Preparation of a four-mode fluorescent anti-counterfeiting material

Abstract

The present invention relates to a Mn 2+ Germanate-doped quadruple-encrypted fluorescent anti-counterfeiting material and preparation method thereof, wherein the general formula of the quadruple-encrypted fluorescent anti-counterfeiting material is Ca 2‑x Mg x Ge7O 16 :yMn 2+ ,0

Description

Technical Field

[0001] The present invention relates to the field of down-conversion fluorescent anti-counterfeiting, and in particular to the synthesis and application of a safer four-mode fluorescent anti-counterfeiting material. Background Art

[0002] With the development of economic globalization, commodities are also becoming increasingly globalized. Many commodities are traded around the world every day. However, with the globalization of commodities, the problem of counterfeit goods has become increasingly prominent. Counterfeit and shoddy goods seriously damage the reputation and interests of commodity producers, and also seriously affect the user experience of commodities consumers, and even endanger their physical health. Therefore, commodity anti-counterfeiting is an indispensable part of commodity globalization.

[0003] The valence states of Mn ions that can achieve fluorescence emission are mainly Mn 2+ 、Mn 4+ , Mn 5+ ions, including Mn 2+ With 3D 5 The electronic configuration, in which the outer electrons are directly exposed to the crystal field environment, makes Mn 2+ The emission of ions is easily affected by the external coordination situation and the crystal field strength, so it can be adjusted by adjusting the Mn 2+ The crystal field environment around the ion affects the Mn 2+ The ion luminescence range is regulated. 2+ Ions in a weak crystal field achieve high energy emission (short-wave emission), and in a strong crystal field achieve low energy emission (long-wave emission). 2+ When doped into the matrix lattice, it is very easy to form electron traps and vacancy defects to cause afterglow. Mn ions are cheaper than rare earth ion doping, so Mn 2+ Ions are ideal doping ions for fluorescent anti-counterfeiting materials.

[0004] In the past decade or so, various anti-counterfeiting technologies have rapidly developed, including radio frequency identification (RFID), magnetic response, and laser holograms. However, these technologies have drawbacks such as ease of imitation and high manufacturing costs. In contrast, fluorescent anti-counterfeiting has become widely used due to its advantages such as low manufacturing cost, simple design, easy identification, and mass production. However, the currently widely used single-light-emitting fluorescent anti-counterfeiting materials are extremely easy to imitate, which reduces the security of fluorescent anti-counterfeiting. Summary of the Invention

[0005] In view of the above-mentioned deficiencies in the prior art, the object of the present invention is to provide a transition metal Mn-doped germanate quadruple anti-counterfeiting fluorescent material that is low-cost, easy to mass-produce, and safer.

[0006] Another object of the present invention is to provide a method for preparing a transition metal Mn-doped germanate quadruple anti-counterfeiting fluorescent material with simple synthesis conditions.

[0007] In order to solve the above technical problems, the present invention adopts the following technical solution: a transition metal Mn-doped four-mode fluorescent anti-counterfeiting material, characterized in that the chemical formula is A 2-x B x Ge7O 16 :yMn 2+ , where A is Ca, Sr, or Ba; B is Mg or Zn; 0.05≤x≤0.5; 0.001≤y≤0.1. It exhibits color-tunable multicolor luminescence with afterglow under UV excitation at 222nm and 265nm.

[0008] The excitation spectrum range of the above four-mode fluorescent anti-counterfeiting phosphors is 200-300nm, and they can be effectively excited by 222nm and 265nm ultraviolet light respectively. The main peaks are located at 600nm and 665nm respectively, and each has observable afterglow.

[0009] The method for preparing the above four-mode fluorescent anti-counterfeiting fluorescent powder is as follows: 2-x Mg x Ge7O 16 :yMn 2+ The high-temperature solid-phase method is used for synthesis. The raw materials (CaCO3, MgCO3, GeO2, MnO2) are accurately weighed according to the stoichiometric ratio and placed in an agate mortar for thorough grinding and mixing. The raw material mixture is sintered at 1000°C for 4 hours, cooled naturally to room temperature, and ground to obtain the four-mode fluorescent anti-counterfeiting powder material of the present invention.

[0010] The method for preparing the above four-mode fluorescent anti-counterfeiting phosphor is as follows: when the chemical formula of the phosphor is Sr 2-x Mg x Ge7O 16 :yMn 2+ The high-temperature solid-phase method is used for synthesis. The raw materials (SrCO3, MgCO3, GeO2, MnO2) are accurately weighed according to the stoichiometric ratio and placed in an agate mortar for thorough grinding and mixing. The raw material mixture is sintered at 1200°C for 4 hours, cooled naturally to room temperature, and ground to obtain the four-mode fluorescent anti-counterfeiting powder material of the present invention.

[0011] The method for making the above four-mode fluorescent anti-counterfeiting fluorescent powder is as follows: 2-x Mg x Ge7O 16 :yMn 2+The high-temperature solid-phase method is used for synthesis. The raw materials (BaCO3, MgCO3, GeO2, MnO2) are accurately weighed according to the stoichiometric ratio and placed in an agate mortar for thorough grinding and mixing. The raw material mixture is sintered at 1100°C for 4 hours, cooled naturally to room temperature, and ground to obtain the four-mode fluorescent anti-counterfeiting powder material of the present invention.

[0012] The method for preparing the above four-mode fluorescent anti-counterfeiting fluorescent powder is as follows: 2-x Zn x Ge7O 16 :yMn 2+ The high-temperature solid-phase method is used for synthesis. The raw materials (CaCO3, ZnO, GeO2, MnO2) are accurately weighed according to the stoichiometric ratio and placed in an agate mortar for thorough grinding and mixing. The raw material mixture is sintered at 900°C for 4 hours, cooled naturally to room temperature, and ground to obtain the four-mode fluorescent anti-counterfeiting powder material of the present invention.

[0013] The method for preparing the above four-mode fluorescent anti-counterfeiting phosphor is as follows: when the chemical formula of the phosphor is Sr 2-x Zn x Ge7O 16 :yMn 2+ The high-temperature solid-phase method is used for synthesis. The raw materials (SrCO3, ZnO, GeO2, MnO2) are accurately weighed according to the stoichiometric ratio and placed in an agate mortar for thorough grinding and mixing. The raw material mixture is sintered at 850°C for 4 hours, cooled naturally to room temperature, and ground to obtain the four-mode fluorescent anti-counterfeiting powder material of the present invention.

[0014] The method for making the above four-mode fluorescent anti-counterfeiting fluorescent powder is as follows: 2-x Zn x Ge7O 16 :yMn 2+ The high-temperature solid-phase method is used for synthesis. The raw materials (BaCO3, ZnO, GeO2, MnO2) are accurately weighed according to the stoichiometric ratio and placed in an agate mortar for thorough grinding and mixing. The raw material mixture is sintered at 1150°C for 4 hours, cooled naturally to room temperature, and ground to obtain the four-mode fluorescent anti-counterfeiting powder material of the present invention. BRIEF DESCRIPTION OF THE DRAWINGS

[0015] Figure 1 The present invention synthesizes the anti-counterfeiting fluorescent powder Ca 2-x Ge7O 16 :xMg 2+ ,0.015Mn 2+ XRD patterns of (x=0, 0.05, 0.1, 0.2, 0.4, 0.5).

[0016] Figure 2 1 is the emission and excitation spectrum diagram of Example 1 of the present invention.

[0017] Figure 3 This is a diagram showing the emission and afterglow effects of the phosphor of Example 1 of the present invention under natural light irradiation and excitation at 222nm and 265nm.

[0018] Figure 4 This is a diagram showing the actual anti-counterfeiting effect of Example 1 of the present invention. DETAILED DESCRIPTION

[0019] The present invention is further described below with reference to practical examples. The reagents used in the examples are of high purity (4N) or premium grade purity and are commercially available unless otherwise specified.

[0020] 1. Preparation and application method of a quadruple-encrypted fluorescent anti-counterfeiting material

[0021] Example 1:

[0022] Weigh 0.3003g of calcium carbonate solid powder, 1.4644g of germanium dioxide solid powder, 0.0971g of basic magnesium carbonate solid powder, and 0.0035g of manganese dioxide, and place the above-weighed solid powders into an agate mortar and grind them for 40 minutes to fully mix them. The fully mixed powders are placed into an alumina crucible, and then the crucible is placed into a muffle furnace and sintered at 850°C for 4 hours. After it is naturally cooled to room temperature, the sintered powder material is placed into an agate mortar and further ground to obtain the four-mode anti-counterfeiting fluorescent powder Ca 1.5 Mg 0.5 Ge7O 16 :0.015Mn 2+ .

[0023] The powder material of Example 1 was subjected to XRD test and further analysis, as shown in FIG. Figure 1 shown.

[0024] The fluorescence spectrum of Example 1 was measured and further analyzed, as shown in FIG. Figure 2 shown.

[0025] The phosphor material of Example 1 is excited at 222nm and 265nm and the afterglow effect is as follows Figure 3 shown.

[0026] Example 1 Fluorescent anti-counterfeiting effect is shown as follows Figure 4 shown.

[0027] Example 2:

[0028] Weigh 0.5855g of calcium carbonate solid powder, 2.1966g of germanium dioxide solid powder, 0.0146g of basic magnesium carbonate solid powder, and 0.0052g of manganese dioxide, and put the above-weighed solid powders into an agate mortar for grinding for 40 minutes to fully mix them and put them into an alumina crucible. Then, put the crucible into a muffle furnace and sinter at 950°C for 4 hours. After it is naturally cooled to room temperature, the sintered powder material is put into an agate mortar for further grinding to obtain the four-mode anti-counterfeiting fluorescent powder Ca 1.95 Mg 0.05 Ge7O 16 :0.015Mn 2+ .

[0029] The powder material of Example 2 was subjected to XRD test and further analysis, as shown in FIG. Figure 1 shown.

[0030] The fluorescence spectrum of Example 2 was measured and further analyzed.

[0031] Example 3:

[0032] Weigh 0.5705g of calcium carbonate solid powder, 2.1966g of germanium dioxide solid powder, 0.0291g of basic magnesium carbonate solid powder, and 0.0052g of manganese dioxide, and grind the solid powders into an agate mortar for 40 minutes to fully mix them. Place them into an alumina crucible, and then place the crucible into a muffle furnace and sinter at 1000℃ for 4 hours. After cooling naturally to room temperature, place the sintered powder materials into an agate mortar for further grinding to obtain the four-mode anti-counterfeiting fluorescent powder Ca 1.9 Mg 0.1 Ge7O 16 :0.015Mn 2+ .

[0033] The powder material of Example 3 was subjected to XRD test and further analysis, as shown in FIG. Figure 1 shown.

[0034] The fluorescence spectrum of Example 3 was measured and further analyzed.

[0035] Example 4:

[0036] (1) Weigh 0.5405g of calcium carbonate solid powder, 2.1966g of germanium dioxide solid powder, 0.0583g of basic magnesium carbonate solid powder, and 0.0052g of manganese dioxide, and grind the solid powders into an agate mortar for 40 minutes to fully mix them. Then put them into an alumina crucible, and then put the crucible into a muffle furnace and sinter at 1100℃ for 4 hours. After it cools naturally to room temperature, the sintered powder material is put into an agate mortar for further grinding to obtain the four-mode anti-counterfeiting fluorescent powder Ca 1.8 Mg 0.2 Ge7O 16 :0.015Mn 2+ .

[0037] The powder material of Example 4 was subjected to XRD test and further analysis, as shown in FIG. Figure 1 shown.

[0038] The fluorescence spectrum of Example 4 was measured and further analyzed.

[0039] Example 5:

[0040] (1) Weigh 0.4804g of calcium carbonate solid powder, 2.1966g of germanium dioxide solid powder, 0.1166g of basic magnesium carbonate solid powder, and 0.0052g of manganese dioxide, and grind the solid powders into an agate mortar for 40 minutes to fully mix them. Then put them into an alumina crucible, and then put the crucible into a muffle furnace and sinter at 1200℃ for 4 hours. After it cools naturally to room temperature, the sintered powder material is put into an agate mortar for further grinding to obtain the four-mode anti-counterfeiting fluorescent powder Ca 1.6 Mg 0.4 Ge7O 16 :0.015Mn 2+ .

[0041] The powder material of Example 5 was subjected to XRD test and further analysis, as shown in FIG. Figure 1 shown.

[0042] The fluorescence spectrum of Example 5 was measured and further analyzed.

Claims

1. A four-mode fluorescent anti-counterfeiting material, characterized in that: It includes a four-mode fluorescent anti-counterfeiting material, the general formula of which is Ca 2- x Mg x Ge7O 16 :yMn 2+ , 0 <x<2,0.001≤y≤0.1。 2. The four-mode fluorescent anti-counterfeiting material according to claim 1, characterized in that: The Ca is introduced in the form of a Ca-containing compound, the Mg is introduced in the form of a Mg-containing compound, and the Mn is introduced in the form of a Mn-containing compound.

3. A method for preparing a four-mode fluorescent anti-counterfeiting material, characterized in that: The following steps are involved: 1) According to the general formula Ca 2-x Mg x Ge7O 16 : yMn 2+ , where 0 < x < 2 and 0.001 ≤ y ≤ 0.1, take the corresponding raw materials in the stoichiometric ratio of each substance, and grind them evenly to obtain a mixture; 2) The mixture obtained in step 1) is placed in a high-temperature furnace for calcination. After the reaction is completed, the mixture is naturally cooled and ground to obtain the four-mode fluorescent anti-counterfeiting material.

4. The method for preparing the four-mode fluorescent anti-counterfeiting material according to claim 3, characterized in that: The raw materials are compounds containing Ca, compounds containing Mg, and compounds containing Mn.

5. The method for preparing the four-mode fluorescent anti-counterfeiting material according to claim 3, characterized in that: The high-temperature furnace calcination has a calcination temperature of 850 to 1200 degrees Celsius and a calcination time of 2 to 6 hours.

6. The use of the four-mode fluorescent anti-counterfeiting material according to claim 1, characterized in that: The material generates orange light of 600 nm when excited by 222 nm ultraviolet light, and has afterglow; and generates deep red light of 665 nm when excited by 265 nm ultraviolet light, and also has afterglow.

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