A green light force-induced luminescence material, its preparation method and application

Abstract

The present invention belongs to the technical field of solid luminescent materials, and particularly relates to a green light mechanoluminescent material, a preparation method thereof, and an application thereof. The present invention provides a green light mechanoluminescent material with the chemical formula Ca5Ga 6‑X Al X O 14 :Tb 3+ , where X = 0 to 1.6 and X is not 0. In the present invention, Al is doped into the Ca5Ga6O 14 :Tb 3+ material, and the obtained green light mechanoluminescent material has abundant traps. The high trap concentration and deep traps enable the material to be charged, store electrons, and generate mechanoluminescence under natural light. The green light mechanoluminescent material of the present invention does not require pre-irradiation, has a high mechanoluminescence intensity, high sensitivity, and a long mechanoluminescence time and good stability under non-charging conditions.

Description

Technical Field

[0001] The present invention belongs to the technical field of solid luminescent materials, and particularly relates to a green light force-induced luminescent material, a preparation method thereof, and an application thereof. Background Art

[0002] Force-induced luminescent materials have been widely studied in recent years. By applying pressure, friction, or other forms of force to the materials, the materials can emit light. This kind of luminescent material excited by force is an energy-saving green intelligent material. However, the current force-induced luminescent materials have low luminescence intensity, low sensitivity, and poor stability, and need to be pre-irradiated with ultraviolet rays or X-rays for energy storage before force-induced luminescence can be generated, which seriously hinders the development and application of force-induced luminescent materials. Summary of the Invention

[0003] In view of this, the purpose of the present invention is to provide a green light force-induced luminescent material, a preparation method thereof, and an application thereof. The green light force-induced luminescent material of the present invention does not require pre-irradiation, has high force-induced luminescence intensity, high sensitivity, and long force-induced luminescence time and good stability under the condition of no energy storage.

[0004] The present invention provides a green light force-induced luminescent material with the chemical formula Ca 5 Ga 6-X Al X O 14 :Tb 3+ , where X = 0 to 1.6 and X is not 0.

[0005] Preferably, the X = 0.8 to 1.6.

[0006] The present invention also provides a preparation method of the green light force-induced luminescent material according to the above technical solution, comprising the following steps:

[0007] Mix and calcine H 3 BO 3 , Al 2 O 3 , CaCO 3 , Ga 2 O 3 and Tb 4 O 7 to obtain the green light force-induced luminescent material

[0008] Preferably, the H 3 BO 3 , Al 2 O 3 , CaCO 3 , Ga 2 O 3 and Tb 4 O 7The molar ratio is (0.001~0.003): (0.1~0.8): (4.5~5.5): (2.2~2.9): (0.01~0.09).

[0009] The present invention also provides an application of the green light mechanoluminescent material described in the above technical solution or the green light mechanoluminescent material obtained by the above preparation method in crack detection.

[0010] The present invention also provides a mechanoluminescent composite material, comprising raw materials in the following parts by mass:

[0011] 3~5 parts of green light mechanoluminescent material, 5~7 parts of molding agent and 0.9~1.1 parts of curing agent;

[0012] The green light mechanoluminescent material is the green light mechanoluminescent material described in the above technical solution or the green light mechanoluminescent material obtained by the above preparation method.

[0013] Preferably, the molding agent includes polydimethylsiloxane and / or epoxy resin.

[0014] The present invention also provides a preparation method of the mechanoluminescent composite material described in the above technical solution, comprising the following steps:

[0015] Mix the green light mechanoluminescent material, the molding agent and the curing agent and cure them to obtain the mechanoluminescent composite material.

[0016] Preferably, the temperature of the curing is 65~75 °C and the time is 40~60 minutes.

[0017] Compared with the prior art, the present invention has the following beneficial effects:

[0018] The present invention provides a green light mechanoluminescent material with the chemical formula Ca 5 Ga 6-X Al X O 14 :Tb 3+ , where X = 0~1.6 and X is not 0. In the present invention, Al is doped into the Ca 5 Ga 6 O 14 :Tb 3+ material, and the obtained green light mechanoluminescent material has abundant traps. The high trap concentration and deep traps enable the material to be charged, store electrons and generate mechanoluminescence under natural light. The green light mechanoluminescent material of the present invention does not require pre-irradiation, has high mechanoluminescence intensity, high sensitivity, and long mechanoluminescence time and good stability under the condition of no charging.

[0019] The data of the examples show that the mechanoluminescent material of the present invention can still exhibit obvious mechanoluminescence after being exposed to an air environment in the dark for up to fifteen days, and has a continuous mechanoluminescence of up to 0.183 seconds under instantaneous tensile stress testing. The mechanoluminescent material of the present invention has high stability and excellent optical properties, and can still produce obvious mechanoluminescence under a force of 5 N when applied to crack detection. The present invention provides new ideas and methods for the development of new green intelligent materials. Description of the Drawings

[0020] In order to more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the following will briefly introduce the drawings required for use in the embodiments. Obviously, the drawings in the following description are only some embodiments of the present invention. For those of ordinary skill in the art, without creative efforts, other drawings can also be obtained based on these drawings.

[0021] Figure 1 XRD diffraction patterns of the materials of Comparative Example 1 and Examples 1 to 5;

[0022] Figure 2 SEM image of the material of Example 4;

[0023] Figure 3 Luminescence intensities of the materials of Comparative Example 1 and Examples 2 to 5 under the same applied force;

[0024] Figure 4 Practical diagrams of the stability tests of the materials of Comparative Example 1 and Example 4;

[0025] Figure 5 Luminescence intensity and spectrogram of the composite material of Application Example 1 under 2 - 6 N;

[0026] Figure 6 Practical diagram of the luminescence intensity of the composite material of Application Example 1 under 2 - 6 N;

[0027] Figure 7 Schematic diagram of the application of the composite material of Application Example 1 to crack detection. Detailed Description of the Invention

[0028] The present invention provides a green mechanoluminescent material with the chemical formula Ca 5 Ga 6-X Al X O 14 :Tb 3+ , where X = 0 - 1.6 and X is not 0.

[0029] In the present invention, unless otherwise specified, the materials and equipment used are commercially available products in the art.

[0030] In the present invention, preferably X = 0.8 - 1.6, specifically it can be 0.2, 0.4, 0.8, 1.2 or 1.6. For the green light mechanoluminescent material obtained within the range of X value described in the present invention, the mechanoluminescence intensity is high and the stability is excellent.

[0031] In the present invention, the chemical formula of the green light mechanoluminescent material is preferably Ca 5 Ga 6-X Al X O 14 :0.06Tb 3+ , where X = 0.2, 0.4, 0.8, 1.2 or 1.6.

[0032] The green light mechanoluminescent material of the present invention is an Al 2 O 3 -doped Ca 5 Ga 6 O 14 :Tb 3+ material. The doping of alumina improves the luminescence intensity and stability of the material. It can generate mechanoluminescence without pre-irradiation charging and can still have obvious mechanoluminescence phenomenon after being exposed to the air environment in the dark for up to fifteen days. The green light mechanoluminescent material is a columnar crystal.

[0033] The present invention also provides a preparation method of the green light mechanoluminescent material described in the above technical solution, including the following steps:

[0034] Mix and calcine H 3 BO 3 , Al 2 O 3 , CaCO 3 , Ga 2 O 3 and Tb 4 O 7 to obtain the green light mechanoluminescent material.

[0035] In the present invention, the molar ratio of H 3 BO 3 to CaCO 3 is preferably (0.001 - 0.003):(4.5 - 5.5), specifically it can be 0.002:5. The H 3 BO 3 is a cosolvent, which can reduce the calcination (sintering) temperature.

[0036] In the present invention, the Al 2 O 3 and CaCO 3The molar ratio of is preferably (0.1~0.8):(4.5~5.5), specifically it can be 0.1:5, 0.2:5, 0.4:5, 0.6:5 or 0.8:5. The Al 2 O 3 can adjust the trap concentration of the material, increase the ability of the material to store electrons, and improve the luminescence intensity and stability of the material.

[0037] In the present invention, the molar ratio of CaCO 3 to Ga 2 O 3 is preferably (4.5~5.5):(2.2~2.9), specifically it can be 5:3. The CaCO 3 and Ga 2 O 3 are the main matrix for preparing the green light-induced luminescence material.

[0038] In the present invention, the molar ratio of Tb 4 O 7 to CaCO 3 is preferably (0.01~0.09):(4.5~5.5), specifically it can be 0.03:5. The Tb 4 O 7 in the Tb 3+ provides luminescent ions for the green light-induced luminescence material.

[0039] In the present invention, the molar ratio of H 3 BO 3 , Al 2 O 3 , CaCO 3 , Ga 2 O 3 and Tb 4 O 7 is preferably (0.001~0.003):(0.1~0.8):(4.5~5.5):(2.2~2.9):(0.01~0.09), specifically it can be 0.002:0.1:5:2.9:0.03, 0.002:0.2:5:2.8:0.03, 0.002:0.4:5:2.6:0.03, 0.002:0.6:5:2.4:0.03 or 0.002:0.8:5:2.2:0.03.

[0040] In the present invention, before calcination, it is preferably further included to combine H 3 BO 3 , Al 2 O 3 , CaCO 3 , Ga2 O 3 and Tb 4 O 7 are ground together. The grinding is preferably carried out in an agate mortar; the particle size of the powder after grinding is preferably not greater than 0.075 mm (passing through a 200-mesh sieve).

[0041] In the present invention, the calcination temperature is preferably 1150 - 1250 °C, specifically it can be 1200 °C, and the heat preservation time is preferably 3 - 5 hours, specifically it can be 4 hours. The heating rate from room temperature to the calcination temperature is preferably 5 - 7 °C / min, specifically it can be 6 °C / min. The present invention preferably places H 3 BO 3 、Al 2 O 3 、CaCO 3 、Ga 2 O 3 and Tb 4 O 7 powders in an alumina crucible and conducts the calcination in a box furnace. During the calcination, Ca 5 Ga 6 O 14 :Tb 3+ is synthesized, and at the same time, part of Al 3+ substitutes for Ga 3+ . After the calcination, it preferably further includes cooling, and the cooling is preferably furnace cooling.

[0042] The present invention also provides the application of the green light mechanoluminescent material described in the above technical solution or the green light mechanoluminescent material obtained by the above preparation method in crack detection.

[0043] The present invention also provides a mechanoluminescent composite material, which comprises the following raw materials in parts by mass:

[0044] 3 - 5 parts of green light mechanoluminescent material, 5 - 7 parts of molding agent, and 0.9 - 1.1 parts of curing agent;

[0045] The green light mechanoluminescent material is the green light mechanoluminescent material described in the above technical solution or the green light mechanoluminescent material obtained by the above preparation method.

[0046] In the present invention, the molding agent preferably includes polydimethylsiloxane (PDMS) and / or epoxy resin, and more preferably polydimethylsiloxane. The molding agent forms the green light mechanoluminescent powder material. With polydimethylsiloxane as the molding agent in the present invention, the composite material can produce obvious mechanoluminescence under a relatively small acting force.

[0047] In the present invention, the curing agent is preferably the curing agent in Dow Corning DC184 silicone rubber from the United States. The curing agent promotes the material to form. In the embodiments of the present invention, the forming agent and the curing agent used are Dow Corning DC184 silicone rubber from the United States (including PDMS matrix and curing agent).

[0048] In the present invention, the force-induced luminescence composite material preferably comprises the following raw materials in parts by mass: 4 parts of green light force-induced luminescence material, 6 parts of forming agent and 1 part of curing agent.

[0049] The present invention also provides a preparation method of the force-induced luminescence composite material described in the above technical solution, comprising the following steps:

[0050] Mix the green light force-induced luminescence material, the forming agent and the curing agent and cure them to obtain the force-induced luminescence composite material.

[0051] In the present invention, the curing temperature is preferably 65 - 75 °C, specifically it can be 70 °C, and the time is preferably 40 - 60 minutes, specifically it can be 50 minutes. The present invention preferably places the green light force-induced luminescence material, the forming agent and the curing agent in a polytetrafluoroethylene mold and cures them by heating in an oven.

[0052] The present invention applies the composite material to crack detection. Before the composite material is broken, a force is applied, and the force is evenly distributed, making it difficult to generate force-induced luminescence. However, when microcracks occur in the material, after applying the same acting force again, the acting force on the crack is larger due to uneven force distribution, and strong force-induced luminescence will be generated to achieve crack detection.

[0053] To further illustrate the present invention, the following describes in detail the green light force-induced luminescence material provided by the present invention, its preparation method and application with reference to the drawings and embodiments, but they cannot be understood as limiting the protection scope of the present invention.

[0054] Comparative Example 1

[0055] A preparation method of an efficient green light force-induced luminescence material (without adding Al 2 O 3 ) is as follows:

[0056] Mix the raw materials H 3 BO 3 , Al 2 O 3 , CaCO 3 , Ga 2 O 3 and Tb 4 O 7Put them in an agate mortar according to the molar ratio of 0.002:0:5:3:0.03, grind for 30 minutes to mix evenly, then put them into an alumina crucible, cover it and place it in a box furnace, and sinter at 1200 °C for 4 hours, and then cool down with the furnace to obtain the mechanoluminescent material.

[0057] The mechanoluminescent material obtained in Comparative Example 1 has the chemical formula Ca 3 Ga 4 O 9 : 0.06Tb 3+ .

[0058] Example 1

[0059] The difference from Comparative Example 1 is that the molar ratio of H 3 BO 3 , Al 2 O 3 , CaCO 3 , Ga 2 O 3 and Tb 4 O 7 is 0.002:0.1:5:2.9:0.03, and the remaining steps are the same as those in Comparative Example 1.

[0060] The mechanoluminescent material obtained in Example 1, Ca 5 Ga 6-X Al X O 14 :0.06Tb 3+ , where X = 0.2.

[0061] Example 2

[0062] The difference from Comparative Example 1 is that the molar ratio of H 3 BO 3 , Al 2 O 3 , CaCO 3 , Ga 2 O 3 and Tb 4 O 7 is 0.002:0.2:5:2.8:0.03, and the remaining steps are the same as those in Comparative Example 1.

[0063] The mechanoluminescent material obtained in Example 2, Ca 5 Ga 6-X Al X O 14 :0.06Tb 3+ , where X = 0.4.

[0064] Example 3

[0065] The difference from Comparative Example 1 is that the molar ratio of H 3 BO 3 to Al 2 O 3 to CaCO 3 to Ga 2 O 3 to Tb 4 O 7 is 0.002: 0.4: 5: 2.6: 0.03, and the remaining steps are the same as those in Comparative Example 1.

[0066] The mechanoluminescent material obtained in Example 3 is Ca 5 Ga 6-X Al X O 14 :0.06Tb 3+ , where X = 0.8.

[0067] Example 4

[0068] The difference from Comparative Example 1 is that the molar ratio of H 3 BO 3 to Al 2 O 3 to CaCO 3 to Ga 2 O 3 to Tb 4 O 7 is 0.002: 0.6: 5: 2.4: 0.03, and the remaining steps are the same as those in Comparative Example 1.

[0069] The mechanoluminescent material obtained in Example 4 is Ca 5 Ga 6-X Al X O 14 :0.06Tb 3+ , where X = 1.2.

[0070] Example 5

[0071] The difference from Comparative Example 1 is that the molar ratio of H 3 BO 3 to Al 2 O 3 to CaCO 3 to Ga 2 O 3 to Tb 4 O 7 is 0.002: 0.8: 5: 2.2: 0.03, and the remaining steps are the same as those in Comparative Example 1.

[0072] The stress luminescence material obtained in Example 5, Ca 5 Ga 6-X Al X O 14 :0.06Tb 3+ , where X = 1.6.

[0073] Performance characterization:

[0074] Figure 1 The XRD diffraction patterns of the materials of Comparative Example 1 and Examples 1 to 5 are shown. By increasing the doping amount of Al 3+ ions, the transformation from Ca 3 Ga 4 O 9 to Ca 5 Ga 6 O 16 is achieved. The incorporation of Al changes the crystal form, and some Al ions replace the gallium ions.

[0075] Figure 2 The SEM image of the material of Example 4 is shown. It can be seen from the figure that this material is columnar crystals.

[0076] Figure 3 The spectrograms of the materials of Comparative Example 1 and Examples 2 to 5 under the same tensile force of 5 N are shown. From bottom to top, they are Comparative Example 1 (gray), Example 2 (blue), Example 3 (red), Example 5 (yellow), and Example 4 (green); the abscissa in the inset corresponds to the doping amount of Al 3+ ions, and the ordinate corresponds to the relative intensity at a wavelength of 544 nm. It can be seen from the figure that the main peak of the spectrum is located at 544 nm, belonging to green light emission, indicating that the stress luminescence intensity of the material is significantly improved after doping with Al 2 O 3 . When the doping amount is X = 1.2 mol Al 3+ , the stress luminescence performance is the best.

[0077] Figure 4 The physical pictures of Comparative Example 1 and the material of Example 4 in a ceramic mortar, continuously sliding tested with a glass rod in a dark environment for 15 days are shown. The results show that the stress luminescence of the material of Example 4 is very obvious, and it can still produce stress luminescence after being placed in the dark for 15 days without charging, indicating that the material has very excellent stability, and the stress luminescence performance is significantly improved compared with Comparative Example 1 without doping Al 3+ .

[0078] Application Example 1

[0079] The mechanoluminescent material of Example 4, polydimethylsiloxane (PDMS) and curing agent are fully mixed in a mass ratio of 4: 6: 1 and put into a mold, and then heated at a constant temperature of 70° C. in an oven for 50 minutes to cure and form a mechanoluminescent composite material, which is then applied to crack detection.

[0080] Figure 5 The figure is a test diagram of the mechanoluminescence performance of the composite material in Application Example 1; the small figure is the mechanoluminescence spectrum of the composite material under different forces, from bottom to top, they are the spectra corresponding to 2N~6N. It can be seen from the figure that the main peak of mechanoluminescence is at 544 nanometers, which belongs to Tb 3+ The luminescence of ions gradually increases with increasing the applied tensile stress intensity (2N~6N), and strong mechanoluminescence is exhibited under a tensile force of 6N.

[0081] Figure 6 This is a photo of the mechanoluminescent composite material in Application Example 1. As can be seen from the figure, the mechanoluminescence becomes more obvious as the force increases, and the mechanoluminescence duration reaches 0.183 seconds when the mechanoluminescent composite material is stretched once under a force of 5N.

[0082] Figure 7 This is a scene diagram of the application of mechanoluminescent composite materials for crack detection in Application Example 1. Before the composite material is broken, the force is uniform, and it is difficult to produce mechanoluminescence when a force of 5N is applied. However, after the material has microcracks, when a force of 5N is applied again, the force on the crack is larger due to the uneven force, which will produce strong mechanoluminescence and realize crack detection.

[0083] The present invention is achieved by 5 Ga 6 O 14 :Tb 3+ Al doped 2 O 3 The mechanoluminescent material of the present invention has high mechanoluminescence intensity and excellent stability, and the preparation method of the present invention is simple. The mechanoluminescent material of the present invention has very sensitive mechanoluminescence in the powder state and in the composite state with PDMS. The composite material is applied to crack detection and can generate obvious mechanoluminescence under a force of 5N.

[0084] Although the above-mentioned embodiments have made a detailed description of the present invention, they are only some embodiments of the present invention, rather than all embodiments. People can also obtain other embodiments based on the embodiments of the present invention without creative work, and these embodiments all fall within the scope of protection of the present invention.

Claims

1. A green light mechanoluminescent material, characterized in that: The chemical formula is Ca5Ga 6-X Al X O 14 :Tb 3+ , where X=1.

2.

2. The method for preparing the green light mechanoluminescent material according to claim 1, characterized in that: The following steps are involved: H3BO3, Al2O3, CaCO3, Ga2O3 and Tb4O7 are mixed and calcined to obtain the green light electroluminescent material.

3. The preparation method according to claim 2, characterized in that: The calcination temperature is 1150-1250° C., and the heat preservation time is 3-5 hours.

4. The preparation method according to claim 2 or 3, characterized in that: The molar ratio of H3BO3, Al2O3, CaCO3, Ga2O3 and Tb4O7 is (0.001~0.003):(0.1~0.8):(4.5~5.5):(2.2~2.9):(0.01~0.09).

5. Use of the green mechanoluminescent material according to claim 1 or the green mechanoluminescent material obtained by the preparation method according to any one of claims 2 to 4 in crack detection.

6. A mechanoluminescent composite material, characterized in that: Including the following raw materials by mass: 3-5 parts of green light luminescent material, 5-7 parts of molding agent and 0.9-1.1 parts of curing agent; The green mechanoluminescent material is the green mechanoluminescent material according to claim 1 or the green mechanoluminescent material obtained by the preparation method according to any one of claims 2 to 4.

7. The mechanoluminescent composite material according to claim 6, characterized in that: The molding agent includes polydimethylsiloxane and / or epoxy resin.

8. The method for preparing the mechanoluminescent composite material according to claim 6 or 7, characterized in that: The following steps are involved: The green light mechanoluminescent material, the molding agent and the curing agent are mixed and cured to obtain the mechanoluminescent composite material.

9. The preparation method according to claim 8, characterized in that: The curing temperature is 65-75° C. and the curing time is 40-60 minutes.

Images