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WO1993022656A1 - Colorimetric measurement device - Google Patents

Colorimetric measurement device Download PDF

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Publication number
WO1993022656A1
WO1993022656A1 PCT/FR1993/000418 FR9300418W WO9322656A1 WO 1993022656 A1 WO1993022656 A1 WO 1993022656A1 FR 9300418 W FR9300418 W FR 9300418W WO 9322656 A1 WO9322656 A1 WO 9322656A1
Authority
WO
WIPO (PCT)
Prior art keywords
sampling
calibration
repetitive
analytical
sample
Prior art date
Application number
PCT/FR1993/000418
Other languages
French (fr)
Inventor
Alain Metayer
Paul Chaillot
Christian Patron
Original Assignee
Alliance Instruments S.A.
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 Alliance Instruments S.A. filed Critical Alliance Instruments S.A.
Priority to EP93911836A priority Critical patent/EP0638167A1/en
Priority to JP5519003A priority patent/JPH07506187A/en
Publication of WO1993022656A1 publication Critical patent/WO1993022656A1/en

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Classifications

    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N35/00—Automatic analysis not limited to methods or materials provided for in any single one of groups G01N1/00 - G01N33/00; Handling materials therefor
    • G01N35/00584—Control arrangements for automatic analysers
    • G01N35/00594—Quality control, including calibration or testing of components of the analyser
    • G01N35/00712—Automatic status testing, e.g. at start-up or periodic
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01D—MEASURING NOT SPECIALLY ADAPTED FOR A SPECIFIC VARIABLE; ARRANGEMENTS FOR MEASURING TWO OR MORE VARIABLES NOT COVERED IN A SINGLE OTHER SUBCLASS; TARIFF METERING APPARATUS; MEASURING OR TESTING NOT OTHERWISE PROVIDED FOR
    • G01D18/00—Testing or calibrating apparatus or arrangements provided for in groups G01D1/00 - G01D15/00
    • G01D18/002—Automatic recalibration
    • G01D18/006—Intermittent recalibration
    • 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
    • G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • G01N33/02—Food
    • G01N33/14—Beverages
    • G01N33/146—Beverages containing alcohol
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N35/00—Automatic analysis not limited to methods or materials provided for in any single one of groups G01N1/00 - G01N33/00; Handling materials therefor
    • G01N35/00584—Control arrangements for automatic analysers
    • G01N35/00594—Quality control, including calibration or testing of components of the analyser
    • 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
    • G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
    • G01N21/77—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
    • G01N21/78—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator producing a change of colour
    • G01N21/79—Photometric titration
    • 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
    • G01N2201/02—Mechanical
    • G01N2201/024—Modular construction
    • 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
    • G01N2201/12738—Selectively initiating check
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N35/00—Automatic analysis not limited to methods or materials provided for in any single one of groups G01N1/00 - G01N33/00; Handling materials therefor
    • G01N35/00584—Control arrangements for automatic analysers
    • G01N35/00594—Quality control, including calibration or testing of components of the analyser
    • G01N35/00693—Calibration
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N35/00—Automatic analysis not limited to methods or materials provided for in any single one of groups G01N1/00 - G01N33/00; Handling materials therefor
    • G01N35/08—Automatic analysis not limited to methods or materials provided for in any single one of groups G01N1/00 - G01N33/00; Handling materials therefor using a stream of discrete samples flowing along a tube system, e.g. flow injection analysis

Definitions

  • the invention relates to a measurement device by colorimetry.
  • the invention relates to a device for measuring by colorimetry the concentration of a single parameter in a liquid sample.
  • the samples and standards are placed on the rotating plate of a dispenser (of the carousel type) and sucked successively by a peristaltic pump in a vein of reagents segmented by air bubbles. Mixing the samples and reagents under constant conditions results in a chemical reaction and the development of color. This reaction takes place in an analytical circuit bringing together all the elements necessary for carrying out a given analysis.
  • the circuit logically combines all the analytical functions: mixing (coil), dialysis (elimination of troublesome ions, if necessary), incubation at variable temperature (water bath). The intensity of the final coloration is measured in a spectrophotometer equipped with a continuous flow cell. The results are written in a series of peaks on the computer screen and then on the printer. In continuous flow analysis, all samples and standards are processed under identical analytical conditions, from sampling to reading.
  • the height of the peaks is directly proportional to the concentration of the measured parameter.
  • the computer processing of the signals allows a display of the graphic recording in real time and the edition of bulletins grouping together the set of parameters analyzed.
  • An important characteristic of flow analysis devices therefore resides in the possibility of continuously monitoring what is actually happening in this system. A simple glance is enough to identify any irregularity or possible malfunction. Thus, changing one of the reaction conditions will usually result in a baseline drift. Too small a sample volume, a decrease in sensitivity, the presence of air bubbles in the continuous flow cell, contamination are immediately signaled by a characteristic plot of the analytical curve.
  • a first object of the invention is therefore to propose a measurement device by colorimetry meeting the characteristics mentioned above. More particularly, the object of the present invention is to propose a device for measuring by colorimetry dedicated to the control of an important parameter for a laboratory or a production unit.
  • the invention proposes a device for measuring by colorimetry the concentration of a single parameter in a liquid sample comprising:
  • an analytical module comprising a pump, an analytical cassette and a continuous flow cell detector.
  • an electronic control module - an electronic control module.
  • this device comprises a repetitive calibration means, at any desired time, comprising means for establishing a calibration line at three points (baseline, standard 1, standard 2); means for repetitive measurement sampling, on stable segments of a constant portion of the analytical curve; a phasing means of the sampling means.
  • the repetitive calibration means further comprises means for validating the calibration consisting of a means of detecting the absence of an ascending portion of the analytical curve of the standard solution (s) and a means of calculation of the correlation coefficient of the calibration line, the calibration being validated for a value of the correlation coefficient greater than a configurable threshold.
  • the repetitive sampling means comprises a means of calculating the average of the measurements taken over a period of time from stable segments of the constant portion of the analytical curve and a means of validating the average of the measurements.
  • the means for controlling the sampling means comprises means for programming the times of sample collection, chemistry times, offset for measurement on the baseline, offset for measurement on the pan.
  • the colorimetric measurement device of the invention is available at all times, easy to use, its installation requires only a simple power outlet and can be done both in a laboratory and on a site. production. Just present the sample to be analyzed and press a button. A few minutes later, the result will be given and will make it possible to give information or make a decision.
  • the invention therefore relates to a device for measuring by colorimetry the concentration of a single parameter in a liquid sample.
  • the device of the type of the invention is therefore dedicated to controlling a single and important parameter of interest to an analysis laboratory or a manufacturing unit. This can be for example, in the field of oenology, the control of the volatile acidity of wine. But it is obvious that such a device is also applicable in other fields, such as, for example, hydrology.
  • the colorimetric measurement device of the type of the invention comprises a sampler module, an analytical module and an electronic control module.
  • the function of the sampler module is to regularly sample the sample by needle. Between each aspiration, the needle passes into a rinsing bowl or water is withdrawn.
  • the analytical module conventionally includes a pump, in particular a peristaltic pump, an analytical cassette bringing together all the elements necessary for the chemical reaction and a continuous flow measurement detector, in particular an interference colorometer.
  • the electronic control module notably includes a power card and a central unit card.
  • the power card has for function the general power supply of the analyzer, the power supply and the regulation of the colorimeter lamp, the power control of the heating of the water bath (es), the on / off control of the peristaltic pump, the control of the two solenoid valves for standards, the control of the sampling system, the detection of the presence of the sample, the bidirectional interface with the central unit card.
  • the function of the central unit card is to process the signal from the colorimeter, measure the temperature of the water bath (es), measure the voltage of the colorimeter lamp, convert the analog inputs to digital outputs, work of a program in read-only memory by the microprocessor
  • the measuring device further comprises a repetitive calibration means, at any desired time, comprising means for establishing a calibration line at three points (baseline, standard 1, standard 2); means for repetitive sampling of measurements on stable segments of a constant portion of the analytical curve, means for phasing the sampling means.
  • repetitive calibration means is meant the possibility of calibrating the device when the system is started, at the operator's request, automatically at regular and configurable intervals, automatic calibration always having priority over the sample next.
  • the standards are sampled by solenoid valves sequentially after a configurable delay depending on the chemistry.
  • the measurements are carried out as follows: baseline, standard 1, baseline, standard 2.
  • One of the important characteristics of the device of the invention is the absence of a graphic recording in real time visible to the operator.
  • the repetitive calibration means also comprises means for validating the calibration consisting of a means for detecting the absence of an ascending portion of the analytical curve of the solution (s). standard (s) and a means of calculating the correlation coefficient of the calibration line, the calibration being validated for a value of the correlation coefficient greater than a configurable threshold.
  • This repetitive sampling means comprises a means of calculating the average of the measurements taken over a period of time from stable segments of the constant portion of the analytical curve.
  • the sampling means is done as follows: - average m ⁇ of 20 measurements every second over a period of 10 seconds.
  • the repetitive sampling means also comprises a means for validating the average of the measurements. This means of validation is a means of calculating the standard deviation.
  • the phasing means of the sampling means comprises means for programming the sampling times TO / T1 of the sample, the chemistry delays
  • the phasing means makes it possible to fix the times T4 and T2, times which are decisive for the measurement respectively of I corresponding to the light intensity of the reagents associated with the standard or with the sample and Io corresponding to the light intensity of the reagents alone without the addition of standards or samples.
  • the device of the invention makes it possible to ensure that the system is in phase and that the recordings do take place on stable segments of the constant portion of the analytical curve.
  • the phasing means further comprises means for programming the propagation time of the sample from the sampler module to the pump.
  • the phasing and detection of anomalies can occur during the actual performance of the analysis and not afterwards.

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biochemistry (AREA)
  • Analytical Chemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Immunology (AREA)
  • Pathology (AREA)
  • Quality & Reliability (AREA)
  • Food Science & Technology (AREA)
  • Mathematical Physics (AREA)
  • Theoretical Computer Science (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Medicinal Chemistry (AREA)
  • Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
  • Automatic Analysis And Handling Materials Therefor (AREA)

Abstract

A device for colorimetrically measuring the concentration of a single parameter in a liquid sample. The device comprises a pump, an analytical cassette, a sensor with a continuous flux measurement vessel, and an electronic control module. The device further comprises a repetitive calibrating means which may be used at any time and includes a means for drawing a straight calibration line through three points; a repetitive means for sampling measurements on stable segments of a constant portion of the analytical curve; and a means for phasing the sampling means.

Description

DISPOSITIF DE MESURE PAR COLORIMETRIE COLORIMETRY MEASURING DEVICE
L'invention concerne un dispositif de mesure par colorimétrie.The invention relates to a measurement device by colorimetry.
Plus particulièrement, l'invention concerne un dispositif de mesure par colorimétrie de la concentration d'un paramètre unique dans un échantillon liquide.More particularly, the invention relates to a device for measuring by colorimetry the concentration of a single parameter in a liquid sample.
La technique d'analyse en flux continu, développée pendant les années 1950, est de nos jours le principe fondamental de nombreux analyseurs par dosage colorimétrique. Elle fonctionne sur le principe suivant :The continuous flow analysis technique, developed during the 1950s, is today the fundamental principle of many colorimetric analyzers. It works on the following principle:
- Les échantillons et étalons sont placés sur le plateau tournant d'un distributeur (du type carrousel) et aspirés successivement par une pompe péristaltique dans une veine de réactifs segmentée par des bulles d'air. Le mélange des échantillons et des réactifs dans des conditions constantes aboutit à une réaction chimique et au développement d'une coloration. Cette réaction prend place dans un circuit analytique regroupant la totalité des éléments nécessaires à la réalisation d'une analyse donnée.- The samples and standards are placed on the rotating plate of a dispenser (of the carousel type) and sucked successively by a peristaltic pump in a vein of reagents segmented by air bubbles. Mixing the samples and reagents under constant conditions results in a chemical reaction and the development of color. This reaction takes place in an analytical circuit bringing together all the elements necessary for carrying out a given analysis.
- Le circuit regroupe logiquement toutes les fonctions analytiques : mélange (bobine) , dialyse (élimination des ions gênants, si nécessaire) , incubation à température variable (bain-marie) . On mesure l'intensité de la coloration finale dans un spectrophotomètre équipé d'une cuve à flux continu. Les résultats s'inscrivent en une série de pics sur l'écran de l'ordinateur puis sur l'imprimante. Dans l'analyse à flux continu, tous les échantillons et étalons sont traités dans des conditions analytiques identiques, depuis le prélèvement jusqu'à la lecture.- The circuit logically combines all the analytical functions: mixing (coil), dialysis (elimination of troublesome ions, if necessary), incubation at variable temperature (water bath). The intensity of the final coloration is measured in a spectrophotometer equipped with a continuous flow cell. The results are written in a series of peaks on the computer screen and then on the printer. In continuous flow analysis, all samples and standards are processed under identical analytical conditions, from sampling to reading.
La hauteur des pics est directement proportionnelle à la concentration du paramètre mesuré. — Le traitement informatique des signaux permet un affichage de l'enregistrement graphique en temps réel et l'édition de bulletins regroupant l'ensemble de paramètres analysés. Une caractéristique importante des appareils d'analyse en flux continu réside donc dans la possibilité de contrôler continuellement ce qui se passe réellement dans ce système. Un simple regard suffit à identifier toute irrégularité ou mauvais fonctionnement éventuel. Ainsi, le changement de l'une des conditions de la réaction se traduira généralement par une dérive de la ligne de base. Un volume d'échantillon trop faible, une diminution de la sensibilité, la présence de bulles d'air dans la cuve à flux continu, une contamination se signalent immédiatement par un tracé caractéristique de la courbe analytique.The height of the peaks is directly proportional to the concentration of the measured parameter. - The computer processing of the signals allows a display of the graphic recording in real time and the edition of bulletins grouping together the set of parameters analyzed. An important characteristic of flow analysis devices therefore resides in the possibility of continuously monitoring what is actually happening in this system. A simple glance is enough to identify any irregularity or possible malfunction. Thus, changing one of the reaction conditions will usually result in a baseline drift. Too small a sample volume, a decrease in sensitivity, the presence of air bubbles in the continuous flow cell, contamination are immediately signaled by a characteristic plot of the analytical curve.
L'état de la technique peut être illustré par le document US-A-3 988 591 qui concerne un procédé photométrique et un photomètre photo-électrique pour la détermination quantitative d'une substance ou d'un produit dans une substance d'analyse. L'échantillon d'analyse, l'échantillon de référence et le ou les échantillon(s) d'étalonnage sont éclairés et pour chaque échantillon sont déterminées, de façon approximativement simultanée, les valeurs des intensités de mesures optiques et, au moyen de ces dernières valeurs est déterminée mathématiquement à partir de l'allure de la courbe d'étalonnage déterminée par ces valeurs d'intensité et la concentration connue du produit à analyser dans l'échantillon de référence, la concentration du produit ou de la substance dans l'échantillon d'analyse.The state of the art can be illustrated by document US-A-3 988 591 which relates to a photometric method and a photoelectric photometer for the quantitative determination of a substance or a product in an analytical substance. The analysis sample, the reference sample and the calibration sample (s) are illuminated and for each sample are determined, approximately simultaneously, the values of the optical measurement intensities and, by means of these last values is determined mathematically from the shape of the calibration curve determined by these intensity values and the known concentration of the product to be analyzed in the reference sample, the concentration of the product or substance in the analysis sample.
Le document US-A-3 975 727 décrit un appareil de calibration et d'étalonnage d'un niveau de signal de sortie analogique d'un équipement d'analyse automatique. Un tel appareil comprend un convertisseur A/D, des moyens de génération de la fonction inverse de la fonction analytique. De tels appareils d'analyse à flux continu sont destinés a être utilisés par exemple en oenologie pour le dosage des sucres, de l'acidité volatile, du Sθ2,... en hydrologie pour le dosage des nitrates, de l'ammoniaque, des chlorures, etc.The document US Pat. No. 3,975,727 describes an apparatus for calibrating and calibrating an analog output signal level of an automatic analysis equipment. Such an apparatus includes an A / D converter, means for generating the inverse function of the analytical function. Such continuous flow analysis devices are intended to be used for example in oenology for the determination of sugars, volatile acidity, Sθ2, ... in hydrology for the determination of nitrates, ammonia, chlorides, etc.
Ces appareils sont donc dédiés au contrôle de plusieurs paramètres et nécessitent autant d'échantillons, de réactifs et d'étalons que de paramètres à mesurer.These devices are therefore dedicated to the control of several parameters and require as many samples, reagents and standards as parameters to be measured.
Il s'ensuit : - Premièrement, la préparation de tout un lot d'échantillons, de réactifs et d'étalons, chaque étalon et réactif étant évidemment spécifique à la réaction chimique développant la coloration. Il en résulte des préparatifs longs et minutieux engendrant une augmentation considérable du temps nécessaire à analyser.It follows: - First, the preparation of a whole batch of samples, reagents and standards, each standard and reagent being obviously specific to the chemical reaction developing the coloration. This results in long and meticulous preparations generating a considerable increase in the time required to analyze.
- Deuxièmement, un enregistrement des valeurs obtenues et leur traitement informatique là encore grandement retardés du fait du nombre de paramètres d'analyses. - Enfin, la nécessité d'être spécialiste ou tout au moins compétent pour utiliser un tel appareil d'analyse à flux continu et notamment pour la préparation des étalons et réactifs nécessaires, l'interprétation des courbes d'analyses et l'identification de dysfonctionnements par étude des tracés des enregistrements.- Second, a recording of the values obtained and their computer processing, again greatly delayed due to the number of analysis parameters. - Finally, the need to be a specialist or at least competent to use such a continuous flow analysis device and in particular for the preparation of the necessary standards and reagents, the interpretation of the analysis curves and the identification of malfunctions by studying the traces of the recordings.
C'est pourquoi, la demande pour des dispositifs de mesure par colorimétrie, d'utilisation simple et rapide, et pour lesquels aucune compétence particulière n'est requise pour son utilisation de routine, est actuellement importante.This is why the demand for devices for measuring by colorimetry, of simple and rapid use, and for which no particular skill is required for its routine use, is currently important.
Un premier objet de l'invention est donc de proposer un dispositif de mesure par colorimétrie répondant aux caractéristiques mentionnées ci-dessus. Plus particulièrement, le but de la présente invention est de proposer un dispositif de mesure par colorimétrie dédié au contrôle d'un paramètre important pour un laboratoire ou une unité de production.A first object of the invention is therefore to propose a measurement device by colorimetry meeting the characteristics mentioned above. More particularly, the object of the present invention is to propose a device for measuring by colorimetry dedicated to the control of an important parameter for a laboratory or a production unit.
A cet effet, l'invention propose un dispositif de mesure par colorimétrie de la concentration d'un paramètre unique dans un échantillon liquide comportant :To this end, the invention proposes a device for measuring by colorimetry the concentration of a single parameter in a liquid sample comprising:
- un module préleveur,- a sampler module,
- un module analytique comportant une pompe, une cassette analytique et un détecteur à cuve de mesure à flux continu. - un module électronique de commande.- an analytical module comprising a pump, an analytical cassette and a continuous flow cell detector. - an electronic control module.
Selon l'invention , ce dispositif comprend un moyen répétitif d'étalonnage, à tout moment désiré, comprenant des moyens d'établir une droite d'étalonnage sur trois points (ligne de base, étalon 1, étalon 2) ; un moyen d'échantillonnage répétitif de mesure, sur des segments stables d'une portion constante de la courbe analytique ; un moyen de phasage du moyen d'échantillonnage.According to the invention, this device comprises a repetitive calibration means, at any desired time, comprising means for establishing a calibration line at three points (baseline, standard 1, standard 2); means for repetitive measurement sampling, on stable segments of a constant portion of the analytical curve; a phasing means of the sampling means.
Le moyen répétitif d'étalonnage comprend en outre des moyens de validation de l'étalonnage consistant en un moyen de détection de l'absence de portion ascendante de la courbe analytique de la ou les solution(s) étalon(s) et un moyen de calcul du coefficient de corrélation de la droite d'étalonnage, l'étalonnage étant validé pour une valeur du coefficient de corrélation supérieure à un seuil paramétrable.The repetitive calibration means further comprises means for validating the calibration consisting of a means of detecting the absence of an ascending portion of the analytical curve of the standard solution (s) and a means of calculation of the correlation coefficient of the calibration line, the calibration being validated for a value of the correlation coefficient greater than a configurable threshold.
Le moyen d'échantillonnage répétitif comprend un moyen de calcul de la moyenne des mesures prises sur une période de temps de segments stables de la portion constante de la courbe analytique et un moyen de validation de la moyenne des mesures.The repetitive sampling means comprises a means of calculating the average of the measurements taken over a period of time from stable segments of the constant portion of the analytical curve and a means of validating the average of the measurements.
Le moyen de contrôle du moyen d'échantillonnage comprend des moyens de programmation des temps de prélèvement de l'échantillon, de délais de chimie, de décalage pour la mesure sur la ligne de base, de décalage pour la mesure sur le plateau. Ainsi, un dispositif de mesure par colorimétrie du type de l'invention permet : d'une part, d'établir, à tout moment et rapidement, une droite d'étalonnage, de la valider, permettant de ce fait la détermination de la concentration d'un paramètre unique dans l'échantillon par comparaison avec la dernière droite d'étalonnage établie ; la fiabilité du système s'en trouve donc accrue. - d'autre part, de s'affranchir d'un enregistrement graphique en temps réel grâce aux moyens d'échantillonnage répétitif et de phasage du moyen d'échantillonnage.The means for controlling the sampling means comprises means for programming the times of sample collection, chemistry times, offset for measurement on the baseline, offset for measurement on the pan. Thus, a measurement device by colorimetry of the type of the invention makes it possible: on the one hand, to establish, at any time and quickly, a calibration line, to validate it, thereby allowing the determination of the concentration a single parameter in the sample by comparison with the last established calibration line; the reliability of the system is therefore increased. - on the other hand, to get rid of a graphic recording in real time thanks to the means of repetitive sampling and phasing of the sampling means.
Il en résulte que le dispositif de mesure par colorimétrie de l'invention est à tout instant disponible, simple d'utilisation, son installation ne nécessite qu'une simple prise de courant et peut être faite aussi bien dans un laboratoire que sur un site de production. Il suffit de présenter l'échantillon à analyser et de presser sur un bouton. Quelques minutes après, le résultat sera rendu et permettra de donner une information ou de prendre une décision.As a result, the colorimetric measurement device of the invention is available at all times, easy to use, its installation requires only a simple power outlet and can be done both in a laboratory and on a site. production. Just present the sample to be analyzed and press a button. A few minutes later, the result will be given and will make it possible to give information or make a decision.
Les autres caractéristiques de l'invention seront bien comprises grâce à la description qui suivra en référence à la figure unique annexée qui est une représentation théorique sur un graphique intensité (I) - temps (T) des moyens d'échantillonnage et de phasage du moyen d'échantillonnage.The other characteristics of the invention will be clearly understood thanks to the description which follows with reference to the single appended figure which is a theoretical representation on a graph of intensity (I) - time (T) of the sampling and phasing means of the means sampling.
L'invention concerne donc un dispositif de mesure par colorimétrie de la concentration d'un paramètre unique dans un échantillon liquide.The invention therefore relates to a device for measuring by colorimetry the concentration of a single parameter in a liquid sample.
Le dispositif du type de l'invention est donc dédié au contrôle d'un paramètre unique et- important intéressant un laboratoire d'analyse ou une unité de fabrication. Ce peut être par exemple, dans le domaine de l'oenologie, le contrôle de l'acidité volatile du vin. Mais il est bien évident qu'un tel dispositif est également applicable dans d'autres domaines, comme par exemple, l'hydrologie.The device of the type of the invention is therefore dedicated to controlling a single and important parameter of interest to an analysis laboratory or a manufacturing unit. This can be for example, in the field of oenology, the control of the volatile acidity of wine. But it is obvious that such a device is also applicable in other fields, such as, for example, hydrology.
Le dispositif de mesure par colorimétrie du type de l'invention comporte un module préleveur, un module analytique et un module électronique de commande.The colorimetric measurement device of the type of the invention comprises a sampler module, an analytical module and an electronic control module.
Le module préleveur a pour fonction le prélèvement régulier par aiguille de l'échantillon. Entre chaque aspiration, l'aiguille passe dans une cuvette de rinçage ou de l'eau est prélevée.The function of the sampler module is to regularly sample the sample by needle. Between each aspiration, the needle passes into a rinsing bowl or water is withdrawn.
Entre chaque position de prélèvement de l'échantillon ou de l'eau de.rinçage, pendant le mouvement du bras supportant l'aiguille, une bulle d'air est aspirée et permet la division du flux d'échantillon en un grand nombre de segments distincts.Between each position for taking the sample or rinsing water, during the movement of the arm supporting the needle, an air bubble is sucked in and allows the division of the sample flow into a large number of segments separate.
Le module analytique comporte de façon classique une pompe, notamment une pompe peristaltique, une cassette analytique rassemblant l'ensemble des éléments nécessaires à la réaction chimique et un détecteur de mesure à flux continu, notamment un colori ètre interférentiel.The analytical module conventionally includes a pump, in particular a peristaltic pump, an analytical cassette bringing together all the elements necessary for the chemical reaction and a continuous flow measurement detector, in particular an interference colorometer.
Le module électronique de commande comprend notamment une carte puissance et une carte unité centrale.The electronic control module notably includes a power card and a central unit card.
La carte puissance a pour fonction l'alimentation générale de l'analyseur, l'alimentation et la régulation de la lampe du colorimètre, la commande de puissance du chauffage du ou des bains-marie, la commande marche/arrêt de la pompe peristaltique, la commande des deux électrovannes pour étalons, la commande du système de prélèvement, la détection de la présence de l'échantillon, l'interface bidirectionnelle avec la carte unité centrale.The power card has for function the general power supply of the analyzer, the power supply and the regulation of the colorimeter lamp, the power control of the heating of the water bath (es), the on / off control of the peristaltic pump, the control of the two solenoid valves for standards, the control of the sampling system, the detection of the presence of the sample, the bidirectional interface with the central unit card.
La carte unité centrale a pour fonction le traitement du signal issu du colorimètre, la mesure de la température du ou des bains-marie, la mesure de la tension de la lampe du colorimètre, la conversion des entrées analogiques en sorties numériques, la mise en oeuvre d'un programme en mémoire morte par le microprocesseurThe function of the central unit card is to process the signal from the colorimeter, measure the temperature of the water bath (es), measure the voltage of the colorimeter lamp, convert the analog inputs to digital outputs, work of a program in read-only memory by the microprocessor
FEUILLE DE REMPLACEMENT permettant la gestion de l'ensemble de l'analyseur, l'interface bidirectionnelle avec la carte unité de puissance, l'interface imprimantes interne et externe, l'interface bidirectionnelle avec un ordinateur extérieur. Le dispositif de mesure selon l'invention comprend en outre un moyen répétitif d'étalonnage, à tout moment désiré, comprenant des moyens d'établir une droite d'étalonnage sur trois points (ligne de base, étalon 1, étalon 2) ; un moyen d'échantillonnage répétitif de mesures sur des segments stables d'une portion constante de la courbe analytique, un moyen de phasage du moyen d'échantillonnage.REPLACEMENT SHEET allowing the management of the whole analyzer, the bidirectional interface with the power unit card, the internal and external printer interface, the bidirectional interface with an external computer. The measuring device according to the invention further comprises a repetitive calibration means, at any desired time, comprising means for establishing a calibration line at three points (baseline, standard 1, standard 2); means for repetitive sampling of measurements on stable segments of a constant portion of the analytical curve, means for phasing the sampling means.
On entend ici par moyen répétitif d'étalonnage la possibilité d'étalonner le dispositif à la mise en route du système, à la demande de l'opérateur, en automatique à intervalle régulier et paramétrable, l'étalonnage automatique étant toujours prioritaire sur le prélèvement suivant.By repetitive calibration means is meant the possibility of calibrating the device when the system is started, at the operator's request, automatically at regular and configurable intervals, automatic calibration always having priority over the sample next.
L'équation de la droite d'étalonnage est alors mémorisée jusqu'au prochain étalonnage.The equation of the calibration line is then stored until the next calibration.
Les étalons sont prélevés par électrovannes séquentiellement après un délai paramétrable dépendant de la chimie. Les mesures sont effectuées comme suit : ligne de base, étalon 1, ligne de base, étalon 2. Une des caractéristiques importantes du dispositif de l'invention est l'absence d'un enregistrement graphique en temps réel visible par l'opérateur.The standards are sampled by solenoid valves sequentially after a configurable delay depending on the chemistry. The measurements are carried out as follows: baseline, standard 1, baseline, standard 2. One of the important characteristics of the device of the invention is the absence of a graphic recording in real time visible to the operator.
Cette caractéristique est permise par le fait que le moyen répétitif d'étalonnage comprend en outre des moyens de validation de l'étalonnage consistant en un moyen de détection de l'absence de portion ascendante de la courbe analytique de la ou des solution(s) étalon(s) et un moyen de calcul du coefficient de corrélation de la droite d'étalonnage, l'étalonnage étant validé pour une valeur du coefficient de corrélation supérieure à un seuil paramétrable. Ainsi, dès la mise en route du système et à tout moment paramétrable, il est possible d'avertir l'opérateur du manque de fiabilité de l'étalonnage.This characteristic is enabled by the fact that the repetitive calibration means also comprises means for validating the calibration consisting of a means for detecting the absence of an ascending portion of the analytical curve of the solution (s). standard (s) and a means of calculating the correlation coefficient of the calibration line, the calibration being validated for a value of the correlation coefficient greater than a configurable threshold. Thus, as soon as the system is started and at any time configurable, it is possible to warn the operator of the unreliability of the calibration.
L'absence d'enregistrement graphique en temps réel visible par l'opérateur est également permise grâce aux moyens d'échantillonnage répétitif de mesure sur des segments stables d'une portion constante de la courbe analytique et de phasage du moyen d'échantillonnage.The absence of real-time graphical recording visible to the operator is also permitted by means of repetitive measurement sampling means on stable segments of a constant portion of the analytical curve and of phasing of the sampling means.
Ce moyen d'échantillonnage répétitif comprend un moyen de calcul de la moyenne des mesures prises sur une période de temps de segments stables de la portion constante de la courbe analytique.This repetitive sampling means comprises a means of calculating the average of the measurements taken over a period of time from stable segments of the constant portion of the analytical curve.
A titre d'exemple non limitatif, le moyen d'échantillonnage se fait de la façon suivante : - moyenne m^ de 20 mesures toutes les secondes sur une période de 10 secondes.By way of nonlimiting example, the sampling means is done as follows: - average m ^ of 20 measurements every second over a period of 10 seconds.
- la mesure globale sera : Ml = (m + 2• • • m2o)/10.- the global measurement will be: Ml = (m + 2 • • • m 2 o) / 10.
Le moyen d'échantillonnage répétitif comprend en outre un moyen de validation de la moyenne des mesures. Ce moyen de validation est un moyen de calcul de l'écart type.The repetitive sampling means also comprises a means for validating the average of the measurements. This means of validation is a means of calculating the standard deviation.
Ainsi, par exemple, si l'écart type du segment Ml est supérieur à un seuil paramétrable, une deuxième mesureThus, for example, if the standard deviation of the segment Ml is greater than a configurable threshold, a second measurement
M2 sera effectuée. De la même manière, si l'écart type du deuxième segment M2 est supérieur au seuil paramétrable, l'opérateur sera averti du manque de fiabilité des résultats.M2 will be performed. Likewise, if the standard deviation of the second segment M2 is greater than the configurable threshold, the operator will be warned of the unreliability of the results.
Le moyen de phasage du moyen d'échantillonnage comprend des moyens de programmation des temps de prélèvement TO/Tl de l'échantillon, de délais de chimieThe phasing means of the sampling means comprises means for programming the sampling times TO / T1 of the sample, the chemistry delays
T1/T3, de décalage pour la mesure sur la ligne de baseT1 / T3, offset for baseline measurement
T3/T2, de décalage pour la mesure sur le plateau T3/T4.T3 / T2, offset for measurement on the T3 / T4 stage.
On comprend ainsi que le moyen de phasage permet de ixer les temps T4 et T2, temps qui sont déterminants pour la mesure respectivement de I correspondant à l'intensité lumineuse des réactifs associés à l'étalon ou à l'échantillon et de Io correspondant à l'intensité lumineuse des réactifs seuls sans addition d'étalons ou d'échantillons.It is thus understood that the phasing means makes it possible to fix the times T4 and T2, times which are decisive for the measurement respectively of I corresponding to the light intensity of the reagents associated with the standard or with the sample and Io corresponding to the light intensity of the reagents alone without the addition of standards or samples.
Par le biais du moyen de phasage et du moyen de validation, le dispositif de l'invention permet de s'assurer que le système est en phase et que les enregistrements ont bien lieu sur des segments stables de la portion constante de la courbe analytique.By means of the phasing means and the validation means, the device of the invention makes it possible to ensure that the system is in phase and that the recordings do take place on stable segments of the constant portion of the analytical curve.
Le moyen de phasage comprend en outre un moyen de programmation du temps de propagation de l'échantillon du module préleveur à la pompe.The phasing means further comprises means for programming the propagation time of the sample from the sampler module to the pump.
Grâce au dispositif de mesure par colorimétrie de l'invention, la mise en phase et la détection des anomalies peuvent intervenir pendant la réalisation même de l'analyse et non après.Thanks to the colorimetric measurement device of the invention, the phasing and detection of anomalies can occur during the actual performance of the analysis and not afterwards.
En effet, en se reportant à la figure, on peut voir que si le système est mal phase c'est-à-dire par exemple que le temps de décalage pour la mesure sur le plateau T3/T4 est mal programmé et intervient à cheval sur la portion constante et la portion descendante de la courbe analytique, à la suite du moyen d'échantillonnage entrera en jeu le moyen de validation qui ne validera pas la mesure et l'indiquera à l'opérateur par affichage sur écran et impression d'un ticket. Indeed, by referring to the figure, it can be seen that if the system is out of phase, that is to say for example that the offset time for the measurement on the T3 / T4 stage is badly programmed and intervenes on horseback on the constant portion and the descending portion of the analytical curve, following the sampling means will come into play the validation means which will not validate the measurement and will indicate it to the operator by display on screen and printing of a ticket.

Claims

REVENDICATIONS
1. Dispositif de mesure par colorimétrie de la concentration d'un paramètre unique dans un échantillon liquide comportant un module préleveur, un module analytique comportant une pompe, une cassette analytique et un détecteur à cuve de mesure à flux continu, un module électronique de commande, caractérisé en ce qu'il comprend un moyen répétitif d'étalonnage, à tout moment désiré, comprenant des moyens d'établir une droite d'étalonnage sur trois points (ligne de base, étalon 1, étalon 2) ; un moyen d'échantillonnage répétitif de mesures sur des segments stables d'une portion constante de la courbe analytique ; et un moyen de phasage du moyen d'échantillonnage.1. Device for colorimetric measurement of the concentration of a single parameter in a liquid sample comprising a sampling module, an analytical module comprising a pump, an analytical cassette and a detector with a flow-through measuring cell, an electronic control module , characterized in that it comprises a repetitive calibration means, at any desired time, comprising means for establishing a calibration line at three points (baseline, standard 1, standard 2); means for repetitive sampling of measurements on stable segments of a constant portion of the analytical curve; and a means for phasing the sampling means.
2. Dispositif selon la revendication 1, caractérisé en ce que le moyen répétitif d'étalonnage comprend en outre des moyens de validation de l'étalonnage consistant en un moyen de détection de l'absence de portion ascendante de la courbe analytique de la ou les solution(s) étalon(s) et un moyen de calcul du coefficient de corrélation de la droite d'étalonnage, l'étalonnage étant validé pour une valeur du coefficient de corrélation supérieure à un seuil paramétrable.2. Device according to claim 1, characterized in that the repetitive calibration means further comprises means for validating the calibration consisting of a means for detecting the absence of an ascending portion of the analytical curve of the one or more standard solution (s) and a means of calculating the correlation coefficient of the calibration line, the calibration being validated for a value of the correlation coefficient greater than a configurable threshold.
3. Dispositif selon la revendication 1, caractérisé en ce que le moyen d'échantillonnage répétitif comprend un moyen de calcul de la moyenne des mesures prises sur une période de temps de segments stables de la portion constante de la courbe analytique.3. Device according to claim 1, characterized in that the repetitive sampling means comprises a means of calculating the average of the measurements taken over a time period of stable segments of the constant portion of the analytical curve.
4. Dispositif selon la revendication 3 caractérisé en ce que le moyen d'échantillonnage répétitif comprend un moyen de validation de la moyenne des mesures. 4. Device according to claim 3 characterized in that the repetitive sampling means comprises means for validating the average of the measurements.
5. Dispositif selon la revendication 4 caractérisé en ce que le moyen de validation de la moyenne est un moyen de calcul de l'écart type.5. Device according to claim 4 characterized in that the means for validating the average is a means of calculating the standard deviation.
6. Dispositif selon la revendication 1, caractérisé en ce que le moyen de phasage du moyen d'échantillonnage comprend des moyens de programmation des temps de prélèvement (TO/Tl) de l'échantillon, de délais de chimie (T1/T3) , de décalage pour la mesure sur la ligne de base (T3/T2) , de décalage pour la mesure sur le plateau (T3/T4) .6. Device according to claim 1, characterized in that the phasing means of the sampling means comprises means for programming the sampling times (TO / Tl) of the sample, of chemistry delays (T1 / T3), offset for measurement on the baseline (T3 / T2), offset for measurement on the pan (T3 / T4).
7. Dispositif selon la revendication 6, caractérisé en ce que le moyen de phasage comprend en outre un moyen de programmation du temps de propagation de l'échantillon du module préveleur à la pompe. 7. Device according to claim 6, characterized in that the phasing means further comprises means for programming the propagation time of the sample from the preveleur module to the pump.
PCT/FR1993/000418 1992-04-29 1993-04-28 Colorimetric measurement device WO1993022656A1 (en)

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EP93911836A EP0638167A1 (en) 1992-04-29 1993-04-28 Colorimetric measurement device
JP5519003A JPH07506187A (en) 1992-04-29 1993-04-28 colorimetric measuring device

Applications Claiming Priority (2)

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FR92/05321 1992-04-29
FR9205321A FR2690746B1 (en) 1992-04-29 1992-04-29 COLORIMETRY MEASURING DEVICE.

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FR2852694B1 (en) * 2003-03-19 2006-05-26 Bernard Pierre Andre Genot OPTOELECTRONIC MEASURING APPARATUS WITH MULTIPLE MODULAR COMPOSITION
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3975727A (en) * 1974-06-28 1976-08-17 Technicon Instruments Corporation Automated calibration and standardization apparatus
US3988591A (en) * 1974-06-10 1976-10-26 Dr. W. Killer Ag Photometric method for the quantitative determination of a material or substance in an analysis substance and photoelectric photometer for the performance of the aforesaid method

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3988591A (en) * 1974-06-10 1976-10-26 Dr. W. Killer Ag Photometric method for the quantitative determination of a material or substance in an analysis substance and photoelectric photometer for the performance of the aforesaid method
US3975727A (en) * 1974-06-28 1976-08-17 Technicon Instruments Corporation Automated calibration and standardization apparatus

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FR2690746B1 (en) 1994-07-22
EP0638167A1 (en) 1995-02-15
FR2690746A1 (en) 1993-11-05

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