Mechanoluminescent material as well as preparation method and application thereof

Abstract

The invention discloses a mechanoluminescent material as well as a preparation method and application thereof. The chemical formula of the mechanoluminescent material is Y3Al2Ga3O12: xBi, x is equal to 0.001-0.015, Y3Al2Ga3O12 is a matrix, and a doped ion Bi < 3 + > is an active ion. The preparation method of the material comprises the following steps: mixing raw materials including an yttrium-containing compound, an aluminum-containing compound, a gallium-containing compound, a bismuth-containing compound and boric acid according to a ratio, and sintering through a high-temperature solid-phase method. The mechanoluminescent material disclosed by the invention can realize zero-background visual light signal response under indoor light, so that the mechanoluminescent material is used for visual stress detection under a bright field environment; the preparation method is wide in raw material source, low in cost, simple in preparation process and easy to implement industrially. In addition, the material has high luminous intensity and signal-to-noise ratio under the action of mechanical stress, the application form can be adjusted as required, and the flexibility and adaptability are high.

Description

Technical Field

[0001] This application belongs to the field of luminescent materials, and particularly relates to a stress-induced luminescent material, a preparation method thereof, and an application thereof. Background Art

[0002] Stress-induced luminescence is a special luminescence phenomenon, which refers to the conversion of energy into light under the action of different mechanical stresses (such as friction, impact, compression, tension, bending, torsion, grinding, etc.). Due to its remote sensing and self-powered characteristics, stress-induced luminescent materials have attracted extensive attention in the field of mechanical sensing.

[0003] At present, a large number of stress-induced luminescent materials have been developed by scientific researchers, and most of their emission wavelengths are concentrated in the visible light region (400 - 650 nm). However, these visible light band stress-induced luminescent materials cannot meet the stress detection requirements in a bright field environment due to insufficient brightness. This severely limits the application of stress-induced luminescent materials in daily life. Although scientific researchers have made great efforts to improve the stress-induced luminescence intensity, due to the large overlap between the visible light band and the solar spectrum band, it is always difficult to obtain a satisfactory signal-to-noise ratio for stress-induced luminescent materials in this band in a bright field environment. Compared with the visible light band, the infrared light band has less overlap with the solar spectrum. In view of this, materials with emission wavelengths in the infrared region (the near-infrared (NIR) wavelength range is 700 - 2500 nm, the mid-infrared (MIR) band range is 2500 - 25000 nm, and the far-infrared (FIR) wavelength range is 25000 - 1000000 nm) are expected to solve the signal-to-noise ratio problem of stress-induced luminescent materials in a bright field environment, thereby realizing stress detection in a bright field environment. Summary of the Invention

[0004] To solve at least one of the above problems, this application aims to provide a stress-induced luminescent material with a stable structure and an emission wavelength in the near-infrared region. This stress-induced luminescent material can achieve a zero-background visual response in an indoor light environment, and thus can be used for visual stress detection in a bright field environment.

[0005] According to one aspect of this application, a stress-induced luminescent material is provided. The chemical formula of the stress-induced luminescent material is Y3Al2Ga3O 12 :xBi, where x = 0.001 - 0.015;

[0006] Among them, Y3Al2Ga3O 12 is the matrix, and the doped ion Bi 3+ is the activator ion.

[0007] Optionally, the stress-induced luminescent wavelength of the stress-induced luminescent material is located at 650 - 950 nm, and the stress-induced luminescence peak is located at 715 nm.

[0008] Optionally, the upper limit of the mechanoluminescence wavelength of the mechanoluminescent material is independently selected from 950 nm, 932 nm, 914 nm, 896 nm, 878 nm, 860 nm, 842 nm, 824 nm, 806 nm, 788 nm, 770 nm, 752 nm, 734 nm, and 716 nm, and the lower limit is independently selected from 714 nm, 706 nm, 698 nm, 690 nm, 682 nm, 674 nm, 666 nm, 658 nm, and 650 nm.

[0009] Optionally, in the chemical formula, x is independently any value selected from 0.001, 0.002, 0.003, 0.004, 0.005, 0.006, 0.007, 0.008, 0.009, 0.010, 0.011, 0.012, 0.013, 0.014, and 0.015 or a range value between any two of them.

[0010] Optionally, in the chemical formula, x = 0.006 - 0.008.

[0011] Preferably, in the chemical formula, x = 0.007.

[0012] According to another aspect of the present application, a method for preparing the mechanoluminescent material as described above is provided, including:

[0013] Mixing raw materials including a yttrium-containing compound, an aluminum-containing compound, a gallium-containing compound, a bismuth-containing compound, and boric acid according to the ratio of the chemical formula, and sintering by a high-temperature solid-phase method to obtain the mechanoluminescent material.

[0014] Optionally, the method includes the following steps:

[0015] a) Mixing the raw materials, adding ethanol, and grinding for 0.2 - 2 h;

[0016] b) Sintering and cooling the mixture obtained in step a) to obtain the mechanoluminescent material.

[0017] Optionally, the grinding time is independently any value selected from 0.2 h, 0.25 h, 0.3 h, 0.35 h, 0.4 h, 0.45 h, 0.5 h, 0.55 h, 0.6 h, 0.65 h, 0.7 h, 0.75 h, 0.8 h, 0.85 h, 0.9 h, 0.95 h, 1.0 h, 1.1 h, 1.2 h, 1.3 h, 1.4 h, 1.5 h, 1.6 h, 1.7 h, 1.8 h, 1.9 h, and 2.0 h or a range value between any two of them.

[0018] Optionally, in step a), the volume ratio of the ethanol to the raw material is 1:0.8 - 1:1.2.

[0019] Optionally, in step a), the volume ratio of the ethanol to the raw material is independently any value selected from 1:0.8, 1:0.85, 1:0.9, 1:0.95, 1:1, 1:1.05, 1:1.1, 1:1.15, and 1:1.2 or a range value between any two of them.

[0020] In one embodiment, the ethanol and the raw material are added in equal volumes.

[0021] Optionally, the ethanol is anhydrous ethanol.

[0022] Optionally, in step b), the sintering temperature is 1450 - 1600 °C.

[0023] Optionally, in step b), the sintering temperature is independently any value selected from 1450 °C, 1460 °C, 1470 °C, 1480 °C, 1490 °C, 1500 °C, 1510 °C, 1520 °C, 1530 °C, 1540 °C, 1550 °C, 1560 °C, 1570 °C, 1580 °C, 1590 °C, and 1600 °C or a range value between any two of them.

[0024] Optionally, in step b), the sintering time is 3.0 - 8.0 h.

[0025] Optionally, in step b), the sintering time is independently any value selected from 3.0 h, 3.5 h, 4.0 h, 4.5 h, 5.0 h, 5.5 h, 6.0 h, 6.5 h, 7.0 h, 7.5 h, and 8.0 h or a range value between any two of them.

[0026] Optionally, in step b), the sintering is carried out in an air atmosphere.

[0027] According to the present application, the boric acid is used as a cosolvent. The present application has no particular limitation on the amount of boric acid, as long as it can enable other raw materials to be fully mixed and dispersed.

[0028] Optionally, the amount of boric acid is 2.0 - 4.0 mol%, based on the total molar amount of the raw materials.

[0029] Optionally, the amount of boric acid is independently any value selected from 2.0 mol%, 2.1 mol%, 2.2 mol%, 2.3 mol%, 2.4 mol%, 2.5 mol%, 2.6 mol%, 2.7 mol%, 2.8 mol%, 2.9 mol%, 3.0 mol%, 3.1 mol%, 3.2 mol%, 3.3 mol%, 3.4 mol%, 3.5 mol%, 3.6 mol%, 3.7 mol%, 3.8 mol%, 3.9 mol% and 4.0 mol%, or a range value between any two of them, based on the total number of moles of the raw materials.

[0030] Preferably, the amount of boric acid is 2.8 - 3.2 mol%, based on the total number of moles of the raw materials.

[0031] Optionally, the yttrium-containing compound is yttrium oxide Y2O3.

[0032] Optionally, the aluminum-containing compound is aluminum oxide Al2O3.

[0033] Optionally, the gallium-containing compound is gallium oxide Ga2O3.

[0034] Optionally, the bismuth-containing compound is gadolinium oxide Bi2O3.

[0035] In the stress-luminescent material Y3Al2Ga3O 12 :xBi according to the present application, the doped ion Bi 3+ acts as a luminescence center.

[0036] According to another aspect of the present application, there is provided a stress-luminescent composite, comprising the stress-luminescent material as described above and a transparent polymer.

[0037] Optionally, the method for preparing the stress-luminescent composite comprises: mixing the powder of the stress-luminescent material and the transparent polymer, and then curing in a mold.

[0038] Optionally, the mass ratio of the stress-luminescent material powder to the transparent polymer is 1:1 - 2:1.

[0039] Optionally, the mass ratio of the stress-luminescent material powder to the transparent polymer is independently any value selected from 1.0:1, 1.1:1, 1.2:1, 1.3:1, 1.4:1, 1.5:1, 1.6:1, 1.7:1, 1.8:1, 1.9:1 and 2.0:1, or a range value between any two of them.

[0040] Optionally, the curing temperature is 60 - 100 °C.

[0041] Optionally, the curing temperature is independently any value selected from 60°C, 65°C, 70°C, 75°C, 80°C, 85°C, 90°C, 95°C, and 100°C or a range value between any two of them.

[0042] In some embodiments of the present application, the morphology of the mechanoluminescent complex is determined according to the expected usage mode. For example, the mechanoluminescent complex can be directly made into the form of a structural member and used as an inherent component in a product; alternatively, the mechanoluminescent complex can be made into the form of a thin film and used in combination with the product as an additional component.

[0043] Optionally, the mechanoluminescent complex is in the form of a bulk elastomer, a columnar elastomer, or a thin film. Here, the present application has no particular limitation on the shape of the elastomer, and the above are only examples.

[0044] Optionally, the mechanoluminescent complex is a mechanoluminescent film.

[0045] Optionally, the transparent polymer is at least one selected from polyurethane, silica gel, and polydimethylsiloxane, preferably polydimethylsiloxane (PDMS).

[0046] According to another aspect of the present application, there is provided the use of the mechanoluminescent material or the mechanoluminescent complex as described above in stress detection in a bright field environment.

[0047] In one embodiment, the mechanoluminescent material or the mechanoluminescent complex is made into a sticky mechanoluminescent film and wrapped around a flexible hose for standby.

[0048] In a specific embodiment, the mechanoluminescent material is prepared by the following steps:

[0049] Mechanoluminescent material Y3Al2Ga3O 12 :xBi

[0050] Accurately weigh the raw materials of analytical pure Y2O3, Al2O3, Ga2O3, and Bi2O3 according to the molar ratio of 3:2:3:x (where 0.001 ≤ x ≤ 0.015), and add an appropriate amount of boric acid. Add the same volume of anhydrous ethanol to an agate mortar, and grind the raw materials for more than half an hour to make them evenly mixed. Then, place the obtained mixture in an alumina crucible, put it into a high-temperature furnace, heat it to 1450 - 1600°C and keep it warm for 3 - 8 hours, and then take it out after cooling to room temperature and grind it to obtain the Y3Al2Ga3O 12 :xBi series of mechanoluminescent materials.

[0051] In a specific embodiment, the mechanoluminescent film is prepared by the following steps:

[0052] The Y3Al2Ga3O 12 :0.007 Bi stress - induced luminescence material powder and a transparent polymer (which can be polyurethane, silica gel, polydimethylsiloxane, etc., and polydimethylsiloxane PDMS is used here) are mixed at a mass ratio of 1:1 - 2:1 and stirred for 10 minutes, then poured into a mold and placed in an oven, and cured and heat - insulated at 60 - 80 °C. After curing, the obtained stress - induced luminescence film is taken out. The prepared stress - induced luminescence film is evenly wrapped on a flexible plastic hose for subsequent visual stress detection in a bright - field environment.

[0053] The beneficial effects that this application can produce include:

[0054] 1) The stress - induced luminescence material of this application has an emission wavelength in the near - infrared region, and can achieve a visual light - signal response with zero background under indoor light environment, so it can be used for visual stress detection in a bright - field environment.

[0055] 2) The preparation method of the stress - induced luminescence material of this application has wide raw material sources, low cost, simple preparation process, easy industrial implementation, and strong controllability.

[0056] 3) The stress - induced luminescence material of this application has high luminescence intensity and signal - to - noise ratio under mechanical stress, is less affected by ambient light, and can adjust the application form according to needs, with strong flexibility and adaptability. Description of the Drawings

[0057] Figure 1 It is the X - ray diffraction spectrum of a typical sample of the stress - induced luminescence material in Example 1.

[0058] Figure 2 It is the stress - induced luminescence spectrum of the stress - induced luminescence film prepared from the stress - induced luminescence material in Example 1.

[0059] Figure 3 It is the stress - response infrared luminescence photo of a typical sample of the stress - induced luminescence film prepared in Example 2. Detailed Embodiments

[0060] To make the purpose, technical solutions and advantages of this application clearer, the following will describe this application through specific embodiments. Obviously, the described embodiments are only a part of the embodiments of this application, rather than all embodiments. Based on the embodiments in this application, all other embodiments obtained by those of ordinary skill in the art without creative efforts belong to the scope protected by this application.

[0061] The experimental methods without specific conditions noted in the following embodiments are usually carried out according to conventional conditions or according to the conditions recommended by the manufacturer.

[0062] Unless otherwise specified, the raw materials and reagents used in the examples of this application are purchased through commercial channels and used directly without treatment.

[0063] The instruments and methods used for analysis in the examples of this application are as follows:

[0064] X-ray diffraction uses [X-ray powder diffractometer, Rigaku, Japan, Rigaku-miniflex600, using Cu target Kα radiation (λ = 0.154 nm) as the excitation source, the working current and voltage are 30 mA and 15 kV respectively, the scanning mode is continuous scanning, the step size is 0.02°, the scanning rate is 10° / min, and the 2θ range is selected from 5 to 80°].

[0065] Mechanoluminescence spectrum uses [fiber optic spectrometer, Ocean Optics, QEPro, integration time 5 s].

[0066] Infrared photography uses [indoor infrared camera, Hikvision, MV-CH250-90GN].

[0067] Example 1

[0068] Accurately weigh the raw materials of analytical pure Y2O3, Al2O3, Ga2O3 and Bi2O3 according to the molar ratio of 3:2:3:x, where x is set to 0.001, 0.003, 0.005, 0.007, 0.009, 0.011, 0.013 and 0.015 respectively, and then add 3 mol% boric acid as a cosolvent. Place the above raw materials in an agate mortar, add the same volume of anhydrous ethanol, grind for more than half an hour to make them evenly mixed, then transfer to an alumina crucible, put it into a high-temperature furnace and heat to 1580 °C and keep it warm for 5 hours. Then, cool the obtained product to room temperature with the furnace, take it out and grind it to obtain the mechanoluminescent material Y3Al2Ga3O 12 :xBi (x is 0.001, 0.003, 0.005, 0.007, 0.009, 0.011, 0.013, 0.015) powder samples.

[0069] Example 2

[0070] Mix the mechanoluminescent material powder samples prepared in Example 1 with polydimethylsiloxane (corresponding chemical formula (C2H6OSi) n ) in a mass ratio of 1:1, stir evenly, pour it into a mold and place it in an oven to cure at 70 °C. After curing, take out the prepared mechanoluminescent film sample for standby.

[0071] Experimental Example 1

[0072] Perform X-ray diffraction test on the mechanoluminescent material powder samples prepared in Example 1. Figure 1shows a partial typical sample Y3Al2Ga3O in Example 1 12 : X-ray diffraction pattern of 0.001 / 0.003 / 0.007 Bi. From Figure 1 it can be seen that compared with JCPDS No. 75-0556 (corresponding to the inorganic substance Y3Al2Ga3O 12 ), the diffraction peak positions of the synthesized samples after doping did not change significantly, indicating that the prepared samples are all pure phases.

[0073] Experimental Example 2

[0074] Perform a force-induced luminescence spectrum test on the force-induced luminescence film samples prepared from each of the force-induced luminescence material powders (Y3Al2Ga3O 12 : xBi, where x is 0.001, 0.003, 0.005, 0.007, 0.009, 0.011, 0.013, 0.015) in Example 1 (the force-induced luminescence spectrum was tested using an Ocean Optics fiber optic spectrometer QEPro. The tensile test was carried out using a Shimadzu AGS-X 50N mechanical testing machine under dark conditions, with a tensile speed of 10 mm / s and a tensile force of 10 N. At the same time, the fiber optic spectrometer was used to record the force-induced luminescence spectrum, and the integration time was 5 s), and the results are as Figure 2 shown. From Figure 2 it can be seen that the force-induced luminescence peaks shown by each force-induced luminescence film sample are all located at 715 nm, indicating that the force-induced luminescence materials corresponding to these film samples all belong to near-infrared region luminescence materials. From Figure 2 it can also be seen that when x approaches 0.007, the force-induced luminescence intensity of the force-induced luminescence material is relatively high.

[0075] Experimental Example 3

[0076] Wrap each of the force-induced luminescence film samples prepared in Example 2 evenly on a flexible plastic hose, and then perform a visualization stress response luminescence test under a bright field environment. Figure 3 shows a photograph of the test results of the typical sample Y3Al2Ga3O 12 : 0.007 Bi. As Figure 3 shown, under natural light, inflating causes the part of the hose wrapped with the force-induced luminescence film sample to expand and generate stress. When taking pictures with a visible light camera, no obvious luminescence phenomenon was photographed at different hose expansion degrees; while when taking pictures with an infrared CCD camera, as the hose expansion degree increases, corresponding to the increase in the stress at this part, a brighter luminescence phenomenon was photographed, indicating photon emission in the infrared region. The situations of other force-induced luminescence film samples are similar, with different luminescence degrees.

[0077] The above are only several embodiments of the present application, and do not impose any form of limitation on the present application. Although the present application is disclosed above with preferred embodiments, these embodiments are not used to limit the present application. Any person skilled in the art, without departing from the scope of the technical solution of the present application, makes some changes or modifications using the technical content disclosed above, which are equivalent to equivalent embodiments and all fall within the scope of the technical solution of the present application.

Claims

1. A force-induced luminescence material, characterized in that, The chemical formula of the stress luminescent material is Y3Al2Ga3O 12 :xBi, where x = 0.001 - 0.015; Among them, Y3Al2Ga3O 12 is the matrix, and the doped ion Bi 3+ is the activating ion.

2. The mechanoluminescent material according to claim 1, wherein The mechanoluminescence wavelength of the mechanoluminescent material is in the range of 650 - 950 nm, and the mechanoluminescence peak is at 715 nm; Preferably, x = 0.006 - 0.

008.

3. A method for preparing the mechanoluminescent material according to claim 1 or 2, characterized in that, Comprising: Mixing raw materials including a yttrium compound, an aluminum compound, a gallium compound, a bismuth compound, and boric acid according to the ratio of the chemical formula, and sintering by the high-temperature solid-phase method to obtain the mechanoluminescent material.

4. The method according to claim 3, wherein Including the following steps: a) Mix the raw materials, add ethanol, and grind for 0.2 - 2 h; b) Sinter the mixture obtained in step a), and cool to obtain the mechanoluminescent material.

5. The method according to claim 4, characterized in that In step a), the volume ratio of the ethanol to the raw materials is 1:0.8 - 1:1.2; Preferably, in step b), the sintering temperature is 1450 - 1600 °C; Preferably, in step b), the sintering time is 3.0 - 8.0 h.

6. The method according to claim 3, characterized in that The amount of the boric acid is 2.0 - 4.0 mol%, based on the total molar amount of the raw materials; Preferably, the yttrium compound is yttrium oxide Y2O3; Preferably, the aluminum compound is aluminum oxide Al2O3; Preferably, the gallium compound is gallium oxide Ga2O3; Preferably, the bismuth compound is bismuth oxide Bi2O3.

7. A force-induced luminescence complex, characterized in that, Comprising the mechanoluminescent material according to claim 1 or 2 and a transparent polymer.

8. The mechanoluminescent complex according to claim 7, wherein The mechanoluminescent composite is in the form of a bulk elastomer, a columnar elastomer, or a film; Preferably, the mechanoluminescent composite is a mechanoluminescent film; Preferably, the transparent polymer is at least one selected from polyurethane, silica gel, and polydimethylsiloxane, preferably polydimethylsiloxane.

9. The mechanoluminescent complex according to claim 7, wherein The preparation method of the mechanoluminescent composite includes: mixing the mechanoluminescent material powder and the transparent polymer, and then curing in a mold; Preferably, the mass ratio of the mechanoluminescent material powder to the transparent polymer is 1:1 - 2:1; Preferably, the curing temperature is 60 - 100 °C.

10. Use of the mechanoluminescent material according to claim 1 or 2 or the mechanoluminescent composite according to any one of claims 7 to 9 for stress detection in a bright-field environment.

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