High degree of flexibility in selection of peak current, frequency and current waveforms Enables optimization of all figures of merit for each metal Achieves best accuracy, sensitivity and reproducibility Compact design close to spark stand in a Faraday cage Suppresses RF leakage and improves general stability All other CCD based instruments utilize HIREP type of sources with limited flexibilityAll other CCD based instruments utilize HIREP type of sources with limited flexibility

    15. Choice of technical solution Source: Our solution ARL QUANTRIS optics with limited resolution in comparison to Paschen-Runge optics with 1 m focal length CCS source best tool to compensate limitations and achieve best results ? CCS source selected Knowing that the optics was more limited in resolution, the decision was made to utilize the most flexible and high-end source to compensate as much as possible some of the limitations. The current waveform is computer controlled and can be selected for each type of metal. The high degree of flexibility in selection of peak current (250 A max.), frequency (1000 Hz max.) and current waveforms enables the optimization of all analytical figures. Knowing that the optics was more limited in resolution, the decision was made to utilize the most flexible and high-end source to compensate as much as possible some of the limitations. The current waveform is computer controlled and can be selected for each type of metal. The high degree of flexibility in selection of peak current (250 A max.), frequency (1000 Hz max.) and current waveforms enables the optimization of all analytical figures.

    16. Long-term stability of utmost importance in harsh environments to ensure quality analytical data Key influence on precision, accuracy and speed of analysis Time spent in drift correction is time lost Drift corrections are expensive Frequent drift correction can contribute to errors Metals production depends on stable analytical instruments to ensure the process is under control First generation of CCD based instruments dont have best stability reputation Exception being ARL ASSURE thanks to flat field architecture Thermo established reputation with stable instruments Company knowledge exploited to provide stable instruments All the Thermo knowledge and experience was put to achieve the best stability possibleAll the Thermo knowledge and experience was put to achieve the best stability possible

    17. Easier to achieve stability with simple flat field architecture Well proven cast iron spectrometer Provides unrivaled stability both on short and long term Spectrometer running under vacuum Provides rigidity Independant from atmospheric pressure variations Thermo-controlled CCDs to 0.5C at 0.5-2C Achieves low noise in addition to stability Water-cooled stand Automatic optical alignment and spectrum profiling on each CCD Choice of technical solution Stability The optical alignment and spectrum profiling is performed in hidden time at each analysis The spectrum measured is compared to a standard spectrum and shifted when necessary to compensate for any drift. The optical alignment and spectrum profiling is performed in hidden time at each analysis The spectrum measured is compared to a standard spectrum and shifted when necessary to compensate for any drift.

    18. Hardware description Stand Stand main features With 3 optical channels Argon flow optimized by computer simulation Casted analysis table for light passes, argon admission and exhaust optimization Quick analysis table exchange Indirect water cooling table Very low stand-by flow Fast flush and dust blow out system Use of short pulsed argon jets Allow to reduce argon flush time even with Nitrogen analysis Keep the spark chamber free of extra dust over extended time Consequently reduces maintenance frequency and down time

    19. Hardware description Optical system main features Spectrometer in cast iron, under dry vacuum 3 spectrographs with flat field diffraction system Focal length: 200 mm Primary slit width: 15 m Holographic aberration corrected concave gratings VUV spectrograph: 3240 gr/mm (at grating center) Basic spectrograph: 1105 gr/mm (at grating center) Optional alkaline spectrograph: 590 gr/mm (at grating center) Average dispersion: VUV spectrograph: 1.2 nm/mm Basic spectrograph: 3.5 nm/mm Optional alkaline spectrograph: 6.7 nm/mm Average bandpass per pixel : VUV spectrograph: 8 pm/pixel Basic spectrograph: 24 pm/pixel Optional alkaline spectrograph: 43 pm/pixel

    20. Hardware description Optical system Spectrometer views

    21. Analytical development Analytical conditions (2) Fe base Standard timings and source parameters CCD and acquisition parameters If exposed through the complete integration period, the CCDs would be overexposed Therefore sub-integrations lasting from 18 ms minimal to 4.2 s maximal are performed on each CCD The sub-integration time is currently specific to each spectrograph. It could also depend on the various matrices and even on the various qualitiesIf exposed through the complete integration period, the CCDs would be overexposed Therefore sub-integrations lasting from 18 ms minimal to 4.2 s maximal are performed on each CCD The sub-integration time is currently specific to each spectrograph. It could also depend on the various matrices and even on the various qualities

    22. Analytical development Preliminary Manipulation of Spectral Data After summation of intensities of elementary integration times: 3 spectra obtained for each CCD line (RGB) Added to obtain 1 spectrum for each CCD with up to ? 3 x better S/N Pixel intensities of all CCDs used for computations (next slides) Pixel intensities of all CCDs also stored in a file allowing graphical display of the spectra With header with various information With polynomial coefficients and pixel intensities for each CCD Coefficients make spectra in nm from different instruments comparable Apart from an innovative architecture built on proven modern technologies, a real progress in the performance of the instrument has been made thanks to appropriate mathematical treatment of the spectra. While limited with PMT spectrometers, post-acquisition treatment of the spectral intensities recorded by the CCDs offers a multitude of methods, which allow partly filling of the performance gap between the two types of instruments. A prerequisite for the implementation of such methods on commercial instruments is their robustness, which ensures that they work properly on each sample, on every instrument. This is only possible if the characteristics of the spectrometer are reproducible and if the stability is excellent. The design of the ARL QUANTRIS clearly provides this. Apart from an innovative architecture built on proven modern technologies, a real progress in the performance of the instrument has been made thanks to appropriate mathematical treatment of the spectra. While limited with PMT spectrometers, post-acquisition treatment of the spectral intensities recorded by the CCDs offers a multitude of methods, which allow partly filling of the performance gap between the two types of instruments. A prerequisite for the implementation of such methods on commercial instruments is their robustness, which ensures that they work properly on each sample, on every instrument. This is only possible if the characteristics of the spectrometer are reproducible and if the stability is excellent. The design of the ARL QUANTRIS clearly provides this.

    23. Analytical development Numerical Processing - Generalities Weaker performance of CCDs vs. PMTs Sensitivity typically 2-3 orders of magnitude lower Lower precision Numerical processing offers unique differentiators to the ARL QUANTRIS Because spectrum available and almost no limitation on line selection Drawbacks partly compensated by "massaging" spectra with Drift correction at each acquisition Processing windows with full flexibility Various filtering modes Various intensity modes Various background subtraction modes Use of best internal standard for each analyte line Deconvolution Enormous potential, at every level ! While on PMT instruments with a 1 m Paschen-Runge spectrometer, the spectrum is projected onto a 80 cm wide circle, on the ARL Quantris the spectrum is projected only onto a width of 18 cm (3 x 6 cm per CCD) All lines and particularly the interfering lines are now about 5 times narrower, resulting in a clearly degraded sensitivity and precision. However with the full spectrum being available digitally, numerous signal treatment functions, that are not available on PMT instruments, permit now to compensate for some of the limitations and even in some cases exceed the PMT performance. While on PMT instruments with a 1 m Paschen-Runge spectrometer, the spectrum is projected onto a 80 cm wide circle, on the ARL Quantris the spectrum is projected only onto a width of 18 cm (3 x 6 cm per CCD) All lines and particularly the interfering lines are now about 5 times narrower, resulting in a clearly degraded sensitivity and precision. However with the full spectrum being available digitally, numerous signal treatment functions, that are not available on PMT instruments, permit now to compensate for some of the limitations and even in some cases exceed the PMT performance.

    24. Analytical development Numerical Processing For drift correction Drift correction Drifts unavoidable ! For each CCD, at each acquisition Well defined and resolved lines compared to a "mask" Set of reference lines Drift correction algorithm "moves and deforms" spectrum in order to find the smallest difference with reference lines Special algorithms to find accurate maxima positions of measured lines Parameters similar to a and b for restandardization A manual profile function is not requested anymore The drift is now measured and compensated at each measurement A manual profile function is not requested anymore The drift is now measured and compensated at each measurement

    25. Analytical development Numerical Processing Processing window Chosen to eliminate interferences as much as possible Chosen to solve desperate situations Can be shrunk to a line ? amplitude measurement Due to the limited time available in this presentation, only some of the digital signal handling are presented Processing windows correspond in fact to the secondary slits of PMT instruments, but with a fa rbetter flexibilityDue to the limited time available in this presentation, only some of the digital signal handling are presented Processing windows correspond in fact to the secondary slits of PMT instruments, but with a fa rbetter flexibility

    26. Analytical development Numerical Processing Filtering Smoothing filters matched to line characteristics Improve pixel reproducibility Reduce noise Improve reproducibility of integration Noises from various sources are present in the spectrum They are responsible for lower sensitivity and precision They are partially reduced by working temperature of CCDs ? 0C In order to reduce the remaining noise, various numerical filters can be applied to the spectrum. Filters matching the characteristics of the spectral region of interest (resolution, integration wavelength window) allow optimal smoothing of the noisy intensities. A graphical illustration of the concept of numerical filtering on the line C 133.57 is shown. A low-pass filter with different parameters (cut-off frequency and gauge) is tested. Numerical filtering induces a small broadening of the peak and a reduction in the signal to background ratio. As can be seen with an expanded vertical scale (lower diagram) the fluctuations of the background signal (pure sample) are diminished, which improves the reproducibility. Noises from various sources are present in the spectrum They are responsible for lower sensitivity and precision They are partially reduced by working temperature of CCDs ? 0C In order to reduce the remaining noise, various numerical filters can be applied to the spectrum. Filters matching the characteristics of the spectral region of interest (resolution, integration wavelength window) allow optimal smoothing of the noisy intensities. A graphical illustration of the concept of numerical filtering on the line C 133.57 is shown. A low-pass filter with different parameters (cut-off frequency and gauge) is tested. Numerical filtering induces a small broadening of the peak and a reduction in the signal to background ratio. As can be seen with an expanded vertical scale (lower diagram) the fluctuations of the background signal (pure sample) are diminished, which improves the reproducibility.

    27. Analytical development Numerical Processing Filtering Typical improvements due to smoothing filters SD calculated on 10 runs performed on SUS RE12 The benefits of filtering are shown on the precision achieved without and with filtering. Some huge improvements (I.e. N and P) are achievedThe benefits of filtering are shown on the precision achieved without and with filtering. Some huge improvements (I.e. N and P) are achieved

    28. Analytical development Numerical Processing Background Subtraction Various modes Off-Peak ( = Bg ) On-peak If off-line background signal not available Rectangular or trapezoidal None Quality of background on- peak not always sufficient If good background improves sensitivity, bad background can degrade reproducibility Background subtraction can now be performed both off- and on-peak For on-peak subtraction, both rectangular and trapezoidal corrections can be applied in function of the type of background surrounding the peak (constant, fluctuating). Background subtraction can now be performed both off- and on-peak For on-peak subtraction, both rectangular and trapezoidal corrections can be applied in function of the type of background surrounding the peak (constant, fluctuating).

    29. Outline Introduction Market requirements What is the ARL QUANTRIS? Instrument description Software Analytical performance Customer benefits Conclusions

    30. Software WinOE the powerful assistant First Windows based version launched 1991 Regular releases (13) to add functions, improve ease-of-use, support new OS Current version 3.1 Runs on all Thermos PMT based instruments Runs on Windows 2000 Most powerful package on market Most robust package on market Simplest to use package on market Thermo was first to release an analytical software for spectrometers running under Windows. The long experience expired along the 13 releases done meanwhile makes WinOE the most complete, flexible and robust package on the market. WinOE is available with all current PMT based Thermo Optical Emission spectrometers. It can also be supplied as a retrofit package on earlier instruments from ARL and from the sisters companies Baird and Hilger. The latest version was adapted to support the ARL QUANTRIS spectrometer.Thermo was first to release an analytical software for spectrometers running under Windows. The long experience expired along the 13 releases done meanwhile makes WinOE the most complete, flexible and robust package on the market. WinOE is available with all current PMT based Thermo Optical Emission spectrometers. It can also be supplied as a retrofit package on earlier instruments from ARL and from the sisters companies Baird and Hilger. The latest version was adapted to support the ARL QUANTRIS spectrometer.

    31. Software New WinOE 3.2 Main novelty: supports ARL QUANTRIS now! Line library manager Libraries managed per matrix Graphical tool to display the spectra acquired from the 3 CCD's and identity unknown peaks From the version 3.2 onwards, WinOE supports ARL QUANTRIS. This version will also be available for the other ARL optical emission spectrometers. From the version 3.2 onwards, WinOE supports ARL QUANTRIS. This version will also be available for the other ARL optical emission spectrometers.

    32. Software New WinOE 3.2: Lines library manager Lines libraries organized per base: Fe, Al, Cu A base lines library includes selected spectral lines, spectrum processing algorithms and information Lines libraries available separately Multi-base capability New elements added without hardware change Easy addition in analytical programs of any line included within the installed lines libraries Lines of other bases need corresponding library Each lines library includes informations about the lines, the parameters used in algorithms and useful information to help select lines. Each lines library includes informations about the lines, the parameters used in algorithms and useful information to help select lines.

    33. Software New WinOE 3.2: Qualitative analysis Spectra display function, dedicated to the display of analysis spectra On-line and off-line view Spectra manipulation tools Peak search function Also called finger print mode Permits qualitative analysis of any element in wavelength library > 146000 lines Perfect tool for metallurgical research User friendly thanks to a modern look 'n feel Evolving functionality Nice tool for metallurgical research WinOE, the analytical software of the ARL QUANTRIS includes a tool allowing qualitative analysis of samples, the ARL QUANTRIS Spectra Viewer. Either for identifying elements in unknown samples or to help developing analytical programs, i.e. checking the spectrum at particular lines. Two modes of operation are possible. The tool is modern and include powerful functions to customize the spectra display, like zoom. It also permits the identification of elements by searching wavelengths in the complete wavelength table. Spectra Viewer has an evolving design allowing to add new functions with future releases.WinOE, the analytical software of the ARL QUANTRIS includes a tool allowing qualitative analysis of samples, the ARL QUANTRIS Spectra Viewer. Either for identifying elements in unknown samples or to help developing analytical programs, i.e. checking the spectrum at particular lines. Two modes of operation are possible. The tool is modern and include powerful functions to customize the spectra display, like zoom. It also permits the identification of elements by searching wavelengths in the complete wavelength table. Spectra Viewer has an evolving design allowing to add new functions with future releases.

    34. Outline Introduction Market requirements What is the ARL QUANTRIS? Instrument description Software Analytical performance Customer benefits Conclusions

    35. Analytical Performance New detection limit definition Traditional DL calculation method DL = 3 * s relative * BEC s relative relative standard deviation stored for the pure matrix sample with 10 runs With background subtraction, too easy to artificially show very low DLs Alternative method had to be defined DL =t*s*Sensitivity t : Extracted from Student table for p =99.5 % (3 s) and df=9? t = 3.2498 s : standard deviation in intensity measured on pure sample Sensitivity : slope of calibration curve at zero concentration (C1- Co/(I1-Io) Definition already used by some customers Most accurate method Gives very similar results on PMT based instruments with definition above X is confidence interval; X=0.05 equivalent to a probability of 95%, i.e. 2 sigma for a gaussian distribution. V is the degree of freedom X is confidence interval; X=0.05 equivalent to a probability of 95%, i.e. 2 sigma for a gaussian distribution. V is the degree of freedom

    36. Key elements: Steel: C, N, P, S, Pb, Si, Mn Cast iron : Pb, Mg, La, CeN Garanteed values at Thermo Calculation according to norms Not every competitor calculated according to norms ARL QUANTRIS in steel 4 x inferior to ARL 3460 C better 5 x better than ARL ASSURE ARL QUANTRIS in cast iron Equivalent to 3460 Analytical Performance Fe base: detection limits (3 s) A ratio > 1 indicates QUANTRIS is better, a ratio < 1 indicates QUANTRIS is worse Clearly superior to benchtop CCD instruments C 25-50 ppm, N n.a., S 10-25 ppm, P 15-40 ppm, B 5-20 ppm, Pb 30-50 ppm Permits analysis of key elements even at lowest concentrations Lowest quantitative determination limit : at least 3 times DL, while Spectro gives DLA ratio > 1 indicates QUANTRIS is better, a ratio < 1 indicates QUANTRIS is worse Clearly superior to benchtop CCD instruments C 25-50 ppm, N n.a., S 10-25 ppm, P 15-40 ppm, B 5-20 ppm, Pb 30-50 ppm Permits analysis of key elements even at lowest concentrations Lowest quantitative determination limit : at least 3 times DL, while Spectro gives DL

    37. Low alloy steel 10 runs per sample Key elements Minor : C, N, P, S, Pb, Si, Mn Major : Co, Cr, Ni, Mn, Mo, W ARL QUANTRIS 15 % < ARL 3460 4 x better than ARL ASSURE Analytical Performance Fe base: reproducibility example (1 s) A ratio > 1 indicates QUANTRIS is better, a ratio < 1 indicates QUANTRIS is worseA ratio > 1 indicates QUANTRIS is better, a ratio < 1 indicates QUANTRIS is worse

    38. Cast iron Sample CKD 248 10 runs per sample Key elements Minor : Pb, Mg, La, Ce Major : C, Cr, Ni, Mo ARL QUANTRIS 50 % better than ARL 3460 7 x better than ARL ASSURE RSD major elements C, Ni: > ARL 3460 Cr, Mo: < ARL 3460 RSD trace elements Pb: = ARL 3460 Analytical Performance Fe base: reproducibility example (1 s)

    39. Analytical Performance Fe base: reproducibility Excellent element Due to the smaller spectrum available, the following story is applicable almost in each matrix: The higher the concentrations, the better the QUANTRIS performance If numerous lines are available in the spectrum, and some of these lines are not interfered, the digital signal handling fully compensates for the limited resolution and the results can be excellent (even superior to the ARL 4460) as shown above for carbon If only a few lines are available in the spectrum, and these few lines are interfered, the digital signal handling cannot fully compensate for the limited resolution and the results remain worse as shown above for phosphorus. In these cases, the results remain however clearly superior to benchtop CCD instruments All possibilities being not explored, it is to be expected that these limited performance will be improved in the future. Due to the smaller spectrum available, the following story is applicable almost in each matrix: The higher the concentrations, the better the QUANTRIS performance If numerous lines are available in the spectrum, and some of these lines are not interfered, the digital signal handling fully compensates for the limited resolution and the results can be excellent (even superior to the ARL 4460) as shown above for carbon If only a few lines are available in the spectrum, and these few lines are interfered, the digital signal handling cannot fully compensate for the limited resolution and the results remain worse as shown above for phosphorus. In these cases, the results remain however clearly superior to benchtop CCD instruments All possibilities being not explored, it is to be expected that these limited performance will be improved in the future.

    40. Calibration curves examples Excellent linearity Reduced absorption effects Excellent Standard Errors of Estimate (SEE) Analytical Performance Fe base: accuracy The calibration curves show a by far better linearity and reduced self-absorption efects The accuracy achieved better better than on PMT based instruments. Be careful that the C curve covers concentrations between 0 and 5 %. On PMT instruments this is normally achieved with 2 different lines. The appearing non-linearity is only due to the large concentration range covered.The calibration curves show a by far better linearity and reduced self-absorption efects The accuracy achieved better better than on PMT based instruments. Be careful that the C curve covers concentrations between 0 and 5 %. On PMT instruments this is normally achieved with 2 different lines. The appearing non-linearity is only due to the large concentration range covered.

    41. Cr-Ni calibration Same ranges and samples on both instruments Key elements Minor : C, N, P, Pb, S Major : Co, Cr, Ni, Mn, Mo, W Residual errors, QUANTRIS Better on key elements Cr, Mn Analytical Performance Fe base: accuracy (SEE) SSE differences of only 20 % show clearly the excellent accuracy of the ARL QUANTRIS. SSE differences of only 20 % show clearly the excellent accuracy of the ARL QUANTRIS.

    42. Analytical Performance Fe base: stability These stability tests were performed while the argon flow were not optimum, better stability figures should currently be achieved. The results are astonishing, considering that the control limits were put at only 2 sigma. The N drifted slightly over one week, but this is the element that drift the most on PMT instruments The Mg signal didnt shown any drift over one week.These stability tests were performed while the argon flow were not optimum, better stability figures should currently be achieved. The results are astonishing, considering that the control limits were put at only 2 sigma. The N drifted slightly over one week, but this is the element that drift the most on PMT instruments The Mg signal didnt shown any drift over one week.

    43. Typical values yet Application still in development Guaranteed values to be slightly higher Key elements: As, Ca, Cd, Li, Na, P, Pb, Sb, Sn ARL QUANTRIS in Al 10 x inferior to ARL 3460 Analytical Performance Al base: detection limits (3 s) A ratio > 1 indicates QUANTRIS is better, a ratio < 1 indicates QUANTRIS is worse Permits analysis of key elements even at lowest concentrations Lowest quantitative determination limit : at least 3 times DL, while Spectro gives DLA ratio > 1 indicates QUANTRIS is better, a ratio < 1 indicates QUANTRIS is worse Permits analysis of key elements even at lowest concentrations Lowest quantitative determination limit : at least 3 times DL, while Spectro gives DL

    44. Al-Si-Cu sample 10 runs per sample ARL QUANTRIS Clearly better on major elements Sometimes inferior on minor elements Analytical Performance Al base: reproducibility example (1 s) A ratio > 1 indicates QUANTRIS is better, a ratio < 1 indicates QUANTRIS is worse Apart Ti at 43 ppm, the QUNATRIS shows systematically superior resultsA ratio > 1 indicates QUANTRIS is better, a ratio < 1 indicates QUANTRIS is worse Apart Ti at 43 ppm, the QUNATRIS shows systematically superior results

    45. Analytical Performance Al base: reproducibility example (1 s) On major elements, and independently of the sample analyzed, the ARL Quantris shows its superiority to the ARL 3460On major elements, and independently of the sample analyzed, the ARL Quantris shows its superiority to the ARL 3460

    46. Outline Introduction Market requirements What is the ARL QUANTRIS? Instrument description Software Analytical performance Customer benefits Conclusions

    47. Customer benefits Stability Feature Instrument virtually drift free Simple flat field architecture Well proven cast iron spectrometer running under vacuum Thermo-controlled CCDs to 0.5 C at 5C Water-cooled stand Automatic optical alignment and spectrum profiling on each spectrograph Benefit Instrument delivers dependable performance 24 x 7 x 365 Minimizes drift correction procedures and keeps instrument available for its primary task Analysis of unknown samples Minimizes consumption of expensive drift correction samples Competitors dont like publishing stability figures, particularly if they use Paschen-Runge spectrometers with CCD sensors. We know for instance that the Spectrolab Jr CCD had to be drift corrected every two hours and so should the Spectromax be. Insist on this point and push prospects getting stability figures according to clearly defined stability test rules from competitionCompetitors dont like publishing stability figures, particularly if they use Paschen-Runge spectrometers with CCD sensors. We know for instance that the Spectrolab Jr CCD had to be drift corrected every two hours and so should the Spectromax be. Insist on this point and push prospects getting stability figures according to clearly defined stability test rules from competition

    48. Features and benefits Reproducibility Feature Instrument divided in 3 spectrographs Thermally controlled CCDs for low noise Optimal analytical line for each matrix and even each quality Optimal Internal Standard, optimized for each analytical line Optimal data treatment for each line (smoothing, filtering, background substraction) Digital source with optimum waveform for each matrix Benefit Confidence in reproducibility of results delivered Precision of minor elements (RSD 1-5 %) enough to comply with specifications and norms Precision of major elements (RSD 0.2-1 %) permits minimal usage of alloying elements and save production costs Be very careful with competition and the numbers of runs they take to calculate a reproducibility. We know for instance that Spectro argues with the Spectromax that as the samples are homogeneous, three runs are enough to calculate a reproducibility From a statistical point of view, this is a non-sense, each norms requesting typically 10 runs to be taken Normally the reproducibility improves with the number of runs taken. This is however true only if the instrument has a good short term stability. If not a poor short term stability can bias the results and show better reproducibility with less runs performed We made the exercise with an ARL Assure, better reproducibility ise achieved with 3 runs instead of 10. The contrary happens with the ARL QUANTRIS (or the ARL MA). The reproducibility is better with 10 runs, which conforms to the laws of statistics. If you are confronted to good performance from competition, challenge the prospect on the numbers of runs performed, explained the phenomenon and push then to request reproducibility with 10 runs.Be very careful with competition and the numbers of runs they take to calculate a reproducibility. We know for instance that Spectro argues with the Spectromax that as the samples are homogeneous, three runs are enough to calculate a reproducibility From a statistical point of view, this is a non-sense, each norms requesting typically 10 runs to be taken Normally the reproducibility improves with the number of runs taken. This is however true only if the instrument has a good short term stability. If not a poor short term stability can bias the results and show better reproducibility with less runs performed We made the exercise with an ARL Assure, better reproducibility ise achieved with 3 runs instead of 10. The contrary happens with the ARL QUANTRIS (or the ARL MA). The reproducibility is better with 10 runs, which conforms to the laws of statistics. If you are confronted to good performance from competition, challenge the prospect on the numbers of runs performed, explained the phenomenon and push then to request reproducibility with 10 runs.

    49. Features and benefits Flexibility Feature Full spectrum available with no spectral line compromize Wavelength coverage from 129 nm to 780 nm Extension of analytical needs with no hardware modifications In some cases spectrograph 410-780 nm could be requested Fast change tables and electrodes for multi-matrix applications Benefit All elements requested by the metals industry can be analyzed Easy identification of unknown elements Low investment costs Up-grades performed with minimal downtime Easier operation in multi-matrix applications Lowest operating costs

    50. Outline Introduction Market requirements What is the ARL QUANTRIS? Instrument description Software Analytical performance Customer benefits Conclusions

    51. Conclusions Thermo not first with CCD-based OE spectrometers But when we do it, we do it right !! For first time CCD based spectrometer with true performance of PMT based instruments All spectral lines for all metals types Full and continuous wavelength coverage from 129-870 nm For the first time low C, N analysable with CCD-based instrument Detection limits, reproducibility, accuracy, stability, reliability Rugged construction to be used in hostile environments Stability to minimize drift corrections Automatic optical alignment and spectrum profiling

    52. Conclusions Perfect instrument for metals producers and transformers Lower operating costs, flexibility for identification of unknown elements Perfect instrument for industrial central laboratories, analytical services contract laboratories Multi-matrix applications without any compromizes Permits also lowest costs of ownership Price difference rapidly offset by savings on costs of ownership Easily up-gradable at lower costs