EP1238262A2 - Procede et dispositif pour mesurer des grandeurs caracteristiques d'un echantillon - Google Patents

Procede et dispositif pour mesurer des grandeurs caracteristiques d'un echantillon

Info

Publication number
EP1238262A2
EP1238262A2 EP00991062A EP00991062A EP1238262A2 EP 1238262 A2 EP1238262 A2 EP 1238262A2 EP 00991062 A EP00991062 A EP 00991062A EP 00991062 A EP00991062 A EP 00991062A EP 1238262 A2 EP1238262 A2 EP 1238262A2
Authority
EP
European Patent Office
Prior art keywords
reference samples
parameters
calibration
sample
calculated
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP00991062A
Other languages
German (de)
English (en)
Inventor
Peter Maier
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Siemens AG
Original Assignee
Siemens AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Siemens AG filed Critical Siemens AG
Publication of EP1238262A2 publication Critical patent/EP1238262A2/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
    • G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
    • G01N21/27—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands using photo-electric detection ; circuits for computing concentration
    • G01N21/274—Calibration, base line adjustment, drift correction
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N2201/00—Features of devices classified in G01N21/00
    • G01N2201/12—Circuits of general importance; Signal processing
    • G01N2201/127—Calibration; base line adjustment; drift compensation
    • G01N2201/12723—Self check capacity; automatic, periodic step of checking

Definitions

  • the invention relates to a method for measuring characteristic quantities of a sample by means of spectral analysis, the characteristic quantities being calculated from the spectral data obtained thereby using a calibration model created on the basis of reference samples.
  • the invention further relates to a device for measuring characteristic quantities of a sample with a spectrometer for spectral analysis of the sample and with a calibration model created on the basis of reference samples, which calculates the characteristic quantities from spectral data supplied by the spectrometer.
  • NIR spectroscopy in which the molecular structure in the sample material is excited with radiation quanta in the near infrared range (NIR). The molecules get into vibrational states according to their structure and show typical energy absorption. In the resulting spectrum, the energy absorption is recorded using a detector based on discrete wavelengths. From the spectral data thus obtained, characteristic quantities of the sample to be determined are calculated using a calibration model. These parameters can basically include all parameters of the sample that correlate with the information content of the spectrum. The parameters therefore include in particular the molecular structure of the sample and the resulting physical and chemical properties.
  • the calibration model is based on the spectral data and using chemometric methods such as MLR (Multiple Linear Regression) or PLS (Partial Least Squares)
  • Characteristics of selected or prepared reference samples created the characteristics of the reference samples already are known and / or determined by reference analysis, for example in the laboratory.
  • the reference samples must correspond as closely as possible to the samples to be analyzed and cover the range of variation of the characteristic quantities of the samples to be determined.
  • the invention is based, with as little effort possible measurement deviations before an object
  • the object is achieved in that in the method of the type mentioned at the beginning, by means of at least one further calibration model created on the basis of further reference samples, a further calculation of the parameters of the sample is carried out and that deviations between the parameters calculated in each case by the calibration models determined and output.
  • a further calculation of the parameters of the sample is carried out and that deviations between the parameters calculated in each case by the calibration models determined and output.
  • Posted for the initially mentioned device is the on ⁇ handover characterized solved in that at least one of additional reference samples created on the basis of another calibration model is present, theteurbowt a further calculation of the ISIN large, and that the calibration models comparing means is arranged downstream of the deviations between determines and outputs the parameters calculated by the calibration models.
  • the two or multiple calculation of the parameters in independent calibration models and the determination of the deviations between the calculated parameters lead to an improvement in the reliability of the measurements and their robustness against undetected error influences. Since the determined deviations are available together with the calculated parameters, the user can assess the quality of the measurement for each sample. In particular, it can be determined by monitoring the deviations ascertained that a predetermined threshold is exceeded if the measurement error becomes too large. This can be carried out automatically in routine operation by the measuring device according to the invention, so that it can also be used in otherwise unmonitored on-line operation; Regular control measurements are then not necessary and a recalibration is only necessary when an automatically detected and reported threshold is exceeded.
  • the additional calibration and computational effort caused by the at least one further calibration model is only slight and corresponds to the number and selection of the
  • Calibration used calibration samples.
  • the possible objection with a summary of the reference samples used for the independent calibration models to create a single, more comprehensive calibration model, a comparable improvement in the measurement behavior could only be achieved in particularly favorable cases, since the distribution of the reference samples carefully according to the facial point of a uniform coverage of the measuring range must be selected.
  • the reference samples and the other reference samples each cover different ranges of variation in the parameters to be determined for the samples.
  • the one calibration model can be formed by covering a relatively large range of variation with naturally selected reference samples, while the further calibration model is created over a relatively narrow range of variation with specially prepared samples; one calibration model then calculates the parameters in the larger range of variation with a relatively low resolution, while the other calibration model calculates the parameters in the narrower range with high resolution.
  • a high degree of robustness of the measurement is achieved in the narrower coverage area of the two calibration models, while a still usable measurement result is achieved in the wide area.
  • the calibration models can be created with reference samples or other reference samples under slightly different boundary conditions or with reference samples and other reference samples from different times.
  • the calibration models can of course also be based on partially identical reference samples.
  • the type of selection of the other calibration models whose range of validity must of course overlap in the normal measuring range, offers the possibility of taking into account, as experience has shown, deviations or changes in the samples that are associated with a further calibration were recorded, with the previous experience being re-calibrated.
  • the measuring device can be adapted step by step to changes or a new calibration can be tested for preservation in measuring operation and can be improved step by step.
  • the selection of already determined spectral data from samples of known composition is a step that is varied and optimized several times, so that the further calibration models can be created without any significant additional effort.
  • a sample 1 is subjected to a spectral analysis in a spectrometer 2.
  • the polychromatic light 3 is fed to a radiation source 4, for example a halogen lamp, to a monochromator 5.
  • the monochromatic light 6 is fed to a measuring cell 7, in which it interacts with the sample for 1 m.
  • the molecules of sample 1 come into oscillation states according to their structure and show typical energy absorptions.
  • the light 8 transmitted or reflected by the sample 1 reaches a detector 9 which detects the energy absorption and provides it on the output side as spectral data 10.
  • Data 10 parameters 12 to be determined of sample 1, for example a specific molecular concentration, are calculated.
  • first spectral data 10 'and known or determined by analytical reference characteristic Great 12' of selected or specially prepared reference samples l 1 determines are being calculated by means of a chemometric method weighting functions in the form of a Kalibrationsmat ⁇ x 13, its application to the spectral data 10 'or 10 gives the parameters 12' or 12 except for a certain amount of error.
  • the two calibration models 11 and 14 are shown here as separate circuit blocks because of their independence, but in practice the associated calibration matrices 13, 14 can be combined to form a single matrix in which the input and output variables can occur two or more times from the further calibration model 14 from the spectral data 10 of sample 1, calculated parameters 16 are compared in a comparison 17 with parameters 12 calculated by calibration model 11. If the deviation between the calculated parameters 12 and 16 exceeds a predetermined threshold, the comparison device 17 generates a warning 18, which indicates an excessive measurement error.
  • the calibration models 11 and 14 can be followed by a selection device 19 which, on the basis of predetermined criteria 20, e.g. Temperature or sample consistency, decides which of the calculated parameters 12, 16 are the most trustworthy and outputs them as the result 21 of the measurement.
  • predetermined criteria e.g. Temperature or sample consistency

Landscapes

  • Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Mathematical Physics (AREA)
  • Theoretical Computer Science (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Immunology (AREA)
  • Pathology (AREA)
  • Investigating Or Analysing Materials By Optical Means (AREA)

Abstract

L'invention concerne un procédé et un dispositif pour mesurer des grandeurs caractéristiques d'un échantillon par analyse spectrale. Selon ce procédé, les grandeurs caractéristiques sont calculées à partir des données spectrales obtenues, au moyen d'un modèle d'étalonnage établi sur la base d'échantillons de référence. L'invention vise à accroître la stabilité de la mesure. A cet effet, un autre calcul des grandeurs caractéristiques (6) des échantillons (1) est effectué au moyen d'au moins un autre modèle d'étalonnage (14) établi sur la base d'autres échantillons de référence (1''). Les écarts entre les grandeurs caractéristiques (12, 16) calculées par les modèles d'étalonnage (11, 14) sont déterminés et sortis.
EP00991062A 1999-12-15 2000-12-14 Procede et dispositif pour mesurer des grandeurs caracteristiques d'un echantillon Withdrawn EP1238262A2 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19960586 1999-12-15
DE19960586A DE19960586B4 (de) 1999-12-15 1999-12-15 Verfahren und Einrichtung zur Messung von Kenngrössen einer Probe durch Spektralanalyse
PCT/DE2000/004456 WO2001044788A2 (fr) 1999-12-15 2000-12-14 Procede et dispositif pour mesurer des grandeurs caracteristiques d'un echantillon

Publications (1)

Publication Number Publication Date
EP1238262A2 true EP1238262A2 (fr) 2002-09-11

Family

ID=7932810

Family Applications (1)

Application Number Title Priority Date Filing Date
EP00991062A Withdrawn EP1238262A2 (fr) 1999-12-15 2000-12-14 Procede et dispositif pour mesurer des grandeurs caracteristiques d'un echantillon

Country Status (4)

Country Link
US (1) US6671629B2 (fr)
EP (1) EP1238262A2 (fr)
DE (1) DE19960586B4 (fr)
WO (1) WO2001044788A2 (fr)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AUPS059002A0 (en) * 2002-02-15 2002-03-14 Airservices Australia Determination of solution concentration
DE10350075A1 (de) * 2003-10-27 2005-06-09 Siemens Ag Verfahren und Vorrichtung zur Prozessführung bei der Zellstoffkochung
EP1985996A1 (fr) * 2007-04-27 2008-10-29 Roche Diagnostics GmbH Système d'analyse destiné à la détermination photométrique d'un analyte dans un liquide corporel doté d'un appareil d'analyse et d'un support de test destiné à l'enregistrement dans l'appareil d'analyse
DE102018103509B3 (de) * 2017-10-11 2018-12-13 Carl Zeiss Spectroscopy Gmbh Mobiles Inhaltsstoffanalysesystem sowie Verfahren zur probenrichtigen Messung und Nutzerführung mit diesem

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4155009A (en) * 1977-04-07 1979-05-15 Unit Process Assemblies, Inc. Thickness measurement instrument with memory storage of multiple calibrations
US5204532A (en) * 1989-01-19 1993-04-20 Futrex, Inc. Method for providing general calibration for near infrared instruments for measurement of blood glucose
US6198532B1 (en) * 1991-02-22 2001-03-06 Applied Spectral Imaging Ltd. Spectral bio-imaging of the eye
US5872630A (en) * 1995-09-20 1999-02-16 Johs; Blaine D. Regression calibrated spectroscopic rotating compensator ellipsometer system with photo array detector
US6441388B1 (en) * 1998-10-13 2002-08-27 Rio Grande Medical Technologies, Inc. Methods and apparatus for spectroscopic calibration model transfer
US6280381B1 (en) * 1999-07-22 2001-08-28 Instrumentation Metrics, Inc. Intelligent system for noninvasive blood analyte prediction

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO0144788A3 *

Also Published As

Publication number Publication date
WO2001044788A3 (fr) 2001-11-29
WO2001044788A2 (fr) 2001-06-21
US20030028329A1 (en) 2003-02-06
US6671629B2 (en) 2003-12-30
DE19960586A1 (de) 2001-07-12
DE19960586B4 (de) 2008-04-24

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