EP1144986A2 - Analyse par fluorescence x a dispersion d'energie de substance chimique - Google Patents

Analyse par fluorescence x a dispersion d'energie de substance chimique

Info

Publication number
EP1144986A2
EP1144986A2 EP00901071A EP00901071A EP1144986A2 EP 1144986 A2 EP1144986 A2 EP 1144986A2 EP 00901071 A EP00901071 A EP 00901071A EP 00901071 A EP00901071 A EP 00901071A EP 1144986 A2 EP1144986 A2 EP 1144986A2
Authority
EP
European Patent Office
Prior art keywords
sample
packaging
ray fluorescence
substances
analysis
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Withdrawn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
EP00901071A
Other languages
German (de)
English (en)
Inventor
Alexander Henrich
Hans-Helmut Itzel
Peter Hoffmann
Hugo Ortner
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.)
Merck Patent GmbH
Original Assignee
Merck Patent GmbH
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
Priority claimed from DE19921317A external-priority patent/DE19921317A1/de
Application filed by Merck Patent GmbH filed Critical Merck Patent GmbH
Publication of EP1144986A2 publication Critical patent/EP1144986A2/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Withdrawn legal-status Critical Current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
    • G01N23/00—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00
    • G01N23/22—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by measuring secondary emission from the material
    • G01N23/223—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by measuring secondary emission from the material by irradiating the sample with X-rays or gamma-rays and by measuring X-ray fluorescence
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N2223/00—Investigating materials by wave or particle radiation
    • G01N2223/07—Investigating materials by wave or particle radiation secondary emission
    • G01N2223/076—X-ray fluorescence

Definitions

  • the present invention relates to the differentiation and classification by means of X-ray fluorescence analysis of chemical substances whose X-ray fluorescence lines cannot be detected and which therefore cannot be classified by energy-dispersive X-ray fluorescence analysis (EDRFA) alone, through the packaging and without having to carry out a sampling.
  • EDRFA energy-dispersive X-ray fluorescence analysis
  • material flow means taken back chemicals that are returned to the chemical factory by the end users or intermediaries.
  • each material flow is to be regarded as waste until a control plausibly characterizes each material flow. Only then can the material flow be referred to as a product or raw material, secondary raw material or finally as waste.
  • Energy-dispersive X-ray fluorescence analysis is a fast analysis method for the qualitative and quantitative determination of elements in substances. The determination is made by evaluating the X-ray fluorescence lines.
  • the X-ray fluorescence lines of the elements with atomic numbers between 21 and 92 can be detected and assigned by a PE (polyethylene) container.
  • PE polyethylene
  • a large part of the substances consists of elements with atomic numbers between 1 and 20. Characterization of these elements and thus these substances is not possible with the conventional EDRFA evaluation (X-ray fluorescence line determination and evaluation) due to the lack of X-ray fluorescence lines.
  • a statement about the substance and its composition can be made via the coherent (Rayleigh scatter) and incoherent (Compton scatter) scatter of X-rays in the substance. Correlations between the mean atomic number and the ratio between coherent and incoherent scattered radiation are known and are described, for example, by H. Kunzendorf in Nuclear Instruments and methods, 99 (1972) 61 1-612. Various EDRFA providers use the matrix correction of X-ray fluorescence lines based on the inelastic scattered radiation for the quantitative evaluation.
  • the object of the present invention is to safely characterize and distinguish substances from one another whose x-ray fluorescence lines cannot be detected and which therefore cannot be classified by energy-dispersive x-ray fluorescence analysis (EDRFA) alone, without additional, other analysis methods and without having to take a sample to distinguish.
  • EDRFA energy-dispersive x-ray fluorescence analysis
  • the invention therefore relates to a method for classification and identification by means of energy-dispersive X-ray fluorescence analysis of chemical substances whose X-ray fluorescence lines cannot be detected and which cannot therefore be classified solely by energy-dispersive X-ray fluorescence analysis (EDRFA), which is characterized in that the sample to be analyzed in its original packaging or as such without prior preparation in a sample container
  • EDRFA energy-dispersive X-ray fluorescence analysis
  • a) is positioned in an X-ray fluorescence system in front of the measurement opening in a sample chamber, then measured and
  • PCA principal component analysis
  • RDA Regularized Discriminance Analysis
  • the analysis is therefore preferably carried out through the packaging, different packaging materials (glass or polyethylene packaging) being able to be present and having to be taken into account accordingly in the assignment.
  • mapping analytics When checking these substances, the aim is not to completely identify the substances, including the main and secondary constituents. However, a plausible assignment of the substance spectrum recorded by the packaging to the spectrum of the substance name noted on the packaging label is expected. This type of analytics is called mapping analytics.
  • Substances containing elements with an atomic number (OZ)> 22 can be characterized depending on the packaging size by the PE packaging based on their element lines. The detection of the peaks, determination of the peak parameters (peak position, half-width, area) takes place automatically, as does the subsequent comparison of the XRF data with the information from the database. It is new, too, that these substance groups can also be distinguished much better using multivariate, statistical methods. For this purpose, the X-ray fluorescence range of the element is calculated with an OZ> 22 and the Compton and Rayleigh scattering range with the multivariate statistical methods.
  • PCA main component analysis
  • RDA regulating discriminant analysis
  • a further assignment can be made by directly applying multivariate statistical methods to the Compton and Rayleigh scattering range.
  • the various methods can be applied to the scatter spectra alone or both in succession.
  • Classes of recorded spectra of different substances are visualized with the PCA, then their classes are calculated with the RDA. This means that both the spectral range or the main components calculated for the spectral range can be used as variables in the RDA.
  • the number of main components used is determined according to the so-called "Eigenvalue 1 criterion" or by cross-validation.
  • the sample to be analyzed is in its original packaging - opening the package is therefore not necessary and sampling is not necessary - or as such is positioned in a sample chamber in the X-ray fluorescence system in front of the measurement opening in a sample chamber without prior preparation.
  • the packaging or the sample vessel in which the sample to be analyzed is located can consist of a material selected from the group consisting of polyethylene, glass, aluminum, paper and cardboard.
  • the EDRFA spectrum is recorded. Then, if there are no X-ray fluorescence lines of the elements from the substance, the Compton and Rayleigh scattering range from 19.6 to 26.3 keV (note: this range only applies to excitation with an Ag tube, see Table 1) ; when using other excitation sources, this scattering range lies in an area corresponding to the excitation source) for the multivariate, statistical calculations (PCA.RDA). Subsequently - if desired - the main components are calculated with the PCA for the new substance in the new model (incl. Substance), which contains the spectrum of the substance. This step is optional. In the next step, the classes are set up and defined in the RDA with a learning data set (spectral ranges or optionally the main components determined from the previous step).
  • the new substance is then classified / classified
  • Test data set i.e. spectral range or main components
  • main components from the PCA can also be used for the classification instead of the spectrum.
  • the target class must of course be included in the learning data record.
  • the classification is based on the calculations described in the literature. The following references are cited as examples:
  • the comparison is made between the class assigned to the spectrum and the actual class or the substance name described on the label. If the result is the same, the substance is processed further in the form of storage and use in production.
  • This entire evaluation is preferably carried out automatically by using suitably adapted software, which considerably speeds up the entire analysis time and calculation time.
  • the PCA and RDA algorithm is commercially available and can be implemented in the later evaluation data processing.
  • the substances to be analyzed in their packaging usually reach the EDRFA system on a conveyor belt.
  • the position The packaging in front of the measuring opening, the recording of the EDRFA spectrum, the evaluation of the spectra, the subsequent spectrum assignment and the repositioning of the packaging on the conveyor belt are carried out fully automatically. Accordingly, the EDRFA system and the associated components (sample chamber, interfaces to the substance database, control of the EDRFA) must be designed so that automatic control of the individual components is possible.
  • the invention therefore also relates to the fact that the method is used within an automated system for sorting and assigning old or new packaging containing chemical substances.
  • the automated system preferably consists of the following components or steps:
  • An X-ray fluorescence analysis apparatus consisting of an X-ray tube, a generator, an energy-resolving detector and evaluation electronics is preferably used.
  • the following configuration of the EDRFA system is selected: X-ray tube with generator and semiconductor detector, the measurement geometry, that is to say the angle between the excitation source, sample and detector, is selected to be variable between 45 ° and 90 °, so that the Compton and Rayleigh scatter lines are resolved in the detector.
  • the sample chamber must completely enclose the package, since protective mechanisms must be observed when handling ionizing radiation in accordance with the X-ray regulation. It must be ensured that the X-rays emitted do not exceed a defined limit.
  • the sample chamber is preferably made of a material that does not increase the spectra background (scatter) in the sample chamber, can be opened and closed automatically and can be adapted to the EDRFA apparatus.
  • the parameters for routine operation i.e. X-ray tube voltage and current, primary beam filter material and thickness, detector aperture, position coordinates for the pack in front of the EDRFA measurement opening, can be determined and set experimentally depending on requirements and requirements. For a later assignment of the spectra to the substances, the packaging sizes, materials and packaging positions must also be taken into account.
  • the analysis duration should also be short.
  • the measurement time for recording the spectra is preferably ⁇ 30 seconds.
  • Example A Table 1 describes a preferred configuration with the parameters for measurement and evaluation. This is only intended to be an exemplary list that is in no way limiting. Example A also lists the preferred general measurement conditions for the tests.
  • the method according to the invention provides a fast, reliable and effective analysis method for identifying chemical substances through the packaging.
  • the EDRFA is based on such substances from elements with numbers between 1 and 20, which were previously not distinguishable in this way, expanded.
  • a significantly improved characterization and assignment can be achieved when taking back chemicals, without having to use further analysis methods with complex sample preparation and sampling.
  • Table 1 describes the configuration with the parameters for measurement and evaluation, which was used in the following examples.
  • RACK-300 analog electronics in 19 rack with analog power supply, active filter amplifier with triangular pulse shaping, baseline restorer,
  • Pulse pileup rejector and pulse striker, detector high voltage supply continuously adjustable from 0 - 1000 V.
  • ICP-300A industrial PC in 19 "case with 250 W power supply, additional fan, passive bus board with 8 ISA, 2 ISA / PCI and 4 PCI slots, single board computer with Pentium / 133 CPU, 256 kB cache, 32 MB RAM , 2 x ser., 1 x par. Interface E-IDE interface, 1, 44 MB floppy disk drive, 1, 2 GB hard disk, CD-ROM drive, PCI graphics card Matrox-Millenium (2 MB), MF keyboard, MS Mouse, MS DOS 6.22 and MS Windows 3.11 TM
  • the measurement conditions for the substance classification tests can be selected as follows:
  • Table 2 lists the different substances from this series of measurements with their physical data.
  • Measurement series 3 was carried out using substances from the iron group in accordance with the measurement parameters and conditions described in Example A.
  • Table 4 shows the physical data of this series of measurements.
  • the best possible separation of the substances in the new data space and the lowest scatter within the groups is achieved for the no element group by the PCA calculation taking into account the Compton and Rayleigh scattering range.
  • good separation of the groups from one another and little scatter within the groups is achieved by means of the PCA calculation using a combination of the fluorescence line region of the element and the Compton and Rayleigh scatter region.
  • the examples with the RDA calculations show that EDRFA spectra recorded by the packaging can be distinguished from one another with the aid of the respective RDA model if the spectra have spectral similarities which are recognizable for the RDA.
  • the substances can be assigned to a previously defined class with the spectral range (fluorescence line, Compton and Rayleigh scattering range) as well as with the significant HK from the PCA as variables.
  • the classification with the spectral range is even better for the Eisen group (calculated by internal cross-validation of the Eisen data set).

Landscapes

  • Physics & Mathematics (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)
  • Analysing Materials By The Use Of Radiation (AREA)

Abstract

L'invention concerne un procédé de classification et d'identification par analyse par fluorescence X à dispersion d'énergie de substances chimiques dont les lignes de fluorescence X ne peuvent être détectées et qui ne peuvent par conséquent être classifiées uniquement par analyse par fluorescence X à dispersion d'énergie. Ce procédé se caractérise en ce que l'échantillon à analyser situé dans son emballage d'origine ou tel quel sans traitement préalable, dans un récipient d'échantillon, a) est positionné dans une installation de fluorescence X devant l'ouverture de mesure dans une chambre d'échantillon; b) est ensuite mesuré et c) est classifié et identifié sur la base de procédés statistiques multivariables appliqués aux signaux de mesure obtenus, c.-à-d. à la plage de diffusion de Compton et Rayleigh.
EP00901071A 1999-01-23 2000-01-07 Analyse par fluorescence x a dispersion d'energie de substance chimique Withdrawn EP1144986A2 (fr)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
DE19902617 1999-01-23
DE19902617 1999-01-23
DE19921317A DE19921317A1 (de) 1999-01-23 1999-05-08 Energiedispersive Röntgenfluoreszenzanalyse von chemischen Substanzen
DE19921317 1999-05-08
PCT/EP2000/000070 WO2000043761A2 (fr) 1999-01-23 2000-01-07 Analyse par fluorescence x a dispersion d'energie de substance chimique

Publications (1)

Publication Number Publication Date
EP1144986A2 true EP1144986A2 (fr) 2001-10-17

Family

ID=26051454

Family Applications (1)

Application Number Title Priority Date Filing Date
EP00901071A Withdrawn EP1144986A2 (fr) 1999-01-23 2000-01-07 Analyse par fluorescence x a dispersion d'energie de substance chimique

Country Status (4)

Country Link
US (1) US6496562B1 (fr)
EP (1) EP1144986A2 (fr)
JP (1) JP2002535647A (fr)
WO (1) WO2000043761A2 (fr)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6858148B2 (en) * 2003-07-16 2005-02-22 The Regents Of The University Of California Method and apparatus for detecting chemical binding
US20040017884A1 (en) * 2002-07-25 2004-01-29 Havrilla George J. Flow method and apparatus for screening chemicals using micro x-ray fluorescence
US7519145B2 (en) * 2002-07-25 2009-04-14 Los Alamos National Security, Llc Flow method and apparatus for screening chemicals using micro x-ray fluorescence
DE20311760U1 (de) * 2003-07-30 2003-12-11 Trw Automotive Safety Systems Gmbh Fahrzeuglenkrad
DE102005046878A1 (de) * 2005-09-29 2007-04-12 Katz, Elisabeth Vorrichtung und Verfahren zur Schnell- oder Online-Bestimmung der Komponenten eines Zwei- oder Mehrstoffsystems
US8000440B2 (en) * 2006-07-10 2011-08-16 Agresearch Limited Target composition determination method and apparatus
CN106257273B (zh) * 2015-12-28 2018-09-11 国家地质实验测试中心 基于edxrf光谱仪快速检测土壤中稀土总量的方法
CN106153658A (zh) * 2016-09-21 2016-11-23 中国科学院合肥物质科学研究院 一种能量色散x射线荧光光谱中多元素特征谱峰识别方法

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6118850A (en) * 1997-02-28 2000-09-12 Rutgers, The State University Analysis methods for energy dispersive X-ray diffraction patterns
FI110820B (fi) * 1998-08-24 2003-03-31 Outokumpu Oy Menetelmä alkuainepitoisuuksien määrittämiseksi
US6266390B1 (en) * 1998-09-21 2001-07-24 Spectramet, Llc High speed materials sorting using x-ray fluorescence

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO0043761A3 *

Also Published As

Publication number Publication date
JP2002535647A (ja) 2002-10-22
US6496562B1 (en) 2002-12-17
WO2000043761A2 (fr) 2000-07-27
WO2000043761A3 (fr) 2000-11-30

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