Early warning type light-emitting material for ray flexible protection, preparation method and application

Abstract

The invention discloses a luminescent material for early warning type ray flexible protection, the structural general formula of the luminescent material is 2NaEuxGd (1-x) (PO3) 4, and the molar ratio of Eu < 3 + > to Gd < 3 + > in the 2NaEuxGd (1-x) (PO3) 4 is 1-100%; the invention also discloses a preparation method and application of the luminescent material. According to the early warning type luminescent material for ray flexible protection, the problem that in the prior art, a rare earth luminescent material cannot be added in ray flexible protection for early warning is solved.

Description

Technical Field

[0001] The present invention belongs to the technical field of luminescent materials, and specifically relates to luminescent materials for early warning type flexible radiation protection, and also relates to a preparation method and application of the luminescent materials for early warning type flexible radiation protection. Background Art

[0002] In the process of nuclear energy utilization, the X-rays, α-rays, β-rays, γ-rays and neutron rays generated by nuclear radiation can cause varying degrees of damage to the human body. Therefore, nuclear safety issues are receiving more and more attention, and doing a good job in nuclear radiation protection is the key to ensuring nuclear safety.

[0003] The most annoying thing is that radiation is invisible and intangible, and can easily hurt people without being noticed. Therefore, radiation warning is particularly important in various complex environments. Gd2O3 is a fluorescent powder excited by ultraviolet light. Among various dopants, Gd2O3 is considered to be a suitable matrix for doping rare earth ions based on the similarity of ion radius. According to the needs of luminous warning applications, the human eye is most sensitive to red and green light, so researchers have targeted Gd2O3:Eu 3+ and Gd2O3:Tb 3+ After a lot of exploration, the results showed that the rare earth ion Eu 3+ or Tb 3+ The luminescence intensity of doped Gd2O3 nanoparticles increases with the increase of doping concentration within a certain concentration range, but when the optimal concentration is exceeded, concentration quenching will occur. From the current research results, adding rare earth luminescent materials to flexible radiation protection to achieve early warning function has become a common problem faced by technicians in this field. Summary of the invention

[0004] The purpose of the present invention is to provide a luminescent material for early warning flexible radiation protection, which solves the problem in the prior art that rare earth luminescent materials cannot be added to the flexible radiation protection for early warning.

[0005] The second object of the present invention is to provide a method for preparing a luminescent material for early warning type flexible radiation protection.

[0006] The third object of the present invention is to provide an application of luminescent materials for early warning radiation flexible protection.

[0007] The first technical solution adopted by the present invention is a luminescent material for early warning ray flexible protection, the general structural formula of the luminescent material is: 2NaEu x G (1-x) (PO3)4,2NaEu x G (1-x) (PO3)4 in Eu 3+ Relative to Gd 3+ The molar proportion is 1 to 100%.

[0008] The first technical solution of the present invention is also characterized in that:

[0009] 2NaEu x G (1-x) (PO3)4 in Eu 3+ Relative to Gd 3+ The molar proportion is 10 to 70%.

[0010] 2NaEu x G (1-x) (PO3)4 in Eu 3+ Relative to Gd 3+ The molar proportion is 30 to 50%.

[0011] The second technical solution adopted by the present invention is a method for preparing a luminescent material for early warning ray flexible protection, and the specific steps are as follows:

[0012] S1: Grind the mixed powder in an agate mortar to make it uniformly mixed. During grinding, anhydrous ethanol should be added until it can just immerse the mixture;

[0013] S2: sending the mixed powder obtained in S1 to a drying oven for drying;

[0014] S3: The dried powder of S2 is placed in a corundum crucible and calcined in a tube furnace under air atmosphere to obtain a calcined sample;

[0015] S4: The calcined sample obtained in S3 is washed with warm water and nitric acid to remove possible residual reactants, and a luminescent material for early warning type ray flexible protection is obtained. The general structural formula of the luminescent material for early warning type ray flexible protection is: 2NaEu x G (1-x) (PO3)4, of which Eu 3+ Relative to Gd 3+ The molar proportion is 1 to 100%.

[0016] The second technical solution of the present invention is also characterized in that:

[0017] The components of the mixed powder are oxides, (NH4)2HPO4 and Na2CO3. In terms of mass percentage, oxides account for 23-24%, (NH4)2HPO4 accounts for 69-70%, and Na2CO3 accounts for 7%.

[0018] The oxides are Gd2O3 and Eu2O3, and Gd2O3 and Eu2O3 are mixed in a certain proportion.

[0019] In S1, the grinding time is 50 to 70 minutes.

[0020] In S2, the drying temperature is 50-70°C and the time is 20-40 minutes.

[0021] In S3, the calcination temperature is 550-850°C, the calcination time is 22-26h, and the cooling rate after the calcination is 1-3°C / min.

[0022] The third technical solution adopted by the present invention is the application of luminescent materials for early warning flexible radiation protection in biological protection of nuclear submarines, internal protection of nuclear-proof armored vehicles, radiation protection of special-shaped and complex structures of nuclear facilities, and radiation protection of special electronic components.

[0023] The beneficial effects of the present invention are:

[0024] (1) The luminescent material for early warning radiation flexible protection provided by the present invention can obtain a uniform microstructure by blending, drying and calcining the matrix and functional particles and controlling their parameters within a controllable range; at the same time, the luminescent properties of the material can be effectively regulated to realize the radiation early warning function.

[0025] (2) The preparation method of the luminescent material for early warning radiation flexible protection provided by the present invention can effectively regulate the microstructure uniformity of the flexible material, enable it to obtain excellent radiation-induced luminescent properties, and the preparation method is simple and the parameters are easy to control. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] Figure 1 Example 1 of the present invention NaGd(PO3)4:30%Eu 3+ Topography of surface microstructure;

[0027] Figure 2 This is the spatial structure diagram of NaGd(PO3)4 in Example 1 of the present invention

[0028] Figure 3 The energy band structure diagram of NaGd(PO3)4 in Example 1 of the present invention is shown in FIG.

[0029] Figure 4 For example 1 of the present invention, NaGd(PO3)4 and NaGd(PO3)4:Eu 3+ (1~100mol%)XRD X-ray diffraction diagram;

[0030] Figure 5 Example 1 of the present invention NaGd(PO3)4:Eu 3+ X-ray excitation spectrum;

[0031] Figure 6 Example 1 of the present invention NaGd(PO3)4:30% Eu 3+ Schematic diagram of the luminescence of phosphor in an X-ray field. DETAILED DESCRIPTION

[0032] The present invention is described in detail below with reference to the accompanying drawings and specific embodiments.

[0033] The luminescent material for early warning ray flexible protection provided by the present invention has a general structural formula of: 2NaEu x G (1-x) (PO3)4.

[0034] Among them, 2NaEu x G (1-x) (PO3)4 in Eu 3+ Relative to Gd 3+ The molar proportion is 1 to 100%.

[0035] Preferably, 2NaEu x G (1-x) (PO3)4 in Eu 3+ Relative to Gd 3+ The molar proportion is 10 to 70%.

[0036] Preferably, 2NaEu x G (1-x) (PO3)4 in Eu 3+ Relative to Gd 3+ The molar proportion is 30 to 50%.

[0037] The preparation method of the luminescent material for early warning type ray flexible protection in the present invention comprises the following specific steps:

[0038] S1: Grind the mixed powder in an agate mortar to make it uniformly mixed. During grinding, anhydrous ethanol should be added until it can just immerse the mixture;

[0039] Among them, the grinding time is 50 to 70 minutes.

[0040] S2: sending the mixed powder obtained in S1 to a drying oven for drying;

[0041] The drying temperature is 50-70°C and the time is 20-40 minutes.

[0042] S3: The dried powder of S2 is placed in a corundum crucible and calcined in a tube furnace under air atmosphere to obtain a calcined sample;

[0043] The calcination temperature is 550-850°C, the calcination time is 22-26h, and the cooling rate after calcination is 1-3°C / min.

[0044] Among them, the chemical reaction formula for synthesizing europium-doped phosphate is:

[0045] 8(NH4)2HPO4+(1-x)Gd2O3+xEu2O3+Na2CO3→2NaEu x G (1-x) (PO3)4+16NH3+12H2O+CO2.

[0046] S4: The calcined sample obtained in S3 is washed with warm water and nitric acid to remove possible residual reactants, and a luminescent material for early warning type ray flexible protection is obtained. The general structural formula of the luminescent material for early warning type ray flexible protection is: 2NaEu x G (1-x) (PO3)4, of which Eu 3+ Relative to Gd 3+ The molar proportion is 1 to 100%.

[0047] Among them, the components of the mixed powder are oxides, (NH4)2HPO4 and Na2CO3. According to mass percentage, oxides account for 23-24%, (NH4)2HPO4 accounts for 69-70%, and Na2CO3 accounts for 7%. The oxides are Gd2O3 and Eu2O3, and Gd2O3 and Eu2O3 are mixed in a certain proportion.

[0048] The luminescent material for early warning flexible radiation protection prepared by the present invention is used in biological protection of nuclear submarines, internal protection of nuclear-proof armored vehicles, radiation protection of special-shaped and complex structures of nuclear facilities, and radiation protection of special electronic components.

[0049] Example 1

[0050] This embodiment provides a luminescent material for early warning type ray flexible protection and a preparation method thereof. The general structural formula of the luminescent material for early warning type ray flexible protection is: 2NaEu x G (1-x) (PO3)4, of which 2NaEu x G (1-x) (PO3)4 in Eu 3+ Relative to Gd 3+ The molar proportion is 1 to 100%.

[0051] Preferably, 2NaEu x G (1-x) (PO3)4 in Eu 3+ Relative to Gd 3+ The molar proportion is 10 to 70%.

[0052] Preferably, 2NaEu x G (1-x) (PO3)4 in Eu 3+ Relative to Gd 3+ The molar proportion is 30 to 50%.

[0053] The preparation method of the luminescent material for early warning type ray flexible protection comprises the following specific steps:

[0054] S1: Grind the mixed powder in an agate mortar to make it evenly mixed. Add anhydrous ethanol during grinding until it can just immerse the mixture. The grinding time is 60 minutes.

[0055] S2: The mixed powder obtained in S1 is sent to a drying oven for drying at a temperature of 60° C. for 30 min.

[0056] S3: The dried powder of S2 was sent to a corundum crucible and calcined in a tube furnace at 630°C under air atmosphere for 24 hours. After calcination, it was cooled at a rate of 2°C / min to obtain a calcined sample;

[0057] The chemical reaction formula for synthesizing europium-doped phosphate is: 8(NH4)2HPO4+(1-x)Gd2O3+xEu2O3+Na2CO3→2NaEu x G (1-x) (PO3)4+16NH3+12H2O+CO2.

[0058] S4: The calcined sample obtained in S3 is washed with warm water and nitric acid to remove possible residual reactants, and a luminescent material for early warning type ray flexible protection is obtained. The general structural formula of the luminescent material for early warning type ray flexible protection is: 2NaEu x G (1-x) (PO3)4, of which Eu 3+ Relative to Gd 3+ The molar proportion is 1 to 100%.

[0059] Among them, the components of the mixed powder are oxides, (NH4)2HPO4 and Na2CO3. According to mass percentage, oxides account for 23-24%, (NH4)2HPO4 accounts for 69-70%, and Na2CO3 accounts for 7%. The oxides are Gd2O3 and Eu2O3, and Gd2O3 and Eu2O3 are mixed in a certain proportion.

[0060] Example 2

[0061] This embodiment provides a luminescent material for early warning type ray flexible protection and a preparation method thereof. The general structural formula of the luminescent material for early warning type ray flexible protection is: 2NaEuxGd(1-x)(PO3)4, wherein 2NaEu x G (1-x) (PO3)4 in Eu 3+ Relative to Gd 3+ The molar proportion is 1 to 100%.

[0062] Preferably, 2NaEu x G (1-x) (PO3)4 in Eu 3+ Relative to Gd 3+ The molar proportion is 10 to 70%.

[0063] Preferably, 2NaEu x G (1-x) (PO3)4 in Eu 3+ Relative to Gd 3+ The molar proportion is 30 to 50%.

[0064] The preparation method of the luminescent material for early warning type ray flexible protection comprises the following specific steps:

[0065] S1: Grind the mixed powder in an agate mortar to make it evenly mixed. Add anhydrous ethanol during grinding until it can just immerse the mixture. The grinding time is 60 minutes.

[0066] S2: The mixed powder obtained in S1 is sent to a drying oven for drying at a temperature of 60° C. for 30 min.

[0067] S3: The dried powder of S2 was sent to a corundum crucible and calcined in a tube furnace at 630°C under air atmosphere for 24 hours. After calcination, it was cooled at a rate of 2°C / min to obtain a calcined sample;

[0068] Among them, the chemical reaction for synthesizing europium-doped phosphate is:

[0069] 8(NH4)2HPO4+(1-x)Gd2O3+xEu2O3+Na2CO3→2NaEu x G (1-x) (PO3)4+16NH3+12H2O+CO2.

[0070] S4: The calcined sample obtained in S3 is washed with warm water and nitric acid to remove possible residual reactants, and a luminescent material for early warning type ray flexible protection is obtained. The general structural formula of the luminescent material for early warning type ray flexible protection is: 2NaEu x G (1-x) (PO3)4, of which Eu 3+ Relative to Gd 3+ The molar proportion is 1 to 100%.

[0071] Among them, the components of the mixed powder are oxides, (NH4)2HPO4 and Na2CO3. According to mass percentage, oxides account for 23-24%, (NH4)2HPO4 accounts for 69-70%, and Na2CO3 accounts for 7%. The oxides are Gd2O3 and Eu2O3, and Gd2O3 and Eu2O3 are mixed in a certain proportion.

[0072] Example 3

[0073] This embodiment provides a luminescent material for early warning type ray flexible protection and a preparation method thereof. The general structural formula of the luminescent material for early warning type ray flexible protection is: 2NaEu x G (1-x) (PO3)4, of which 2NaEu x G (1-x) (PO3)4 in Eu 3+ Relative to Gd 3+ The molar proportion is 1 to 100%.

[0074] Preferably, 2NaEu x G (1-x) (PO3)4 in Eu 3+ Relative to Gd 3+ The molar proportion is 10 to 70%.

[0075] Preferably, 2NaEu x G (1-x) (PO3)4 in Eu 3+ Relative to Gd 3+ The molar proportion is 30 to 50%.

[0076] The preparation method of the luminescent material for early warning type ray flexible protection comprises the following specific steps:

[0077] S1: Grind the mixed powder in an agate mortar to make it evenly mixed. Add anhydrous ethanol during grinding until it can just immerse the mixture. The grinding time is 50 minutes.

[0078] S2: Send the mixed powder obtained in S1 to a drying oven for drying at a temperature of 50°C for 20 minutes.

[0079] S3: The dried powder of S2 was sent to a corundum crucible and calcined in a tube furnace at 550°C under air atmosphere for 22 hours. After calcination, it was cooled at a rate of 1°C / min to obtain a calcined sample;

[0080] Among them, the chemical reaction for synthesizing europium-doped phosphate is:

[0081] 8(NH4)2HPO4+(1-x)Gd2O3+xEu2O3+Na2CO3→2NaEux G (1-x) (PO3)4+16NH3+12H2O+CO2.

[0082] S4: The calcined sample obtained in S3 is washed with warm water and nitric acid to remove possible residual reactants, and a luminescent material for early warning type flexible radiation protection is obtained. The general structural formula of the luminescent material for early warning type flexible radiation protection is: 2NaEuxGd(1-x)(PO3)4, wherein Eu 3+ Relative to Gd 3+ The molar proportion is 1 to 100%.

[0083] Among them, the components of the mixed powder are oxides, (NH4)2HPO4 and Na2CO3. According to mass percentage, oxides account for 23-24%, (NH4)2HPO4 accounts for 69-70%, and Na2CO3 accounts for 7%. The oxides are Gd2O3 and Eu2O3, and Gd2O3 and Eu2O3 are mixed in a certain proportion.

[0084] Example 4

[0085] This embodiment provides a luminescent material for early warning type ray flexible protection and a preparation method thereof. The general structural formula of the luminescent material for early warning type ray flexible protection is: 2NaEu x G (1-x) (PO3)4, of which 2NaEu x G (1-x) (PO3)4 in Eu 3+ Relative to Gd 3+ The molar proportion is 1 to 100%.

[0086] Preferably, 2NaEu x G (1-x) (PO3)4 in Eu 3+ Relative to Gd 3+ The molar proportion is 10 to 70%.

[0087] Preferably, 2NaEu x G (1-x) (PO3)4 in Eu 3+ Relative to Gd 3+ The molar proportion is 30 to 50%.

[0088] The preparation method of the luminescent material for early warning type ray flexible protection comprises the following specific steps:

[0089] S1: Grind the mixed powder in an agate mortar to make it evenly mixed. Add anhydrous ethanol during grinding until it can just immerse the mixture. The grinding time is 70 minutes.

[0090] S2: The mixed powder obtained in S1 is sent to a drying oven for drying at a temperature of 70° C. for 40 min.

[0091] S3: The dried powder of S2 was sent to a corundum crucible and calcined in a tube furnace at 850°C under air atmosphere for 26 hours. After calcination, it was cooled at a rate of 3°C / min to obtain a calcined sample;

[0092] Among them, the chemical reaction for synthesizing europium-doped phosphate is:

[0093] 8(NH4)2HPO4+(1-x)Gd2O3+xEu2O3+Na2CO3→2NaEu x G (1-x) (PO3)4+16NH3+12H2O+CO2.

[0094] S4: The calcined sample obtained in S3 is washed with warm water and nitric acid to remove possible residual reactants, and a luminescent material for early warning type ray flexible protection is obtained. The general structural formula of the luminescent material for early warning type ray flexible protection is: 2NaEu x G (1-x) (PO3)4, of which Eu 3+ Relative to Gd 3+ The molar proportion is 1 to 100%.

[0095] Among them, the components of the mixed powder are oxides, (NH4)2HPO4 and Na2CO3. According to mass percentage, oxides account for 23-24%, (NH4)2HPO4 accounts for 69-70%, and Na2CO3 accounts for 7%. The oxides are Gd2O3 and Eu2O3, and Gd2O3 and Eu2O3 are mixed in a certain proportion.

[0096] Table 1 Composition and quality of luminescent materials for early warning ray flexible protection

[0097]

[0098] As shown in Table 1, the components and masses of the luminescent materials for early warning type ray flexible protection under different doping ratios of Examples 1 to 6 are shown. Examples 5 and 6 are prepared using the steps provided in Example 1. According to the preparation method of the luminescent material for early warning type ray flexible protection provided in Example 1, the calcined sample obtained in step S3 under the doping ratio in Example 1 is sampled, and the microstructure is observed using a scanning electron microscope, and a scanning electron microscope image is obtained as shown in FIG. Figure 1 As shown. Figure 1 It can be seen that NaGd(PO3)4:30%Eu prepared by high temperature solid phase method 3+ The phosphor particles are in the micron range and have block and rod-like morphologies.

[0099] The forged sample obtained in step S3 under the doping ratio in Example 1 was sampled and the phase structure was tested by XRD. The results are as follows: Figure 4 As shown. Figure 4 It can be seen that the prepared materials are all single-phase, which is consistent with the spectrum in the standard card PDF47-0657 NaGd(PO3)4. The diffraction peaks have a high matching degree and sharp peaks, indicating that the overall crystallinity of the samples is good. 3+ With the increase of doping ratio, the original diffraction peak position does not change, indicating that Eu 3+ The doping has no effect on the crystal structure of NaGd(PO3)4. Figure 2 and Figure 3 As shown, the NaGd(PO3)4 in Example 1 is homogeneous with the original NaGd(PO3)4, that is, most of the Gd 3+ Ions are Eu 3+ Ion substitution, NaGd(PO3)4:Eu 3+ The XRD spectrum of (1~100 mol%) is basically the same as that of NaGd(PO3)4.

[0100] The forged sample obtained in step S3 under the doping ratio in Example 1 was sampled and subjected to X-ray excitation spectrum test. The results are as follows: Figure 5 and Figure 6 As shown. Figure 5 It can be seen that NaGd(PO3)4:Eu 3+ Under X-ray excitation, the phosphor mainly shows Eu 3 + Excitation characteristic peak, corresponding to Eu 3+ From 5D0→7FJ (J=1, 2, 3, 4) excited state transition. Among them, the main peaks are located at 592nm and 614nm, 592nm corresponds to 5D0→7F1 magnetic dipole transition, 614nm corresponds to 5D0→7F2; in addition, lower signals are also observed at 652nm (5D0→7F3) and 698nm (5D0→7F4). With the increase of Eu 3+ As the doping concentration increases, the luminescence intensity first increases and then decreases; when Eu 3+ When the doping rate is 30 mol%, the luminescence intensity of the phosphor is the strongest; then, due to the quenching effect of the phosphor concentration, the luminescence intensity gradually decreases. Figure 6 NaGd(PO3)4:Eu under X-ray excitation in the dark 3+ The phosphor emits bright red light visible to the naked eye. These results show that NaGd(PO3)4:Eu 3+ Phosphors have potential application scenarios in radiation fields.

Claims

1. A luminescent material for early warning radiation flexible protection, characterized in that: The general structural formula of the luminescent material is: 2NaEu x G (1-x) (PO3)4, 2NaEu x G (1-x) (PO3)4 in Eu 3+ Relative to Gd 3+ The molar proportion is 1 to 100%.

2. The luminescent material for early warning radiation flexible protection according to claim 1 is characterized in that: 2NaEu x G (1-x) (PO3)4 in Eu 3+ Relative to Gd 3+ The molar proportion is 10 to 70%.

3. The luminescent material for early warning radiation flexible protection according to claim 1, characterized in that: 2NaEu x G (1-x) (PO3)4 in Eu 3+ Relative to Gd 3+ The molar proportion is 30 to 50%.

4. The method for preparing the luminescent material for early warning type flexible radiation protection according to claim 1, characterized in that: The specific steps are as follows: S1: Grind the mixed powder in an agate mortar to make it uniformly mixed. During grinding, anhydrous ethanol should be added until it can just immerse the mixture; S2: sending the mixed powder obtained in S1 to a drying oven for drying; S3: sending the dried powder from S2 into a corundum crucible, and calcining it in a tube furnace under air atmosphere to obtain a calcined sample; S4: The calcined sample obtained in S3 is washed with warm water and nitric acid to remove possible residual reactants, and a luminescent material for early warning ray flexible protection is obtained. The general structural formula of the luminescent material for early warning ray flexible protection is: 2NaEu x G (1-x) (PO3)4, of which Eu 3+ Relative to Gd 3+ The molar proportion is 1 to 100%.

5. The method for preparing the luminescent material for early warning type flexible radiation protection according to claim 4, characterized in that: The components of the mixed powder are oxide, (NH4)2HPO4 and Na2CO3. In terms of mass percentage, the oxide accounts for 23-24%, the (NH4)2HPO4 accounts for 69-70%, and the Na2CO3 accounts for 7%.

6. The method for preparing the luminescent material for early warning type flexible radiation protection according to claim 5, characterized in that: The oxides are Gd2O3 and Eu2O3, and the Gd2O3 and Eu2O3 are mixed in a certain proportion.

7. The method for preparing the luminescent material for early warning type flexible radiation protection according to claim 4, characterized in that: In S1, the grinding time is 50 to 70 minutes.

8. The method for preparing the luminescent material for early warning type flexible radiation protection according to claim 4, characterized in that: In S2, the drying temperature is 50-70°C and the time is 20-40 minutes.

9. The method for preparing the luminescent material for early warning type flexible radiation protection according to claim 4, characterized in that: In S3, the calcination temperature is 550-850° C., the calcination time is 22-26 hours, and the cooling rate after the calcination is 1-3° C. / min.

10. Application of the luminescent material for early warning flexible radiation protection as claimed in any one of claims 1 to 9 in biological protection of nuclear submarines, internal protection of nuclear-proof armored vehicles, radiation protection of special-shaped and complex structures of nuclear facilities, and radiation protection of special electronic components.

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