CN111778029A - Preparation and application method of luggage hidden identification in travel inspection system - Google Patents

Preparation and application method of luggage hidden identification in travel inspection system Download PDF

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Publication number
CN111778029A
CN111778029A CN202010740225.6A CN202010740225A CN111778029A CN 111778029 A CN111778029 A CN 111778029A CN 202010740225 A CN202010740225 A CN 202010740225A CN 111778029 A CN111778029 A CN 111778029A
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China
Prior art keywords
luminescent
rare earth
luggage
conversion
light
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Pending
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CN202010740225.6A
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Chinese (zh)
Inventor
洪颖
陈国松
陈建松
王金陵
朱园园
方静
吴婷霞
薛鑫
钱斯
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Jiangsu Yangzi Inspection And Certification Co ltd
Jinling Customs Technical Center
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Jiangsu Yangzi Inspection And Certification Co ltd
Jinling Customs Technical Center
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Priority to CN202010740225.6A priority Critical patent/CN111778029A/en
Publication of CN111778029A publication Critical patent/CN111778029A/en
Pending legal-status Critical Current

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    • 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
    • C09K11/7772—Halogenides
    • C09K11/7773—Halogenides with alkali or alkaline earth metal
    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F3/00—Labels, tag tickets, or similar identification or indication means; Seals; Postage or like stamps
    • G09F3/02—Forms or constructions
    • G09F3/0291—Labels or tickets undergoing a change under particular conditions, e.g. heat, radiation, passage of time
    • G09F3/0294—Labels or tickets undergoing a change under particular conditions, e.g. heat, radiation, passage of time where the change is not permanent, e.g. labels only readable under a special light, temperature indicating labels and the like

Abstract

The invention relates to the technical field of hidden marks, in particular to a preparation and application method of a luggage hidden mark in a travel inspection system, which comprises the following steps: s1: construction of a light-emitting system: the construction of the luminescent system comprises an up-conversion rare earth nano phosphorus material and an inorganic luminescent material; s2: development of luminescent materials: yb is doped into rare earth fluoride of up-conversion rare earth nano phosphorus material3+And Er3+Or Ho3+And Tm3+Preparing an up-conversion luminescent material from near infrared to visible light; s3: screening of stable dispersions: the substrate selected for the stable dispersion has a lower phonon energy; s4: measurement and control of luminescence properties: the up-conversion luminous efficiency is improved by doping ions, and the luminous performance is regulated and controlled. Aiming at the target requirements of no sense, concealment, identification and disappearance, the invention displays the concealed mark under the specific light source, is used for customs port supervision activities and gives the customs security inspection certificateThe collection and identification of the data brings great convenience.

Description

Preparation and application method of luggage hidden identification in travel inspection system
Technical Field
The invention relates to the technical field of concealed marks, in particular to a preparation and application method of a luggage concealed mark in a travel inspection system.
Background
The social harmfulness of smuggling is extremely great. In recent years, smuggling means show obvious characteristics of diversification, complication and internationalization, so that the difficulty of anti-smuggling is increased, and great difficulty is brought to the collection and identification of evidence in customs security inspection. For example, in the case of drug smuggling crime, direct evidence is often not readily available; in the criminal process of transshipment of drugs, in order to successfully pass the personal inspection of customs security inspection, suspects often hide the drugs in luggage and attempt to pass customs. When a suspect takes the luggage, the suspect finds that the appearance of the suspect leaves a mark and perceives the abnormality, often abandons the luggage and eliminates the concealment trace, and evades the blame. Therefore, when finding the problem luggage, the customs needs to automatically mark the invisible mark on the luggage, and after the criminal suspect picks up the luggage, the criminal suspect gains the luggage in the country. The method has great significance for customs security inspection and anti-smuggling work;
the automatic identification technology combines multiple subjects such as computers, optics, electricity, communication and networks with technologies such as internet and mobile communication, realizes tracking of articles and sharing of information within a certain range, thereby endowing intelligence to objects, and realizing communication and conversation between people and objects and between objects. Existing identification techniques include: barcode recognition technology, voice recognition technology, face recognition technology, image recognition technology, optical character recognition technology, radio frequency recognition technology, and the like. The stealth materials at home and abroad are mainly radar stealth materials, infrared stealth materials, laser stealth materials and visible light stealth materials, and mainly develop and dynamically comprise nanometer stealth materials, bionic color-changing stealth materials, infrared multi-spectrum camouflage paint, radar stealth coatings and the like. The application of the hidden characteristic of the invisible material in the customs system is not much.
In addition, other invisible luminescent materials to be developed, such as invisible light liquid medicine, plant specific luminescent materials and the like, exist, so that a preparation and application method of the luggage hidden mark in the travel inspection system is provided, the hidden mark is displayed under a specific light source, and the method has great significance for customs supervision.
Disclosure of Invention
The invention provides a preparation and application method of a baggage covert identifier in a travel inspection system, which aims to solve the problems in the background technology.
In order to achieve the purpose, the invention adopts the following technical scheme:
the preparation method of the hidden mark of the baggage in the tour inspection system comprises the following steps:
s1: construction of a light-emitting system: the construction of the luminescent system comprises an up-conversion rare earth nano-phosphor system material and an inorganic luminescent material, wherein the inorganic luminescent material is added into the up-conversion rare earth nano-phosphor system material, near infrared light is converted into short-wave radiation through a multi-photon mechanism, and ultraviolet light or visible light is emitted;
s2: development of luminescent materials: rare earth fluoride LaF of up-conversion rare earth nano phosphorus material3In which the weight fraction of the doped substance is 20% and 2% Yb respectively3+And Er3+Or Ho3+And Tm3+Preparing an up-conversion luminescent material from near infrared to visible light; mixing Yb of different concentrations3+、Er3+And Tm3+Co-doped to NaYF4In the nanoparticles, the visible light is obtained to the nearA multicolor fluorescent material of infrared light; from S1, T1 and T1 were observed simultaneously at room temperature using organic long afterglow materials*The radiation attenuation of (a) causes afterglow luminescence characteristics of fluorescence, phosphorescence and afterglow;
s3: screening of stable dispersions: the selected stable dispersion has low phonon energy and no reduction of emitted light, and ZrO is used2、Yb3+、Er3+As a host material for the light-emitting system;
s4: measurement and control of luminescence properties: the performance of the luminescent material is influenced by the host material and the species and doping amount of the doped ions of the host material, the host material has higher thermal stability and chemical stability, the up-conversion luminescent efficiency is improved by doping the ions, and the luminescent performance is regulated and controlled.
Preferably, the step S1 is to upconvert the rare earth nano-phosphor material and the phosphor material by double doping Yb in a fluoride, oxide, oxyfluoride matrix3+-Er3+、Yb3+-Tm3+、Yb3+-Ho3+The rare earth ions combine to form the up-conversion luminescent material.
Preferably, in step S2, the upconversion efficiency is improved by adding an activator to the upconversion luminescent material, and the suitable activator is selected according to the excitation wavelength of the rare earth ion.
Preferably, the stable matrix material in step S3 needs to have low phonon energy to reduce non-radiative loss so as to ensure radiation transition to the maximum, and the fluoride, oxide and oxysulfide have low phonon energy and relatively stable chemical properties, and β -NaYF is selected4、Y2O3、Ba5Gd8Zn4O21、CaSc2O4、ZrO2And Gd2O2One or more of S.
Preferably, the doping ions in step S4 are Er3Through Er3+And Yb3+Co-doping in specific host materials results in highly efficient up-converting luminescent materials.
The application method of the baggage covert identifier in the tourism inspection system comprises the following specific steps:
when the luggage hidden with drugs or other prohibited articles is found to be abnormal through an X-ray machine or other security inspection links, specific patterns, such as colorless quick-drying reagents of a large five-pointed star, are automatically sprayed on both sides of the luggage;
after several seconds, the solvent is evaporated and dried, and an invisible latent image formed by a very small amount of luminescent materials is left on the surface of the luggage, so that the suspicious person is not easily warned when the luggage is taken;
when the suspect takes the luggage and passes through a security inspection door, under the environment of infrared light irradiation, the latent image of the specific pattern is excited by the exciting light to show the pattern;
the security inspection door automatically identifies and alarms to prompt security inspection personnel to take the suspect and the luggage away for further unpacking inspection;
meanwhile, the specific pattern is used as the mark, so that misjudgment caused by accidental reagent contamination can be reduced.
Compared with the prior art, the invention has the beneficial effects that:
aiming at the target requirements of noninductivity, concealment, identifiability and disappearance, the invention aims to develop a novel invisible luminescent material, develop and develop a concealed mark under a specific light source, develop and develop an automatic identification technology of the concealed mark, be used for the customs port supervision activities, realize the automatic identification of suspected supervision luggage, comprehensively study and judge sensitive information data through background operation, prompt customs supervision personnel to start a checking system for checking through visual display or automatic alarm, and bring great convenience to the collection and identification of evidence in customs security inspection.
Drawings
FIG. 1 is a schematic block diagram of the preparation process of the concealed mark luminescent material of the present invention.
Fig. 2 is a block schematic flow diagram of the covert identification application of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments.
Referring to fig. 1-2, the present invention provides a technical solution:
the preparation method of the hidden mark of the baggage in the tour inspection system comprises the following steps:
s1: construction of a light-emitting system: the construction of the luminescent system comprises an upconversion rare earth nano-phosphor system material and an inorganic luminescent material, wherein the inorganic luminescent material is added into the upconversion rare earth nano-phosphor system material, near infrared light is converted into short-wave radiation through a multiphoton mechanism, ultraviolet or visible light is emitted, namely anti-Stokes luminescence, and the upconversion luminescence is realized by double doping Yb into a fluoride, oxide and oxyfluoride matrix3+-Er3+、Yb3+-Tm3+、Yb3+-Ho3+The material has wide application prospect in a plurality of fields such as three-dimensional display, up-conversion laser, infrared detection, anti-counterfeiting identification, biological detection and the like, and in addition, other invisible luminescent materials to be developed, such as invisible light shadow liquid medicine, plant specific luminescent materials and the like;
s2: development of luminescent materials: the rare earth fluoride LaF of the up-conversion rare earth nano phosphorus material is shown by X-ray diffraction, X-ray photoelectric energy spectrum, scanning electron microscope, high-resolution transmission electrode and static adsorption recording characterization3In which the weight fraction of the doped substance is 20% and 2% Yb respectively3+And Er3+Or Ho3+And Tm3+Preparing an up-conversion luminescent material from near infrared to visible light; mixing Yb of different concentrations3+、Er3+And Tm3+Co-doped to NaYF4Obtaining a multicolor fluorescent material from visible light to near infrared light in the nano particles; by using the organic long afterglow material, afterglow luminescence characteristics of three modes of fluorescence, phosphorescence and afterglow caused by radiation attenuation from S1, T1 and T1 are simultaneously observed at room temperature, and the luminescence efficiency of the organic afterglow is obviously enhanced;
s3: screening of stable dispersions: selected with Stable DispersionThe base material has low phonon energy, so that the emitted light is not weakened, and ZrO is adopted2、Yb3+、Er3+As the host material of the luminescent system, the stable host material needs to have low phonon energy to reduce non-radiative loss so as to ensure radiation transition to the maximum extent, and fluoride, oxide and oxysulfide have lower phonon energy and relatively stable chemical properties, and β -NaYF is selected4(~350cm-1) And Y2O3、Ba5Gd8Zn4O21、CaSc2O4、ZrO2、Gd2O2S(400~600cm-1) One or more of (A), Er3+/Yb3+Codoped β -NaYF4Is a green material with the highest up-conversion efficiency at present, Er3+And Yb3+Co-doping can make Er3+The up-conversion luminous efficiency of the activator is improved by several orders of magnitude;
s4: measurement and control of luminescence properties: the performance of the luminescent material is influenced by the host material and the species and doping amount of the doped ions of the host material, the host material has higher thermal stability and chemical stability, the up-conversion luminous efficiency is improved by doping the ions, the luminescent performance is regulated and controlled, and the doping elements are mainly concentrated in Er3+、Tm3+And Ho3+Wherein, Er3+Has rich energy levels, long service life of partial energy levels and high up-conversion efficiency, is a preferred up-conversion material activator, namely rare earth ion Yb3+Has an excitation wavelength of 980nm, absorbs energy and transfers the energy to Er3+The up-conversion efficiency can be improved by 1-2 orders of magnitude.
Specifically, the application method of the luggage hiding identifier in the travel inspection system comprises the following specific steps:
when the luggage hidden with drugs or other prohibited articles is found to be abnormal through an X-ray machine or other security inspection links, specific patterns, such as colorless quick-drying reagents of a large five-pointed star, are automatically sprayed on both sides of the luggage;
after several seconds, the solvent is evaporated and dried, and an invisible latent image formed by a very small amount of luminescent materials is left on the surface of the luggage, so that the suspicious person is not easily warned when the luggage is taken;
when the suspect takes the luggage and passes through a security inspection door, under the environment of infrared light irradiation, the latent image of the specific pattern is excited by the exciting light to show the pattern;
the security inspection door automatically identifies and alarms to prompt security inspection personnel to take the suspect and the luggage away for further unpacking inspection;
meanwhile, the specific pattern is used as the mark, so that misjudgment caused by accidental reagent contamination can be reduced.
The luggage adopts an optical (or optical excitation mode) to preliminarily identify the mark, the automatic identification of suspected supervision luggage is realized by combining the information linkage of a visual system, the comprehensive study and judgment of sensitive information data are carried out through background operation, and the customs supervision personnel are prompted to start the checking system for checking through visual display or automatic alarm.
In summary, the luminescent material developed by the invention needs to be effectively excited to emit light under infrared radiation, the traditional fluorescent material is a material capable of emitting fluorescence under short-wave ultraviolet radiation, and the short-wave ultraviolet has great harm to human bodies and short effective radiation distance, and is only suitable for being used in an unmanned area in a short distance, some fluorescent materials can be excited by visible light with longer wavelength and lower energy to emit fluorescence through modification, but the requirement of 'concealment' is not met, so that the invention needs to introduce efficient energy receiving-transferring groups into the up-conversion luminescent material, so that the luminescent material can also generate specific luminescence to be identified under the infrared radiation with longer wavelength, lower energy and no harm to human bodies;
secondly, the luminescent material developed by the invention has specific luminescent characteristics which are excellent enough, firstly, the energy threshold of an excitation light source is low enough, secondly, the luminescent intensity is large enough, the threshold and the luminescent efficiency are important characteristic indexes of the luminescent material of the infrared up-conversion material, and also are core measurement standards for selecting a proper luminescent system, and the key point for achieving the invisible luminescent effect is to select and prepare a proper up-conversion nano luminescent material; the material does not emit light under visible light, but can emit specific light under the excitation of an infrared light source, and as a concealed luggage identification material, the material needs to emit fluorescence which can be visually distinguished in a specific environment (such as low-energy infrared radiation);
finally, the luminescent system of the invention is stable enough, avoid appearing the misjudgment, the luminous efficacy of the traditional fluorescent system is restricted by many factors, the whole is "fragile", the medium and the operating condition are controlled improperly and can cause "fluorescence quenching", the purpose that can not be expected is achieved, the host material, the sensitizer and the activator are the main factors influencing the luminescent performance of the luminescent material, and the rare earth ion is especially important in preparing the up-conversion luminescent material as the activator, the algorithm research of the large-flux network monitoring sensitive information is carried out, and the information acquisition and matching research and judgment technology is established; the automatic identification prompting technology is researched based on the information acquisition result, and accurate identification, tracking and checking of the suspected controlled luggage are achieved.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.

Claims (6)

1. The preparation method of the hidden mark of the baggage in the tour inspection system is characterized by comprising the following steps of:
s1: construction of a light-emitting system: the construction of the luminescent system comprises an up-conversion rare earth nano-phosphor system material and an inorganic luminescent material, wherein the inorganic luminescent material is added into the up-conversion rare earth nano-phosphor system material, near infrared light is converted into short-wave radiation through a multi-photon mechanism, and ultraviolet light or visible light is emitted;
s2: development of luminescent materials: rare earth fluoride LaF of up-conversion rare earth nano phosphorus material3In which the weight fraction of the doped substance is 20% and 2% Yb respectively3+And Er3+Or Ho3+And Tm3+Preparing an up-conversion luminescent material from near infrared to visible light; mixing Yb of different concentrations3+、Er3+And Tm3+Co-doped to NaYF4Obtaining multicolor fluorescent material from visible light to near infrared light in nano particlesFeeding; from S1, T1 and T1 were observed simultaneously at room temperature using organic long afterglow materials*The radiation attenuation of (a) causes afterglow luminescence characteristics of fluorescence, phosphorescence and afterglow;
s3: screening of stable dispersions: the selected stable dispersion has low phonon energy and no reduction of emitted light, and ZrO is used2、Yb3+、Er3+As host material for luminescent systems, A of rare earth up-conversion luminescent material hosts2B2O7A mold material;
s4: measurement and control of luminescence properties: the performance of the luminescent material is influenced by the host material and the species and doping amount of the doped ions of the host material, the host material has higher thermal stability and chemical stability, the up-conversion luminescent efficiency is improved by doping the ions, and the luminescent performance is regulated and controlled.
2. The method of claim 1, wherein the step S1 comprises converting the rare earth nanophosphor material and the phosphor material by double-doping Yb in a fluoride, oxide, oxyfluoride matrix3+-Er3+、Yb3+-Tm3+、Yb3+-Ho3+The rare earth ions combine to form the up-conversion luminescent material.
3. The method for preparing concealed identification of baggage in a passenger inspection system according to claim 1, wherein an activator is added to the upconversion luminescent material in step S2 to improve upconversion efficiency, and the suitable activator is selected according to the excitation wavelength of rare earth ions.
4. The method of claim 1, wherein the matrix material stabilized in step S3 is required to have low phonon energy to reduce non-radiative loss and to ensure radiation transition to the maximum extent, and the fluoride, oxide and oxysulfide have low phonon energy and relatively stable chemical properties, and β -NaYF is selected as the matrix material4、Y2O3、Ba5Gd8Zn4O21、CaSc2O4、ZrO2And Gd2O2One or more of S.
5. The method for preparing hidden mark of baggage in passenger inspection system of claim 1, wherein Er is selected as the doping ion in step S43Through Er3+And Yb3+Co-doping in specific host materials results in highly efficient up-converting luminescent materials.
6. The method for applying the concealed baggage identification in the passenger inspection system according to claim 1, comprising the following steps:
when the luggage hidden with drugs or other prohibited articles is found to be abnormal through an X-ray machine or other security inspection links, specific patterns, such as colorless quick-drying reagents of a large five-pointed star, are automatically sprayed on both sides of the luggage;
after several seconds, the solvent is evaporated and dried, and an invisible latent image formed by a very small amount of luminescent materials is left on the surface of the luggage, so that the suspicious person is not easily warned when the luggage is taken;
when the suspect takes the luggage and passes through a security inspection door, under the environment of infrared light irradiation, the latent image of the specific pattern is excited by the exciting light to show the pattern;
the security inspection door automatically identifies and alarms to prompt security inspection personnel to take the suspect and the luggage away for further unpacking inspection;
meanwhile, the specific pattern is used as the mark, so that misjudgment caused by accidental reagent contamination can be reduced.
CN202010740225.6A 2020-07-28 2020-07-28 Preparation and application method of luggage hidden identification in travel inspection system Pending CN111778029A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112500863A (en) * 2021-02-07 2021-03-16 金陵海关技术中心 Preparation and application of core-shell type luminescent material hidden mark of customs security inspection system
CN112521945A (en) * 2021-02-09 2021-03-19 金陵海关技术中心 Preparation method and application of infrared luminescent material hidden mark

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102268259A (en) * 2011-06-14 2011-12-07 中国科学院长春光学精密机械与物理研究所 Luminescent centre regionally doped rare earth upconversion luminescent material and preparation method thereof
CN107304357A (en) * 2016-04-22 2017-10-31 嘉兴雷洲复合材料有限公司 A kind of rare earth nano photoelectric conversion material preparation method
CN110295038A (en) * 2018-03-21 2019-10-01 中国科学院福建物质结构研究所 A kind of rare earth/quantum dot composite upconversion luminescent material and its preparation method and application

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102268259A (en) * 2011-06-14 2011-12-07 中国科学院长春光学精密机械与物理研究所 Luminescent centre regionally doped rare earth upconversion luminescent material and preparation method thereof
CN107304357A (en) * 2016-04-22 2017-10-31 嘉兴雷洲复合材料有限公司 A kind of rare earth nano photoelectric conversion material preparation method
CN110295038A (en) * 2018-03-21 2019-10-01 中国科学院福建物质结构研究所 A kind of rare earth/quantum dot composite upconversion luminescent material and its preparation method and application

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112500863A (en) * 2021-02-07 2021-03-16 金陵海关技术中心 Preparation and application of core-shell type luminescent material hidden mark of customs security inspection system
US11232696B1 (en) 2021-02-07 2022-01-25 Jinling Haiguan Technical Center Preparation of concealed marks with core-shell luminophores for customs security check system and application thereof
CN112521945A (en) * 2021-02-09 2021-03-19 金陵海关技术中心 Preparation method and application of infrared luminescent material hidden mark

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