EP3377593A1 - Material with marker for authentication and sorting of the material - Google Patents
Material with marker for authentication and sorting of the materialInfo
- Publication number
- EP3377593A1 EP3377593A1 EP16797953.3A EP16797953A EP3377593A1 EP 3377593 A1 EP3377593 A1 EP 3377593A1 EP 16797953 A EP16797953 A EP 16797953A EP 3377593 A1 EP3377593 A1 EP 3377593A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- phosphor
- modified
- materials
- phosphors
- minutes
- 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- Withdrawn
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7766—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
- C09K11/7767—Chalcogenides
- C09K11/7769—Oxides
- C09K11/7771—Oxysulfides
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7766—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
- C09K11/7767—Chalcogenides
- C09K11/7769—Oxides
Definitions
- the present application relates to a process for the preparation of modified phosphors, the modified phosphors thus obtained and the use of the phosphors for the simultaneous authentication and sorting of materials contained in a mixture.
- German application DE 102008 060 675 A1 describes ceramic particles into which specific chemical elements are introduced as marking elements.
- the ceramic particles can be introduced homogeneously into other materials, in particular plastics.
- the markers are then detected by chemical analysis of the labeled material. If, for example, X-ray fluorescence spectroscopy is used for this purpose, the authentication of the material and thus of the product can be carried out non-destructively. Disadvantages of this method are the comparatively high cost of detection with X-ray fluorescence spectroscopy.
- European patent EP 1 566 837 B1 discloses another method based on fluorescent markers homogeneously mixed into materials to be marked.
- the fluorescence of the markers is generated and detected. Both spectral and dynamic properties of the fluorescence can be measured here.
- the prior art also discloses methods for marking materials so that they can be recognized and sorted in sorting and separation processes.
- the patent US 8,205,813 B2 describes, for example, that materials of a particular class, in particular plastics, can be specifically marked by fluorescent materials.
- certain emission lines are assigned to the fluorescence of a specific class of materials, products from the marked material and also comminuted Fragments of the marked material can then be detected (detected) by being excited to fluorescence in the sorting process by a radiation source and the fluorescence subsequently evaluated spectrally.
- the concentrations of the markers should remain as small as possible in order not to change the material properties of the marked material.
- the marker materials are foreign substances that have to meet the various approval conditions, in particular for food packaging. For this it is important that the foreign substances are present in as low a concentration as possible.
- a second disadvantage is the additional cost of the marker materials.
- the task can also be formulated as follows.
- the phosphors and markers may be selected from the group of fluorescent materials and / or phosphorescent materials and / or Upconvertern and / or down converters and / or materials that re-emit an excitation wavelength upon excitation.
- Luminescence is the emission of electromagnetic radiation after the entry of energy. It is preferred that the energy input takes place via photons, the observed luminescence is thus photoluminescence.
- the photoluminescence can occur in the UV and / or VIS and / or IR.
- Upconverters are luminescent substances which, upon excitation, emit photons whose wavelength is shorter than the wavelength of the excitation photons.
- Downconverters are luminescent substances which, upon excitation, emit photons whose wavelength is longer than the wavelength of the excitation photons.
- fluorescence and luminescence are used interchangeably.
- Phosphors which can be modified by means of the method according to the invention are known from the prior art, in particular DE10201410S846A1, EP 1556837 Bl and US Pat. No. 8,205,813 B2.
- the content of these publications is therefore to be incorporated herein by reference to the publications the relevant content is deemed to be the disclosure content of the present application. The same applies to the phenomena of afterglow, or the decay behavior.
- the present invention overcomes disadvantages of the prior art by producing and using fluorescent markers, ie modified phosphors within the meaning of the present application, at the same time providing both the basis for the efficient authentication of many different products as well as an efficient comprehensive sorting of various materials that are present in a mixture, for example.
- the annealing processes can take place, for example, in a chamber furnace, continuous furnace or rotary kiln.
- the annealing process can be carried out continuously or discontinuously.
- their properties can also be changed by changing the particle size and / or by changing the particle shape and / or by irradiating the phosphor with high-energy radiation, preferably ⁇ -radiation and / or ⁇ -radiation, for a period of 1 -60 minutes, preferably 1-10 minutes, and / or by irradiating the phosphor with microwave radiation for a period of 1-60 minutes, preferably 1-10 minutes.
- the change in particle sizes can be achieved by adjusting the phosphors produced by primary production. This can be done by mortars by hand or by technical Mills or Mörecreixiraumeen done. Subsequently, the ground material can be separated by sieving into fractions of different particle size. These fractions can
- attack behavior This is understood to mean the excitability of the phosphor for fluorescence emission as a function of the excitation regime.
- the excitation regime describes the type of excitation of the phosphors. It is described by the spectral composition of the excitation radiation, the intensity of the excitation radiation and the timing of the excitation.
- the phosphors in particular the upconversion materials, can be processed in such a way that the intensity of their fluorescence or the intensity of the fluorescence emissions depend very strongly on the correct excitation wavelength.
- the optimal excitation wavelength depends on the chemical and physical structure of the respective marker and can be determined by the skilled person on the basis of known routine examinations easily and without significant effort. If the excitation wavelength differs by only a few nanometers (about 5 ⁇ m) from the optimum excitation wavelength, then the observed intensity corresponds to only a maximum of half the maximum intensity.
- fluorescent phosphors allow a particularly efficient use of semiconductor laser diodes for excitation of fluorescence.
- the intensity of the excitation radiation may be 0.01-1 W / mm 2 , preferably 0, lW / m 2 - 0.5 W / mm 2 .
- the timing of the excitation can be in a continuous stimulus or a Excitation with pulses exist.
- a pulsed excitation can be described by the number of pulses, the duration of the excitation pulses and the duration of the pauses without excitation between the excitation pulses. With multiple excitation, the number of pulses is advantageously 2-10, preferably 2-5.
- the duration of the excitation is lus-lOOms, 1 ⁇ 8-5 ⁇ 8, 10us-lms, more preferably 20u5-500us.
- the duration of excitation can also be in the femtosecond range when using femtosecond lasers.
- Processing processes after primary production can modify the mentioned parameters decay constant, spectral composition of fluorescence emission and annealing behavior independently or in combination.
- a phosphor with a defined chemical composition can be annealed already at its primary production at different temperatures and / or for different lengths of time to produce Leuchtstofr horrn.
- the luminescence narrow-band sources such as lasers, laser diodes, lichtemim 'erende diodes can broadband and / or (LEDs), xenon lamps, halogen lamps, individually or in combination.
- the excitation sources can be activated individually or activated simultaneously or sequentially in different combinations.
- optical filters such as Ipasspass / Shortpass / Bandpass filters can be used.
- a variation of the opening width of the excitation sources can be provided in order to modulate the size of an excitation zone through which material to be identified is transported.
- the excitation zone can also be modulated by arranging a plurality of excitation sources sequentially one behind the other and varying the number of activated excitation sources in this arrangement.
- various detectors such as black-and-white cameras, color cameras, photomultipliers, spectrometers, photocells, photodiodes, phototransistors can be used alone or in combination.
- optical filters such as longpass / shortpass / bandpass filters be used.
- the measuring devices can be designed in stationary or mobile form. They can be integrated in a sorting system or be available as a separate device.
- the excitation wave length is used as a sorting criterion.
- it is a sorting process with 10 sorting stages.
- the sorting material with a different wavelength is excited to fluoresce, preferably by a stationary semiconductor laser optics.
- each sorting stage the sorting material with a different wavelength is excited to fluoresce, preferably by a stationary semiconductor laser optics.
- each optimally 100% of the marker excited and used to generate the signal Luminous pieces of material are detected and separated against all other pieces of dark remaining material.
- variants of the phosphors used for this type of material are used in identical material types from different manufacturers. These may be made by the process methods described in this disclosure.
- dynamic and spectral properties of the fluorescence emission are used, which differ in the variants, although they can be excited to fluorescence emission at the same optimal excitation wavelength.
- variants mixtures of variants of the phosphor can be used in the material type, which results in dynamic and spectral Flucszenzmissionsigenschaften characterized by superposition of the dynamic and spectral fluorescence emission properties of the individual variants, which are characteristic of the variant mixture.
- the authentication of the different manufacturers of a type of material can be used to sort the type of material by manufacturer in further sorting stages.
- phosphors with different emission lines and decay constants are used, but they can all be excited with the same optimal excitation wavelength.
- different individual phosphors or mixtures of phosphors are used in the individual material grades, so that the phosphor or the mixtures of phosphors emit for the recognition of a particular material in certain wavelength windows with intensities which are in a fixed ratio .
- each material optimally uses 100% of the fluorescence markers in the sorting process to generate the signal.
- the detection of the material takes place in that the fluorescence is recorded differentiated after the wavelength windows.
- a uniform sorting machine with a Excitation wavelength can be used.
- the differentiation takes over one or more cameras or one or more spectrometers.
- the dynamic and spectral properties of the phosphor or the mixture of phosphors are measured for authentication.
- a phosphor based on gadolinium oxide doped with ytterbium would be ground by hand in a porcelain crucible and then screened through a sieve of mesh size 45 ⁇ m. This results in a change in the decay constant
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
Abstract
Description
Claims
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE102015119982 | 2015-11-18 | ||
DE102016111347 | 2016-06-21 | ||
PCT/EP2016/078202 WO2017085294A1 (en) | 2015-11-18 | 2016-11-18 | Material with marker for authentication and sorting of the material |
Publications (1)
Publication Number | Publication Date |
---|---|
EP3377593A1 true EP3377593A1 (en) | 2018-09-26 |
Family
ID=57345971
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP16797953.3A Withdrawn EP3377593A1 (en) | 2015-11-18 | 2016-11-18 | Material with marker for authentication and sorting of the material |
Country Status (2)
Country | Link |
---|---|
EP (1) | EP3377593A1 (en) |
WO (1) | WO2017085294A1 (en) |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE202016004745U1 (en) | 2016-07-28 | 2016-09-07 | Willy Lutz | Container device for transponders for tool-free attachment to grids |
DE102017130027A1 (en) | 2017-12-14 | 2019-06-19 | KM Innopat GmbH | Method for producing a security marker substance and method for authentication and authentication of an object and authentication system |
DE102019201529A1 (en) | 2019-02-06 | 2020-08-06 | Hahn-Schickard-Gesellschaft für angewandte Forschung e.V. | Control device for a manufacturing plant, tracking device, manufacturing data determiner, methods and computer program |
DE102020120669B4 (en) | 2020-08-05 | 2022-10-06 | Leibniz-Institut für Oberflächenmodifizierung e.V. | Authentication marker for authenticating an item, method for producing an authentication marker, item marked with an authentication marker and method for examining an item marked with an authentication marker |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5278783A (en) * | 1975-12-26 | 1977-07-02 | Hitachi Ltd | Treatment of fluorescent substance |
US5096614A (en) * | 1989-03-20 | 1992-03-17 | Gte Products Corporation | Process for producing a terbium-activated gadolinium oxysulfide X-ray phosphor wherein the green/blue emission ratio is controlled |
US5879588A (en) * | 1997-09-24 | 1999-03-09 | Osram Sylvania Inc. | Terbium-activated gadolinium oxysulfide phosphor with reduced blue emission |
US6103296A (en) * | 1998-04-22 | 2000-08-15 | Osram Sylvania Inc. | Method for improving the screen brightness of gadolinium oxysulfide x-ray phosphors |
FR2846445B1 (en) | 2002-10-29 | 2005-04-08 | Claude Lambert | METHOD OF AUTHENTICATING BY MARKING OR CHEMICAL TRACING AN OBJECT OR SUBSTANCE. |
FR2901160B1 (en) | 2006-05-22 | 2008-08-29 | Claude Lambert | PROCESS FOR RECYCLING MATERIALS FROM USED OBJECTS |
DE102008060675B4 (en) | 2008-12-08 | 2012-11-08 | Polysecure Gmbh | A method for the unique identification and authentication of products for protection against plagiarism |
PL2570468T3 (en) * | 2011-09-13 | 2014-04-30 | Bundesdruckerei Gmbh | Anti-stokes luminescent substances and use thereof in security documents |
DE102014105846A1 (en) | 2014-04-25 | 2015-10-29 | Polysecure Gmbh | Crystalline material, process for its preparation and use |
-
2016
- 2016-11-18 WO PCT/EP2016/078202 patent/WO2017085294A1/en active Application Filing
- 2016-11-18 EP EP16797953.3A patent/EP3377593A1/en not_active Withdrawn
Also Published As
Publication number | Publication date |
---|---|
WO2017085294A1 (en) | 2017-05-26 |
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Legal Events
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Effective date: 20180514 |
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AX | Request for extension of the european patent |
Extension state: BA ME |
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RIN1 | Information on inventor provided before grant (corrected) |
Inventor name: BAQUE, THOMAS Inventor name: MOESSLEIN, JOCHEN |
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DAV | Request for validation of the european patent (deleted) | ||
DAX | Request for extension of the european patent (deleted) | ||
17Q | First examination report despatched |
Effective date: 20190410 |
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STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: EXAMINATION IS IN PROGRESS |
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STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN |
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18D | Application deemed to be withdrawn |
Effective date: 20200923 |