CN113637478B - Europium-doped barium tetrasilicon mica fluorescent powder and preparation method and application thereof - Google Patents

Europium-doped barium tetrasilicon mica fluorescent powder and preparation method and application thereof Download PDF

Info

Publication number
CN113637478B
CN113637478B CN202110932190.0A CN202110932190A CN113637478B CN 113637478 B CN113637478 B CN 113637478B CN 202110932190 A CN202110932190 A CN 202110932190A CN 113637478 B CN113637478 B CN 113637478B
Authority
CN
China
Prior art keywords
europium
fpl
fluorescent powder
oxide
sample
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.)
Active
Application number
CN202110932190.0A
Other languages
Chinese (zh)
Other versions
CN113637478A (en
Inventor
石士考
刘俊杉
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.)
Hebei Normal University
Original Assignee
Hebei Normal University
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 Hebei Normal University filed Critical Hebei Normal University
Priority to CN202110932190.0A priority Critical patent/CN113637478B/en
Publication of CN113637478A publication Critical patent/CN113637478A/en
Application granted granted Critical
Publication of CN113637478B publication Critical patent/CN113637478B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

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
    • C09K11/7728—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing europium
    • C09K11/77342—Silicates
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
    • Y02B20/00—Energy efficient lighting technologies, e.g. halogen lamps or gas discharge lamps

Landscapes

  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Luminescent Compositions (AREA)

Abstract

The invention relates to the technical field of fingerprint detection, in particular to europium-doped barium tetrasilicon mica fluorescent powder, a preparation method and application thereof, and the preparation method of the europium-doped barium tetrasilicon mica fluorescent powder comprises the following steps: uniformly mixing barium oxide, magnesium oxide, silicon dioxide, magnesium fluoride and europium oxide, and grinding to obtain mixed solid powder; calcining the mixed solid powder at 700-750 ℃ for 2-2.5 h, then calcining at 1100-1170 ℃ for 4.5-5.0 h, cooling and grinding to obtain the fluorescent powder. The europium-doped barium tetrasilicon mica fluorescent powder prepared by the invention can clearly show I-III level fingerprint characteristics under the excitation of ultraviolet light, different I-III level details can be clearly visible on ridge patterns, the juncture transition of ridge and groove areas is obvious, the aim of latent fingerprint appearance on the surfaces of various nonporous and semi-porous objects is fulfilled, the developing effect is obvious, and the europium-doped barium tetrasilicon mica fluorescent powder has a higher application prospect in the fields of forensics, individual identity recognition and the like.

Description

Europium-doped barium tetrasilicon mica fluorescent powder and preparation method and application thereof
Technical Field
The invention relates to the technical field of fingerprint detection, in particular to europium-doped barium tetrasilicon mica fluorescent powder and a preparation method and application thereof.
Background
In crime scene investigation, a fingerprint is an important evidence for identifying personal information by a unique ridge pattern of skin. In general, after an object is contacted by a bare hand, substances such as sweat and sebum secreted and metabolized on the hand leave fingerprint marks on the surface of the object, and in many cases, the marks cannot be seen by naked eyes, so the fingerprints are called latent fingerprints. Typically, fingerprint patterns are classified into three classes, class i features are described by fingerprint ridge flow and general morphological information, exhibiting triangles, loops, and spirals, which are not sufficient to identify individuals; class ii features refer to fine points for detecting individual fingerprint ridges, i.e., bifurcations, intersections, lakes, furrows, short ridges, and islands, which are distinct and unique patterns; class iii features are all attributes of the ridge, including shape, sweat pores and curvature, ridge path deviation and edge profile are extremely important quantitative data for identifying individuals. Class ii and class iii features are very useful for personal identification.
In recent years, the latent fingerprint detection technology has become an effective approach for individual identification, and has been widely applied in the forensic field. The powder developing method is a traditional, effective and widely applied latent fingerprint developing method and has the advantages of low cost, simple operation, time saving, high efficiency and the like. The traditional latent fingerprint detection powder has the defects of low detection sensitivity, high background interference, high toxicity and poor fingerprint appearance effect left on some special objects. In addition, the existing latent fingerprint detection powder cannot clearly enable the characteristics of the grade II and the grade III to be displayed at the same time. Therefore, there is a need for developing a latent fingerprint detection powder that is highly effective, non-toxic, and low cost, and that allows all class i-iii fingerprints to be clearly visible.
Disclosure of Invention
Aiming at the problems that the characteristics of the II level and the III level can not be clearly displayed simultaneously and the toxicity is higher and the like in the prior art of latent fingerprint detection powder, the invention provides europium-doped barium tetrasilicon mica fluorescent powder and a preparation method and application thereof.
In order to solve the technical problems, the technical scheme provided by the invention is as follows:
a preparation method of europium-doped barium tetrasilicon mica fluorescent powder comprises the following steps:
uniformly mixing barium oxide, magnesium oxide, silicon dioxide, magnesium fluoride and europium oxide, and grinding to obtain mixed solid powder;
wherein, the total amount of barium oxide, magnesium oxide, silicon dioxide and magnesium fluoride is taken as 100 percent, and the dosages of the components are as follows: 13.97 to 15.45 percent of barium oxide, 4.77 to 5.27 percent of magnesium oxide, 67.75 to 70.05 percent of silicon dioxide and 11.09 to 12.26 percent of magnesium fluoride; the mol ratio of Eu in the europium oxide to Ba in the barium oxide is 0.07-0.10:1;
and step two, calcining the mixed solid powder at 700-750 ℃ for 2-2.5 h, then calcining at 1100-1170 ℃ for 4.5-5.0 h, cooling and grinding to obtain the europium-doped barium tetrasilicon mica fluorescent powder.
Compared with the prior art, the preparation method of the europium-doped barium tetrasilicon mica fluorescent powder provided by the invention takes mica clay materials as a matrix, and has a unique layered structure, eu 3+ Is easily inserted between the inner layers to form a source O at an excitation wavelength of 252nm 2- -Eu 3+ The absorption broadband is positioned at the position of the ultraviolet region, is highly matched with the 254nm excitation wavelength of the ultraviolet lamp, can be efficiently excited by ultraviolet light, and can quickly and simply display the latent fingerprint in a red fluorescence mode under the irradiation of the ultraviolet lamp; by using equal amounts of Ba 2+ Substitution ofK between layers + At the same time, the Si content is adjusted to promote the octahedral layer in the mica laminate to generate Mg 2+ Vacancies to balance excess positive charge, thereby making the barium tetrasilicon mica more sensitive to crystal field environment 5 D 0 → 7 F 2 Electric dipole transition, greatly enhancing Eu 3+ The luminous intensity of the latent fingerprint detection is enhanced; in addition, the Ba-O bond in the barium tetrasilicate mica is strong and is beneficial to improving the mechanical property of the fluorescent powder, so that the prepared fluorescent powder has strong binding force and high viscosity on fingerprint residues on the surface of an object, each detail of fingerprints can be clearly and accurately reproduced, the definition of the detection effect of the latent fingerprints is enhanced, the detection effect of the latent fingerprints is effectively improved from the two aspects of brightness and definition, the detection device can be used for displaying the latent fingerprints of different objects, the II-level and III-level fingerprint characteristics are clearly displayed, and the developed image has the advantages of high contrast, high sensitivity, high selectivity and the like and has wide application prospect in the field of detection of the latent fingerprints.
Preferably, the total amount of barium oxide, magnesium oxide, silicon dioxide and magnesium fluoride is taken as 100%, and the following components are used: 14.71% of barium oxide, 5.02% of magnesium oxide, 68.58% of silicon dioxide and 11.69% of magnesium fluoride.
The preferable proportion of each substance is favorable for fully reacting each component, obtaining the barium tetrasilicon mica fluorescent material with uniform particle size and good crystallinity, and enhancing the luminous intensity of the prepared fluorescent material.
Preferably, the molar ratio of Eu in the europium oxide to Ba in the barium oxide is 0.075-0.085:1.
Further preferably, the molar ratio of Eu in the europium oxide to Ba in the barium oxide is 0.08:1.
Preferred Eu 3+ The doping concentration can enhance the red fluorescence intensity of the fluorescent powder.
Preferably, in the second step, the temperature is raised to 700-750 ℃ in a temperature programming mode, and the temperature raising rate is 4-6 ℃/min.
Preferably, in the second step, the temperature is raised to 1100-1170 ℃ in a temperature programming mode, and the temperature raising rate is 1.5-2.5 ℃/min.
More preferably, in the second step, the mixed solid powder is calcined at 720 ℃ for 2 to 2.5 hours, and then calcined at 1150 ℃ for 4.5 to 5.0 hours.
Preferably, in the third step, the cooling rate is 1-3 ℃/min.
The preferable calcination temperature, the heating rate and the cooling rate can effectively avoid the aggregation of fluorescent powder in the calcination process, effectively inhibit the growth of crystal grains in the calcination process, improve the crystallinity of the material, reduce the defects on the surfaces of the crystal grains, ensure that the particle size is more uniform, and also facilitate the promotion of Eu 3+ Enters into the crystal lattice of barium tetrasilicate mica to improve the fluorescence intensity of the fluorescent powder.
The invention also provides europium-doped barium tetrasilicon mica fluorescent powder, which is prepared by the preparation method of any one of the europium-doped barium tetrasilicon mica fluorescent powder.
The invention also provides application of the europium-doped barium tetrasilicon mica fluorescent powder in latent fingerprint detection.
The europium-doped barium tetrasilicon mica fluorescent powder prepared by the invention has the advantages of simple preparation method, short reaction time, low production cost and environment-friendly raw materials, can clearly show I-III level fingerprint characteristics under the excitation of ultraviolet light, can clearly see different I-III level details on ridge patterns, has obvious juncture transition of ridge and ditch areas, realizes the aim of latent fingerprint appearance on the surfaces of various non-porous and semi-porous objects, has obvious development effect, and has higher application prospect in the fields of forensics, individual identity recognition and the like.
Drawings
FIG. 1 shows Ba-Fpl/4Si: eu prepared in example 1 3+ Sample, fpl: eu prepared in comparative example 3 3+ Sample, ba-Fpl: eu prepared in comparative example 4 3+ X-ray diffraction pattern of the sample;
FIG. 2 shows Fpl: eu prepared in comparative example 3 3+ Scanning electron microscope images and transmission electron microscope images of the sample, (a) scanning electron microscope images and (b) transmission electron microscope images;
FIG. 3 shows Ba-Fpl: eu prepared in comparative example 4 3+ Scanning electron microscopy and transmission electron microscopy of a sample, (a) scanningAn electron microscope image, (b) a transmission electron microscope image;
FIG. 4 shows Ba-Fpl/4Si: eu prepared in example 1 3+ A sample scanning electron microscope image and a transmission electron microscope image, (a) a scanning electron microscope image, (b) a transmission electron microscope image;
FIG. 5 shows Fpl: eu prepared in comparative example 3 3+ A spectrogram of the sample;
FIG. 6 shows Ba-Fpl: eu prepared in comparative example 4 3+ A spectrogram of the sample;
FIG. 7 shows the Ba-Fpl/4Si:Eu prepared in example 1 3+ A spectrogram of the sample;
FIG. 8 shows Ba-Fpl/4Si: eu prepared in examples 1-3 and comparative example 5 3+ The excitation spectrum obtained by monitoring the sample at 614nm wavelength is shown as an arrow, and comparative example 5, example 2, example 3 and example 1 are sequentially shown from bottom to top;
FIG. 9 shows Ba-Fpl/4Si: eu prepared in examples 1-3 and comparative example 5 3+ The emission spectrum obtained by excitation of the sample at 252nm wavelength shows that comparative example 5, example 2, example 3 and example 1 are shown in sequence from bottom to top according to the direction indicated by the arrow;
FIG. 10 shows Fpl: eu prepared in comparative example 3 3+ Sample, ba-Fpl: eu prepared in comparative example 4 3+ Sample, ba-Fpl/4Si: eu prepared in example 1 3+ A graph comparing the luminous intensity of the sample at the excitation wavelength of 252 nm;
FIG. 11 shows Fpl: eu prepared in comparative example 3 3+ Sample, ba-Fpl: eu prepared in comparative example 4 3+ Sample, ba-Fpl/4Si: eu prepared in example 1 3+ Fluorescence decay profile of sample: (a) comparative example 3, (b) comparative example 4, (c) example 1;
FIG. 12 shows Ba-Fpl/4Si: eu prepared in example 1 and comparative examples 1-2 3+ The emission spectrum of the sample at 252nm excitation wavelength is shown as a comparison example 1, a comparison example 2 and an example 1 from bottom to top according to the direction indicated by an arrow;
FIG. 13 shows Fpl: eu prepared in comparative example 3 3+ Sample and Natural Fpl: eu prepared in comparative example 6 3+ The emission spectrum of the sample at 252nm excitation wavelength is shown below for the emission spectrum of comparative example 6 and above for comparative example 3An emission spectrum;
FIG. 14 shows Fpl: eu prepared in comparative example 3 3+ Sample, ba-Fpl: eu prepared in comparative example 4 3+ Sample, ba-Fpl/4Si: eu prepared in example 1 3+ A latent fingerprint detection image of a sample on plain paper a, (a) comparative example 3, (b) comparative example 4, (c) example 1;
FIG. 15 shows Eu prepared in comparative example 7 3+ Doped calcic tetrasilicon mica powder sample and Eu 3+ Doped strontium tetrasilicon mica powder sample, ba-Fpl/4Si: eu prepared in example 1 3+ Latent fingerprint detection image of sample on plain paper b, wherein (a) Eu 3+ Doped strontium tetrasilicon mica powder sample, (b) Eu 3+ Doped calcium tetrasilicon mica powder sample, (c) Ba-Fpl/4Si Eu 3+ A sample;
FIG. 16 shows Ba-Fpl/4Si: eu prepared in example 1 3+ The sample is subjected to latent fingerprint images on the surfaces of objects with different roughness under a 254nm ultraviolet lamp, wherein aluminum foil (a), glass slide (b), tinfoil (c), plain paper (d), plain paper (e) and plain paper (f);
FIG. 17 shows the Ba-Fpl/4Si:Eu prepared in example 1 3+ A complete and partial fluorescent magnified image of the latent fingerprint of the sample on the surface of the tinfoil under a 254nm uv lamp.
Detailed Description
The present invention will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
In order to better illustrate the present invention, the following examples are provided for further illustration.
Example 1
The embodiment of the invention provides a preparation method of europium-doped barium tetrasilicon mica fluorescent powder, which at least comprises the following steps:
mixing 0.1725g of barium oxide, 0.0589g of magnesium oxide, 0.8040g of silicon dioxide, 0.1370g of magnesium fluoride and 0.0158g of europium oxide, and fully grinding in an agate mortar for 20min to obtain mixed solid powder;
step two, placing the mixed solid powder into a corundum crucible, heating to 720 ℃ in a muffle furnace at a speed of 5 ℃/min, preserving heat for 2 hours, heating to 1150 ℃ at a speed of 2.0 ℃/min, calcining for 5.0 hours, cooling to room temperature at a speed of 2 ℃/min, and grinding to obtain the europium-doped barium tetrasilicon mica fluorescent powder (Ba-Fpl/4 Si:8% Eu 3+ Fluorescent powder).
Example 2
The embodiment of the invention provides a preparation method of europium-doped barium tetrasilicon mica fluorescent powder, which at least comprises the following steps:
mixing 0.1638g of barium oxide, 0.0618g of magnesium oxide, 0.8031g of silicon dioxide, 0.1437 magnesium fluoride and 0.0132g of europium oxide, and fully grinding in an agate mortar for 20min to obtain mixed solid powder;
step two, placing the mixed solid powder into a corundum crucible, heating to 750 ℃ at a speed of 5 ℃/min in a muffle furnace, preserving heat for 2.5 hours, heating to 1170 ℃ at a speed of 1.5 ℃/min, calcining for 5.0 hours, cooling to room temperature at a speed of 2.5 ℃/min, and grinding to obtain the europium-doped barium tetrasilicon mica fluorescent powder (Ba-Fpl/4 Si:7% Eu) 3+ Fluorescent powder).
Example 3
The embodiment of the invention provides a preparation method of europium-doped barium tetrasilicon mica fluorescent powder, which at least comprises the following steps:
mixing 0.1652g of barium oxide, 0.0559g of magnesium oxide, 0.8212g of silicon dioxide, 0.1300g of magnesium fluoride and 0.0191g of europium oxide, and fully grinding in an agate mortar for 20min to obtain mixed solid powder;
step two, placing the mixed solid powder into a corundum crucible, heating to 700 ℃ at a speed of 4 ℃/min in a muffle furnace, preserving heat for 2 hours, heating to 1100 ℃ at a speed of 2.5 ℃/min, calcining for 4.5 hours, cooling to room temperature at a speed of 1 ℃/min, and grinding to obtain the europium-doped barium tetrasilicon mica fluorescent powder (Ba-Fpl/4 Si:10% Eu 3+ Fluorescent powder).
Example 4
The embodiment of the invention provides a preparation method of europium-doped barium tetrasilicon mica fluorescent powder, which at least comprises the following steps:
mixing 0.1811g of barium oxide, 0.0580g of magnesium oxide, 0.7943g of silicon dioxide, 0.1389g of magnesium fluoride and 0.0166g of europium oxide, and fully grinding in an agate mortar for 20min to obtain mixed solid powder;
step two, placing the mixed solid powder into a corundum crucible, heating to 730 ℃ at a speed of 6 ℃/min in a muffle furnace, preserving heat for 2.5h, heating to 1130 ℃ at a speed of 1.8 ℃/min, calcining for 5.0h, cooling to room temperature at a speed of 3 ℃/min, and grinding to obtain the europium-doped barium tetrasilicon mica fluorescent powder (Ba-Fpl/4 Si:8% Eu 3+ Fluorescent powder).
Comparative example 1
The comparative example of the present invention provides a method for preparing europium-doped barium tetrasilicon mica fluorescent powder, which is exactly the same as example 1 except that the second calcination temperature 1150℃in the second step is modified to 1050 ℃.
Comparative example 2
The comparative example of the present invention provides a preparation method of europium-doped barium tetrasilicon mica fluorescent powder, which is exactly the same as that of example 1 except that the second calcination temperature 1150℃in the second step is modified to 1200 ℃.
Comparative example 3
This comparative example provides a europium-doped fluorophlogopite phosphor (Fpl: eu) 3+ ) The preparation method of (2) at least comprises the following steps:
step one, will 0.1307g K 2 SiF 6 、0.1435g MgO、0.0581g Al 2 O 3 、0.1783g SiO 2 And 0.0063g Eu 2 O 3 Fully grinding the mixture in an agate mortar for 20min to obtain mixed solid powder;
step two, placing the mixed solid powder into a corundum crucible, heating to 1050 ℃ in a muffle furnace at a speed of 5 ℃/min, calcining for 5.0h, cooling to room temperature at a speed of 2.0 ℃/min, and grinding to obtain the europium-doped fluorophlogopite fluorescent powder (Fpl: eu) 3+ Fluorescent powder).
Comparative example 4
This comparative example provides europium-doped barium micaFluorescent powder (Ba-Fpl: eu) 3+ ) The preparation method of (2) at least comprises the following steps:
step one, will 0.1725g BaO,0.0884g MgO,0.1160g Al 2 O 3 ，0.4020g SiO 2 ，0.1370g MgF 2 And 0.0058g Eu 2 O 3 Fully grinding the mixture in an agate mortar for 20min to obtain mixed solid powder;
step two, placing the mixed solid powder into a corundum crucible, heating to 720 ℃ in a muffle furnace at a speed of 5 ℃/min, preserving heat for 2 hours, heating to 1150 ℃ at a speed of 2.0 ℃/min, calcining for 5.0 hours, cooling to room temperature at a speed of 2.0 ℃/min, and grinding to obtain the europium-doped barium tetrasilicon mica fluorescent powder (Ba-Fpl: eu) 3+ Fluorescent powder).
Comparative example 5
The comparative example of the present invention provides a method for preparing europium-doped barium tetrasilicon mica fluorescent powder, which is exactly the same as example 1, except that the addition amount of europium oxide is changed to 0.0217g, and Ba-Fpl/4Si:11% Eu is prepared 3+ Fluorescent powder.
Comparative example 6
The invention provides a preparation method of europium-doped natural fluorophlogopite powder, which comprises the following specific steps:
selecting commercially available adjacent mica monocrystal, crushing, grinding, ball milling to obtain fluorophlogopite powder, weighing 0.5g of fluorophlogopite powder, and 0.0063gEu 2 O 3 Fully grinding in an agate mortar, then placing the uniformly grinded solid powder into a corundum crucible, heating to 1050 ℃ in a muffle furnace at a speed of 5 ℃/min, calcining for 5.0h, cooling to room temperature at a speed of 2 ℃/min, and grinding to obtain natural Fpl: eu 3+ Fluorescent powder.
Comparative example 7
The comparative example provides a preparation method of europium-doped calcium tetrasilicon mica fluorescent powder and europium-doped strontium tetrasilicon mica powder, which has the same steps as those of example 1, except that 0.0631g of BaO and 0.1166g of SrO are respectively replaced by BaO, and the other steps are the same, so that Eu is respectively obtained 3+ Doped calcium tetrasilicon mica powder and Eu 3+ Doped strontium tetrasilicon mica powder。
Characterization of materials
FIG. 1 shows Ba-Fpl/4Si: eu prepared in example 1 3+ Sample, fpl: eu prepared in comparative example 3 3+ Sample, ba-Fpl: eu prepared in comparative example 4 3+ X-ray diffraction pattern of sample, at Fpl: eu 3+ In the X-ray diffraction pattern of the sample, the diffraction peak is matched with the monoclinic crystal structure, and the space group is C 2/m . It is apparent that when Eu is doped 3+ No additional diffraction peaks were observed later, indicating Eu 3+ Ion doping hardly affected the crystal structure of fluorophlogopite, and it can be seen that the main diffraction peaks at 8.9 °,17.8 °,26.8 °,34.3 ° and 45.4 ° correspond to (001), (020), (003), (200) and (005) crystal planes, respectively. From (Ba-Fpl: eu) 3+ Sample and Ba-Fpl Eu 3+ As can be seen in the X-ray diffraction pattern of the sample, when the cation Ba 2+ Substituted interlayer K + After that, the (001) plane diffraction peak intensities of Ba-Fpl and Ba-Fpl/4Si are significantly reduced, and this result can be explained by the change of the interlayer cation coordination mode. Due to Ba 2+ And K + The Si/Al content ratio in the tetrahedral sheet changes after substitution with the same stoichiometric ratio and the Ba is caused to be different in the charge number 2+ Octahedral coordination with tetrahedral sheets ultimately results in a significant decrease in diffraction peak intensity. In addition, we can calculate that the interlayer spacing between Ba-Fpl and Ba-Fpl/4Si is slightly reduced, and the corresponding interlayer distances (d values) are respectively
Figure GDA0004147201820000091
And->
Figure GDA0004147201820000092
When using Ba with smaller ionic radius 2+ />
Figure GDA0004147201820000093
Substitution K +
Figure GDA0004147201820000094
When the "radius effect" produces this result. On the other hand, K + With one unitPositive charge, while Ba 2+ The bonding force of the Ba-O bond is stronger than that of the K-O bond with two unit positive charges. Therefore, the mechanical properties of the barium mica are also improved. Meanwhile, the intensity of the (003) diffraction peak of Ba-Fpl/4Si is obviously increased compared with that before structural modification, which shows that the crystallization performance of mica is enhanced along with the increase of Si content.
FIGS. 2 to 4 show Fpl: eu prepared in comparative example 3, respectively 3+ Sample, ba-Fpl: eu prepared in comparative example 4 3+ Sample, ba-Fpl/4Si: eu prepared in example 1 3+ SEM and TEM images of the samples. As can be seen from FIG. 2, although Eu is incorporated into the fluorophlogopite matrix 3+ However, clay particles having a distinct layered structure can be clearly observed in SEM images, and the crystallization effect is very good, fpl: eu 3+ The average particle size of the sample was 3-5. Mu.m. As can be seen from FIGS. 3 and 4, ba-Fpl: eu 3+ Sample and Ba-Fpl/4Si: eu 3+ The average grain diameter of the sample is about 7-15 mu m, which accords with the grain diameter requirement of fingerprint powder, and the lamellar structure of the mica sample can be observed in a TEM image, and the edge of the mica sheet can be easily found to have obvious layering effect; for Ba-Fpl/4Si Eu 3+ Sample, stacking ratio Fpl: eu between adjacent sheets 3+ Sample, ba-Fpl Eu 3+ The sample is more compact and firm, and further proves the analysis result of the X-ray diffraction.
FIGS. 5 to 7 show Fpl: eu prepared in comparative example 3, respectively 3+ Sample, ba-Fpl: eu prepared in comparative example 4 3+ Sample, ba-Fpl/4Si: eu prepared in example 1 3+ EDS plot of sample. In the EDS diagram, the presence of the K, ba, mg, al, si, O, F and Eu elements was observed, except that no other elements were found. Ba-Fpl/4Si: eu 3+ The sample is analyzed by taking an example, the measured content value (20.31%) of Si element and the theoretical content value (21.05%) can be almost matched, and the measured content of other elements can be more accurately corresponding to the theoretical composition of the sample, so that the prepared sample is consistent with the composition of the set sample.
FIGS. 8 to 9 show Ba-Fpl/4Si: eu prepared in examples 1 to 3 and comparative example 5, respectively 3+ Excitation spectrum and emission spectrum of sample. As can be seen from the figure, the excitation peaks and emission peaks of all samples show some column-like shapes. As can be seen from FIG. 8, there is a significantly strong absorption broadband in the region between 230nm and 300nm, centered at 252nm, which is mainly derived from O 2- →Eu 3+ In addition to the broadband, several relatively weak sharp peaks at 365 nm, 3831 nm, 390 nm,414nm and 465nm correspond to Eu, respectively 3+ A kind of electronic device 7 F 0 → 5 D 4 ， 7 F 0 → 5 L 7 ， 7 F 0 → 5 L 6 ， 7 F 0 → 5 D 3 And 7 F 0 → 5 D 2 the excitation peak in the 252nm ultraviolet region is significantly higher than the other sharp peaks, which means that Ba-Fpl/4Si: eu 3+ The sample can be well excited by 252nm uv light, and therefore 252nm in the uv region can be selected as a suitable excitation wavelength. As can be seen from FIG. 9, ba-Fpl/4Si: eu prepared in example 1 3+ The luminescence intensity of the sample at 252nm excitation wavelength is maximum, and Ba-Fpl/4Si Eu prepared in examples 1-3 3+ The luminous intensity of the samples is obviously better than that of comparative example 5. Ba-Fpl/4Si: eu prepared in example 4 3+ The phosphor can achieve a fluorescence effect substantially equivalent to that of example 3.
FIG. 10 shows Fpl: eu prepared in comparative example 3 3+ Sample, ba-Fpl: eu prepared in comparative example 4 3+ Sample, ba-Fpl/4Si: eu prepared in example 1 3+ Graph of luminescence intensity of sample at 252nm excitation wavelength. As can be seen from the figure, ba-Fpl/4Si: eu 3+ The luminous intensity of the sample is higher than Fpl-Eu 3+ The luminous intensity of the sample is obviously enhanced, which is about Fpl: eu 3+ The luminous intensity of the sample is 8-9 times. Ba-Fpl/4Si: eu 3+ The reason for the greatly enhanced luminescence of the samples is due to the change in the density of negative charges in the mica platelets and their spatial arrangement. With equal amounts of Ba 2+ Substituted interlayer K + The Si content in the tetrahedral layer is adjusted to promote the octahedral layer in the mica laminate to generate Mg 2+ Vacancies to balance excess positive charge, thus creating a pair of crystalsThe field environment is more sensitive 5 D 0 → 7 F 2 Electric dipole transition, finally, the fluorescence performance and Fpl: eu are achieved 3+ The sample is significantly enhanced compared to the sample.
FIG. 11 shows Fpl: eu prepared in comparative example 3 3+ Sample, ba-Fpl: eu prepared in comparative example 4 3+ Sample, ba-Fpl/4Si: eu prepared in example 1 3+ Fluorescence decay curve of the sample. As can be seen from the graph, the decay curve shows strong regularity, fpl: eu 3+ The life of the sample decays exponentially, ba-Fpl: eu 3+ Sample and Ba-Fpl/4Si: eu 3+ The lifetime of the sample is attenuated almost in a straight line. The fluorescence lifetime value of the sample corresponds to the fluorescence intensity, and the strongest light is emitted by Ba-Fpl/4Si: eu 3+ The samples had a maximum lifetime value (τ=2.15 ms), which is much higher than Fpl: eu 3+ Lifetime value of sample (τ=0.73 ms). In addition, ba-Fpl/4Si: eu 3+ The quantum yield of the sample is 20.67%, compared with Fpl: eu 3+ The quantum yield of the sample (qy=5.44%) is obviously improved.
FIG. 12 shows Ba-Fpl/4Si: eu prepared in example 1 and comparative examples 1-2 of the present invention 3+ Emission spectrum of the sample at 252nm excitation wavelength. As can be seen from the figure, ba-Fpl/4Si: eu prepared in example 1 3+ The luminous intensity of the sample is obviously better than that of comparative examples 1-2.
FIG. 13 shows Fpl: eu prepared in comparative example 3 3+ Sample and Natural Fpl: eu prepared in comparative example 6 3+ As can be seen from the emission spectrum of the sample, fpl: eu prepared in comparative example 3 3+ The luminous intensity of (C) is obviously higher than that of the natural Fpl: eu prepared in comparative example 6 3+ Is about natural Fpl: eu 3+ And 2.5 times of luminous intensity. This illustrates the synthesis of Eu provided by the present invention 3+ Fluorescent property of doped mica powder is superior to Eu 3+ Fluorescent properties of doped natural mica.
Latent fingerprint detection
The cleaned fingers were pressed against the surfaces of various objects having different roughness, and then the Ba-Fpl/4Si Eu prepared in example 1 was measured as follows 3+ The sample is lightly smeared on the printed latent fingerprints by a soft brushAnd (3) blowing off the residual powder on the surface of the object by using a blower, and observing the development effect of the latent fingerprints under 254nm ultraviolet light.
Fpl: eu prepared in comparative example 3 3+ Sample, ba-Fpl: eu prepared in comparative example 4 3+ The samples were also subjected to latent fingerprint development effect tests according to the above procedure, respectively, and compared with the development results of example 1.
Wherein FIG. 14 shows Fpl: eu prepared in comparative example 3 3+ Sample, ba-Fpl: eu prepared in comparative example 4 3+ Sample, ba-Fpl/4Si: eu prepared in example 1 3+ Latent fingerprint detection image of sample on plain paper a. As is evident from the figure, ba-Fpl/4Si: eu 3+ The sample shows a specific Fpl to Eu 3+ Sample, ba-Fpl Eu 3+ The better detection effect of the sample is on the one hand due to the fact that the ratio of Ba-Fpl/4Si to Eu is that 3+ The sample particles have stronger adhesion with fingerprint residues on the surface of the substrate, and on the other hand, the latent fingerprint patterns detected by using the sample particles show more bright red and bright colors, so that the distribution of the ridge and groove areas in the ridge pattern is more obvious.
FIG. 15 shows Eu prepared in comparative example 7 3+ Doped calcic tetrasilicon mica powder sample and Eu 3+ Doped strontium tetrasilicon mica powder sample, ba-Fpl/4Si: eu prepared in example 1 3+ Latent fingerprint detection image of sample on plain paper b. As can be seen from the figure, eu 3+ Doped calcic tetrasilicon mica powder sample and Eu 3+ The latent fingerprint detection image of the doped strontium tetrasilicon mica powder sample has the advantages of fuzzy overall effect, unobvious ridge and groove area transition, no observation of most I-III level details after image amplification, and weaker fluorescence intensity than Ba-Fpl/4Si Eu 3+ And (3) a sample. Demonstration of Ba-Fpl/4Si: eu prepared in example 1 3+ Sample and Eu 3+ Doped calcium tetrasilicon mica powder sample and Eu 3+ Compared with the doped strontium tetrasilicon mica powder sample, the latent fingerprint detection image has better effects in the aspects of definition and color brightness.
FIG. 16 is Ba-Fpl/4Si: eu prepared in example 1 3+ Samples were exposed to 254nm UV light on surfaces of various objects of varying roughnessA latent fingerprint image in which aluminum foil (a), glass slide (b), tinfoil (c), plain paper (d), plain paper (e) and plain paper (f). As can be seen from the graph, clear fingerprint ridge patterns can be observed on the surfaces of objects with different roughness, and the detection effect is obvious, which proves that the Ba-Fpl/4Si:Eu prepared by the embodiment of the invention 3+ The sample can realize the detection of the latent fingerprints on the surfaces of various objects.
To further confirm the detection effect of the latent fingerprints, FIG. 17 shows Ba-Fpl/4Si Eu prepared in example 1 3+ A complete and partial fluorescent magnified image of the latent fingerprint of the sample on the surface of the tinfoil under a 254nm uv lamp. From the figure, the short ridges, bifurcations, ends of ridges, lakes, bifurcations, nuclei, delta and other class II details in the latent fingerprints, and the fault and sweat pores and other class III details are all clearly visible. All the details presented in stages I-III prove that the Ba-Fpl/4Si: eu prepared in the examples of the invention 3+ The sample shows high selectivity and high sensitivity in latent fingerprint detection. The novel red fluorescent powder prepared by the embodiment of the invention can be used as an ideal candidate in the application of detecting the latent fingerprints.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, or alternatives falling within the spirit and principles of the invention.

Claims (8)

1. The preparation method of the europium-doped barium tetrasilicon mica fluorescent powder is characterized by comprising the following steps of:
uniformly mixing barium oxide, magnesium oxide, silicon dioxide, magnesium fluoride and europium oxide, and grinding to obtain mixed solid powder;
wherein, the total amount of barium oxide, magnesium oxide, silicon dioxide and magnesium fluoride is taken as 100 percent, and the dosages of the components are as follows: 13.97 to 15.45 percent of barium oxide, 4.77 to 5.27 percent of magnesium oxide, 67.75 to 70.05 percent of silicon dioxide and 11.09 to 12.26 percent of magnesium fluoride; the mol ratio of Eu in the europium oxide to Ba in the barium oxide is 0.07-0.10:1;
and step two, heating the mixed solid powder to 700-750 ℃ at a speed of 4-6 ℃/min for calcining for 2-2.5 h, heating to 1100-1170 ℃ at a speed of 1.5-2.5 ℃/min for calcining for 4.5-5.0 h, cooling and grinding to obtain the europium-doped barium tetrasilicon mica fluorescent powder.
2. The method for preparing the europium-doped barium tetrasilicon mica fluorescent powder according to claim 1, wherein the total amount of barium oxide, magnesium oxide, silicon dioxide and magnesium fluoride is 100%, and the following components are used: 14.71% of barium oxide, 5.02% of magnesium oxide, 68.58% of silicon dioxide and 11.69% of magnesium fluoride.
3. The method for preparing europium-doped barium tetrasilicon mica fluorescent powder according to claim 1, wherein the molar ratio of Eu in europium oxide to Ba in barium oxide is 0.075-0.085:1.
4. The method of claim 3, wherein the molar ratio of Eu in europium oxide to Ba in barium oxide is 0.08:1.
5. The method for preparing europium-doped barium tetrasilicon mica fluorescent powder according to claim 1, wherein in the second step, the cooling rate is 1-3 ℃/min.
6. The method of claim 1, wherein in the second step, the mixed solid powder is calcined at 720 ℃ for 2h to 2.5h and then at 1150 ℃ for 4.5h to 5.0h.
7. The europium-doped barium tetrasilicon mica fluorescent powder is characterized by being prepared by a preparation method of the europium-doped barium tetrasilicon mica fluorescent powder according to any one of claims 1 to 6.
8. The use of europium-doped barium tetrasilicon mica fluorescent powder in latent fingerprint detection.
CN202110932190.0A 2021-08-13 2021-08-13 Europium-doped barium tetrasilicon mica fluorescent powder and preparation method and application thereof Active CN113637478B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202110932190.0A CN113637478B (en) 2021-08-13 2021-08-13 Europium-doped barium tetrasilicon mica fluorescent powder and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202110932190.0A CN113637478B (en) 2021-08-13 2021-08-13 Europium-doped barium tetrasilicon mica fluorescent powder and preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN113637478A CN113637478A (en) 2021-11-12
CN113637478B true CN113637478B (en) 2023-06-13

Family

ID=78421673

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202110932190.0A Active CN113637478B (en) 2021-08-13 2021-08-13 Europium-doped barium tetrasilicon mica fluorescent powder and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN113637478B (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114854401A (en) * 2022-05-25 2022-08-05 河北师范大学 Green fluorophlogopite fluorescent powder with high quantum yield and preparation method and application thereof
CN116731711B (en) * 2023-05-29 2024-02-13 河北师范大学 Rare earth doped barium lithium boron mica layered luminescent material and preparation method and application thereof

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5132256A (en) * 1991-03-26 1992-07-21 Corning Incorporated Fiber-reinforced composite comprising mica-doped ceramic matrix
US5609792A (en) * 1992-12-31 1997-03-11 Osram Sylvania Inc. Phosphor and method of making same
CN103333528A (en) * 2013-06-26 2013-10-02 福建师范大学 Preparation method of pearlescent pigment having fluorescent effect
CN107043622A (en) * 2016-12-30 2017-08-15 陕西科技大学 A kind of europium doping strontium silicate blood orange emitting phosphor and preparation method thereof
CN109810705B (en) * 2019-02-26 2020-04-24 武汉理工大学 Europium-doped barium magnesium niobate red fluorescent powder and preparation method thereof
CN110690017B (en) * 2019-10-16 2022-02-08 浦江召日电器有限公司 Improved alloy resistor
CN112662201B (en) * 2020-12-21 2021-10-22 江西善纳新材料科技有限公司 Preparation method of mica-based fluorescent pearlescent pigment

Also Published As

Publication number Publication date
CN113637478A (en) 2021-11-12

Similar Documents

Publication Publication Date Title
Darshan et al. Effective fingerprint recognition technique using doped yttrium aluminate nano phosphor material
CN113637478B (en) Europium-doped barium tetrasilicon mica fluorescent powder and preparation method and application thereof
CN106497555B (en) Long persistence luminescent silicate material and preparation method thereof
RU2672708C2 (en) Zinc-sulphide phosphor having photo- and electroluminescent properties, process for producing same, and security document, security feature and method for detecting same
CN104818023B (en) Rare earth luminescent material preparation method and its product containing crystal defect renovation technique
Yeshodamma et al. Monovalent ions co-doped SrTiO3: Pr3+ nanostructures for the visualization of latent fingerprints and can be red component for solid state devices
CN106833636B (en) It can be by near ultraviolet and blue light activated red fluorescence powder, preparation method and application
Sahu et al. Generation of white light from dysprosium-doped strontium aluminate phosphor by a solid-state reaction method
Sahu et al. Luminescence studies on the europium doped strontium metasilicate phosphor prepared by solid state reaction method
Mamatha et al. Designing orange-red emitting luminescent platform for data security and information encryption based Sm3+ doped BLAO phosphor
CN115991993A (en) Sodium lutetium gallium germanium garnet-based green light fluorescent powder for anti-counterfeiting and preparation method thereof
CN114958351B (en) Ultraviolet excited blue-violet fluorescent powder, preparation method thereof and light-emitting device
Abdou et al. Defect and dopant induced photoluminescence of molten salt synthesized BaZrO3 crystals
Sahu et al. Dysprosium doped di-calcium magnesium di-silicate white light emitting phosphor by solid state reaction method
Yin et al. Effect of Ga3+ ion doping on emission thermal stability and efficiency of MgAl2O4: Cr3+ phosphor
JP2020100703A (en) Producing method of rare earth aluminate phosphor, rare earth aluminate phosphor and light emitting device
CN114854401A (en) Green fluorophlogopite fluorescent powder with high quantum yield and preparation method and application thereof
CN107722972B (en) Green long-afterglow luminescent material and preparation method thereof
CN1810921A (en) Red long afterglow luminescent material and its prepn
CN116731711B (en) Rare earth doped barium lithium boron mica layered luminescent material and preparation method and application thereof
Rajkumar et al. RETRACTED ARTICLE: Development of a new-double perovskite type Sr2YZrO5. 5: Eu3+ red phosphor for latent fingerprint applications
CN113061432A (en) Preparation method and application of high-stability multifunctional whitlockite type fluorescent powder
Li et al. A novel M2Ga2GeO7: N3+ (M= Ca, Ba, Sr; N= Cr, Nd, Er) sub-micron phosphor with multiband NIR emissions: preparation, structure, properties, and LEDs
Kumar et al. Annealing-assisted optimization for persistency of afterglow of SrAl 2 O 4: Eu 2+/Dy 3+ microparticles for forensic detection
CN110452696A (en) A kind of red long afterglow luminous material and preparation method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant