ZnS: Mn-based stress luminescent material as well as preparation method and application thereof

Abstract

The invention provides a ZnS: Mn-based stress luminescent material as well as a preparation method and application thereof, and relates to the technical field of inorganic luminescent materials. The nano particles are introduced into the ZnS-based material, so that the stress luminescence (ML) intensity of the material can be effectively improved, and the optical performance of the material is improved. Due to the addition of a cosolvent Li2CO3, the crystallinity of the ZnS material can be improved, and the optical performance of the material can be enhanced; the introduction of the nanoparticles may then increase the elastic modulus and dilute the particle density of the ML phosphor and enhance light scattering. The ZnS: Mn-based stress luminescent material prepared by the method has excellent luminescent intensity and stability, and the mechanical photoluminescence response of the ZnS: Mn-based stress luminescent material is obviously higher than that of a traditional ZnS-based material. The preparation method provided by the invention is simple and convenient to operate, low in cost and wide in application prospect.

Description

Technical Field

[0001] The invention relates to the technical field of inorganic luminescent materials, and in particular to a ZnS:Mn-based stress luminescent material and a preparation method and application thereof. Background Art

[0002] Stress luminescent materials have attracted extensive attention due to their unique luminescent properties and have important application potential in the fields of stress sensors, stress distribution imaging, structural health diagnosis, new light sources and displays, and optical anti-counterfeiting. However, there is still a lack of non-destructive stress luminescent materials with high stress luminescence intensity and repeatable luminescence, which greatly limits their practical application value.

[0003] Patent CN117004382A discloses a method for connecting nanoparticles and stress luminescent powders through chemical bonds to form a stress luminescent composite material with a micro-nano structure. This technology fixes high-hardness nanoparticles (such as diamond, aluminum oxide, etc.) on the surface of stress luminescent powders through amide bonds, significantly improving the luminescence intensity and structural stability of the material. However, this method is complex, involving particle surface functionalization and chemical reaction steps, and is costly. At the same time, it has a strong selectivity for nanoparticles, which affects the universality of the process.

[0004] Existing stress luminescent material modification technologies mostly improve material performance through surface modification and chemical treatment, but these methods often have problems such as complex preparation process and poor particle distribution uniformity. In addition, although some modification technologies have improved the luminescence intensity, in practical applications, they are limited in their widespread use in many fields due to insufficient stability or difficulty in large-scale production. Therefore, how to simplify the process, optimize the material structure and performance, especially enhance the stress luminescence effect, has become an important direction for the research and development of stress luminescent materials. Summary of the invention

[0005] In view of the defects and deficiencies in the above-mentioned prior art, the purpose of the present invention is to provide a ZnS:Mn-based stress luminescent material and its preparation method and application, by introducing nanoparticles into the ZnS-based stress material, the stress luminescent effect of the material is significantly enhanced. The method of the present invention has a simple preparation method, good chemical stability, and excellent luminescent performance, and is suitable for stress sensing and many other applications.

[0006] In order to achieve the above-mentioned object of the invention, the present invention provides the following technical solutions:

[0007] One of the technical solutions of the present invention provides a method for preparing a ZnS:Mn-based stress luminescent material, comprising the following steps:

[0008] ZnS, MnCO3, flux and nanoparticles (NPs) are mixed to obtain a mixture, the mixture is sintered by a high-temperature solid phase method under a protective atmosphere, the sintered product is cooled to room temperature and ground into powder, and the ZnS:Mn-based stress luminescent material is obtained.

[0009] Furthermore, the flux is any one of Li2CO3, NaCl, B2O3, and Li2O, preferably Li2CO3.

[0010] Furthermore, the nanoparticles are any one of Al2O3, SiO2, and ZrO2; the particle size of the nanoparticles is 100-300nm, preferably 200nm.

[0011] Furthermore, the purity of the ZnS is preferably above 99.99%, the purity of the MnCO3 is preferably above 99.95%, the purity of the flux is preferably above 99%, and the purity of the nanoparticles is preferably above 99%.

[0012] Furthermore, the molar ratio of the ZnS, MnCO3, flux and nanoparticles is 1:(0.002-0.04):(0.01-0.04):(0-0.3); the addition ratio of the nanoparticles can be 0.

[0013] Furthermore, the method for mixing the ZnS, MnCO3, flux and nanoparticles (NPs) is preferably: placing ZnS, MnCO3, nanoparticles and flux in a high-purity mortar, then adding grinding media for uniform mixing, and then drying the resulting mixed system at 40-60°C for 10-30 minutes to obtain a mixture; the grinding medium is preferably anhydrous ethanol, and the grinding time is 20-30 minutes.

[0014] Furthermore, the protective atmosphere is an inert gas or nitrogen, preferably nitrogen.

[0015] Furthermore, the sintering temperature is 1050-1200°C, more preferably 1100-1150°C; the sintering time is 3-6h; the heating rate from room temperature to the sintering temperature is 4-6°C / min; the sintering pressure is 0.015-0.03MPa, more preferably 0.015-0.02MPa.

[0016] A second technical solution of the present invention provides a ZnS:Mn-based stress luminescent material prepared by the preparation method described in the above technical solution.

[0017] In the present invention, the preparation method is simple and low-cost, and is convenient for large-scale industrial production. By reasonably controlling the amount of doping elements and flux added and sintering conditions, the ZnS:Mn-based stress luminescent material prepared by the present invention has high crystallinity and luminescence intensity, and can maintain good stability, and is suitable for stress sensors, structural health monitoring and other fields.

[0018] The present invention provides a ZnS:Mn-based stress luminescent material prepared by the above preparation method, which has a high stress luminescent effect and exhibits high sensitivity and long service life in applications. Compared with traditional commercial manganese-doped ZnS materials, the material of the present invention has significant advantages in luminescent intensity and stability, and is suitable for a wider range of application fields, such as smart sensors, mechanical damage detection, etc.

[0019] A third technical solution of the present invention provides an application of the above-mentioned ZnS:Mn-based stress luminescent material, in which the ZnS:Mn-based stress luminescent material is used as a raw material to prepare a stress luminescent composite material; the stress luminescent composite material includes preparing an elastic polymer stress luminescent composite material, and / or a transparent self-healing polymer elastomer stress luminescent composite material.

[0020] A fourth technical solution of the present invention provides an elastic polymer stress luminescent composite material, wherein the raw materials for preparing the elastic polymer stress luminescent composite material include an elastic polymer material and a stress luminescent material; the elastic polymer material is made of a polymer material and a curing agent, and the stress luminescent material is a ZnS:Mn-based stress luminescent material prepared by the preparation method described in the above technical solution.

[0021] Further, the elastic polymer material is any one of transparent PU potting glue, transparent silicone potting glue, addition-cured silicone rubber resin RTV-2, epoxy resin potting glue, and transparent PMDS elastic potting glue, preferably transparent PU potting glue; the above-mentioned several elastic polymer materials are all made by mixing A glue and B glue, the A glue is a polymer material with bonding and fixing functions, and the B glue is a curing agent, the main function of which is to accelerate the curing process of the A glue; the amount relationship between the A glue and the B glue varies according to the different elastic polymer materials actually used:

[0022] In the transparent PU potting glue, the ratio of glue A to glue B is (0.4-0.6): (0.4-0.6), preferably 1:1; in the transparent silicone potting glue, the ratio of glue A to glue B is (0.4-0.6): (0.4-0.6), preferably 1:1; in the addition-cured silicone rubber resin RTV-2, the ratio of glue A to glue B is (8-10): 1, preferably 9:1; in the epoxy resin potting glue, the ratio of glue A to glue B is (0.4-0.6): (0.4-0.6), preferably 1:1; in the transparent PMDS elastic potting glue, the ratio of glue A to glue B is (9-11): 1, preferably 10:1.

[0023] Furthermore, the mass ratio of the elastic polymer material to the stress luminescent material is 1:(0.4-1), and more preferably 1:(0.4-0.6).

[0024] Furthermore, the preparation method of the elastic polymer stress luminescent composite material comprises the following steps:

[0025] (1) Mixing the polymer material (glue A) and the curing agent (glue B) to form a precursor solution, and removing bubbles;

[0026] (2) adding ZnS:Mn-based stress luminescent material to the above-mentioned precursor solution, stirring continuously until uniform, obtaining a mixed slurry of ZnS:Mn-based stress luminescent material and precursor solution, and removing bubbles;

[0027] (3) Pour the mixed slurry evenly into a mold, dry and solidify it, and obtain an elastic polymer stress luminescent composite material.

[0028] Furthermore, the bubbles are removed in steps (1) and (2) by ultrasonic debubbling or by using a vacuum pump; the ultrasonic debubbling time is 15 to 20 minutes, and the vacuum pump extraction time is 10 to 30 minutes; the vacuum degree of the vacuum pump is 5 to 20 kPa.

[0029] Furthermore, the material of the mold in step (3) is preferably polytetrafluoroethylene.

[0030] Furthermore, the drying and curing in step (3) is preferably carried out in a forced air drying oven; the curing temperature is 60 to 80° C., and the curing time is 2 to 3 hours.

[0031] A fifth technical solution of the present invention provides a transparent self-healing polymer elastomer stress luminescent composite material, wherein the raw materials of the transparent self-healing polymer elastomer stress luminescent composite material include a polymer material, a stress luminescent material, a cross-linking agent and a photoinitiator.

[0032] Furthermore, the stress luminescent material is a ZnS:Mn-based stress luminescent material prepared by the preparation method described in the above technical solution.

[0033] Further, the polymer material is preferably a polymer ChCl-AA-PA made of acrylic acid (AA), choline chloride (ChCl) and phytic acid (PA), wherein the molar ratio of acrylic acid to choline chloride is 1: (1-3), preferably (1-1.5): 2, more preferably 1: 2, and the molar ratio of the total amount of acrylic acid, choline chloride and phytic acid is (500-5000): 1, preferably 1000: 1. The purity of the ChCl is preferably 98% or more, the purity of the AA is preferably 99% or more, and the purity of the PA is preferably 50% or more.

[0034] Furthermore, the crosslinking agent is polyethylene glycol diacrylate (PEG (200) DA), and the photoinitiator is 2959 (component is 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone). The mass ratio of the crosslinking agent and the photoinitiator to the mass ratio of the acrylic acid is 1: (500-1500), and more preferably 1: 1000.

[0035] Furthermore, the mass ratio of the total mass of the polymer material, the crosslinking agent and the photoinitiator to the stress luminescent material is (1-4):10.

[0036] Furthermore, a preferred embodiment is provided, in which the transparent self-healing polymer elastomer stress luminescent composite material is ChCl-AA-PA, and the preparation method thereof comprises the following steps:

[0037] (1) Mixing dried ChCl and AA, heating and stirring to obtain a ChCl-AA PDES (Polymerizable DES, PDES) polymerizable low eutectic solvent;

[0038] (2) adding the PA solution to the above-mentioned ChCl-AA PDES, mixing and stirring to obtain ChCl-AA-PA PDES;

[0039] (3) adding a crosslinking agent and a photoinitiator to ChCl-AA-PA PDES and mixing and stirring to form a polymer precursor solution, and removing bubbles;

[0040] (4) adding ZnS:Mn-based stress luminescent material to the polymer precursor solution, stirring evenly to obtain a mixed slurry of ZnS:Mn-based stress luminescent material and polymer, and removing bubbles;

[0041] (5) placing the mixed slurry in a mold; irradiating the mixed slurry with a UV light source at room temperature to initiate a polymerization reaction and solidify the mixed slurry to obtain the transparent self-healing polymer elastomer stress luminescent composite material ChCl-AA-PA.

[0042] Furthermore, the heating and stirring temperature in step (1) is 60 to 90° C., and the stirring time is 4 to 6 hours.

[0043] Furthermore, the bubbles are removed in steps (3) and (4) by ultrasonic debubbling or by using a vacuum pump; the ultrasonic debubbling time is 15 to 20 minutes, and the vacuum pump extraction time is 10 to 30 minutes; the vacuum degree of the vacuum pump is 5 to 20 kPa.

[0044] Furthermore, the material of the mold in step (5) is preferably polytetrafluoroethylene. The wavelength of the UV light source is 365nm, and the irradiation time is 1 to 10 minutes.

[0045] Compared with the prior art, the present invention has at least the following advantages and beneficial effects:

[0046] (1) The technical solution provided by the present invention optimizes the structure of ZnS:Mn-based stress luminescent materials by introducing nanoparticles to improve the luminescence intensity and stability. Nanoparticles can promote stress transfer and effectively improve the stress luminescence performance of materials, thereby enabling them to exhibit superior performance in a variety of application fields (such as stress sensors, structural health monitoring, etc.).

[0047] (2) The present invention discloses a method for preparing a ZnS:Mn-based stress luminescent material, which specifically comprises the following steps: mixing ZnS, MnCO3, flux and nanoparticles in a certain proportion, and performing high-temperature solid-phase sintering under a protective atmosphere to obtain the ZnS:Mn-based stress luminescent material. By using MnCO3 as a manganese source for manganese doping, the luminescent properties of the material are significantly enhanced. At the same time, the addition of a flux can effectively reduce the melting point of the material during the sintering process, promote the better entry of Mn ions into the ZnS lattice, and reduce the required sintering temperature, making the calcination more sufficient. In addition, the present invention also introduces nanoparticles, which can improve the mechanical properties of the material, improve the dispersibility of the stress luminescent powder, and further improve the stress luminescent effect. The addition of these nanoparticles not only optimizes the microstructure of the material, but also enhances its stress response performance.

[0048] (3) The ZnS:Mn-based stress luminescent material prepared by the method of the present invention has significant advantages, including high crystallinity, excellent luminescence intensity and outstanding stability. Its structure has been finely optimized, which can effectively improve the stress luminescence effect of the material, so that it performs well in applications such as stress sensing, structural health monitoring, and mechanical damage detection. Compared with traditional commercial manganese-doped ZnS materials, the materials of the present invention not only have obvious advantages in luminescence intensity, but can also be prepared efficiently at low cost in industrial production, and have broad application prospects. Whether in the field of smart sensors, display technology, or high-performance stress sensors, the materials provided by the present invention can provide more stable and efficient performance, which will further promote the application of stress luminescent materials in a wider range of fields. BRIEF DESCRIPTION OF THE DRAWINGS

[0049] Figure 1 This is the SEM spectrum of the ZnS:Mn-based stress luminescent material ZnS:0.002Mn.0.01Li2CO3 prepared in Example 1;

[0050] Figure 2 The SEM spectrum of the ZnS:Mn-based stress luminescent material ZnS:0.02Mn.0.01Li2CO3.0.1Al2O3 prepared in Example 2;

[0051] Figure 3 A schematic diagram of the ZnS:Mn-based stress luminescent material ZnS:0.02Mn.0.01Li2CO3.0.1Al2O3 provided in Example 2 of the present invention;

[0052] Figure 4 The stress luminescence spectra of the elastic polymer stress luminescent material ZnS:0.02Mn.0.1Li2CO3.0.1NPs / PU prepared in Examples 2, 3 and 4 under the same test conditions;

[0053] Figure 5 X-ray diffraction spectra of ZnS:Mn-based stress luminescent materials prepared in Examples 1, 2, 3, and 4;

[0054] Figure 6 These are stress luminescence spectra of the transparent self-healing stress luminescent polymer elastomer ZnS:0.02Mn.0.1Li2CO3.0.1NPs / PEG prepared in Examples 5, 6, 7 and Comparative Example 8 under the same test conditions. DETAILED DESCRIPTION

[0055] In order to enable those skilled in the art to better understand the technical solution of the present invention, the present invention is described in detail below in conjunction with specific embodiments. It should be noted that the following embodiments will help those skilled in the art to further understand the present invention, but do not limit the present invention in any form. It should be noted that for those of ordinary skill in the art, several variations and improvements can also be made without departing from the concept of the present invention. These all belong to the protection scope of the present invention.

[0056] All raw materials of the present invention have no particular limitation on their sources, and can be purchased from the market or prepared according to conventional methods known to those skilled in the art.

[0057] Sources and specifications of raw materials involved in this application:

[0058] ZnS (Aladdin);

[0059] Li2CO3 (Shanghai Titan Technology Co., Ltd.);

[0060] MnCO3 (Shanghai MacLean Biochemical Technology Co., Ltd.);

[0061] Al2O3, SiO2, ZrO2 (MCC New Materials, 200nm);

[0062] Transparent PU potting glue (Tinglan Leining Glue Industry);

[0063] ChCl (McLean's reagent);

[0064] AA (McLean's reagent);

[0065] PA (McLean's reagent);

[0066] PEG(200)DA (Shanghai Yinchang New Materials Co., Ltd.);

[0067] Photoinitiator 2959 (Shanghai Yinchang New Materials Co., Ltd.);

[0068] Example 1

[0069] A ZnS:Mn-based stress luminescent material, the preparation method is as follows:

[0070] (1) Weigh ZnS, MnCO3, and Li2CO3 according to the stoichiometric ratio (ZnS:xMn.yLi2CO3; x=0.002, y=0.01), put the weighed raw materials into an agate mortar, add an appropriate amount of anhydrous ethanol, continue grinding until uniformly mixed, put them into an oven to dry, and then move them into a corundum crucible;

[0071] (2) The corundum crucible containing the sample is placed in a porcelain boat, and the porcelain boat is placed in a tube furnace of model GSL-1600X for sintering. It is calcined at a constant temperature of 1150°C for 3 hours (heating rate of 5°C / min), and a protective atmosphere of nitrogen is passed throughout the calcination process with a gas flow rate of 0.15L / min. After the tube furnace program is completed and the tube cools to room temperature, the corundum crucible is taken out, and the sample is moved back into an agate mortar and ground into powder to obtain the ZnS:Mn-based stress luminescent material, recorded as ZnS:0.002Mn.0.01Li2CO3 stress luminescent material.

[0072] The SEM spectrum of the ZnS:Mn-based stress luminescent material ZnS:0.002Mn.0.01Li2CO3 prepared in this example is shown in Figure 1 As shown, it can be seen that the sample surface presents a clear granular structure, the particle size distribution is relatively uniform, and the diameter of most particles is at the submicron level. It is worth noting that no obvious particle agglomeration phenomenon is observed in the sample, which indicates that Li2CO3 as a flux not only promotes the uniform dispersion of particles during sample preparation, but also effectively inhibits the formation of agglomerates. This uniform particle distribution and non-agglomeration characteristics provide a structural basis for the excellent performance of the sample.

[0073] An elastic polymer stress luminescent composite material, wherein the elastic polymer material is a transparent PU potting glue, and the preparation method is as follows:

[0074] (a) Mix the transparent PU potting glue according to the ratio of A glue (transparent PU potting glue LN-3002A): B glue (curing agent LN-3002B) = 1:1 (mass ratio), and continue stirring until the mixture is uniform to obtain a transparent PU potting glue mixed liquid;

[0075] (b) The ZnS:0.002Mn.0.01Li2CO3 stress luminescent material obtained in the above step (2) and the transparent PU potting glue mixture obtained in step (a) are mixed in a ratio of 0.4:2 (mass ratio), and stirred continuously until the mixture is uniform to obtain a composite material mixture. The composite material mixture is transferred into an ultrasonic cleaning machine for debubbling (40kHz, 15min), or a vacuum pump is used to extract and debubble (room temperature, vacuum degree 200Pa, 10min), and then the composite material mixture is transferred into a rectangular polytetrafluoroethylene mold (size is 10cm*2cm*1cm);

[0076] (c) placing the rectangular polytetrafluoroethylene mold containing the composite material mixture into an oven and curing at 60° C. for 2 h to obtain an elastic stress luminescent composite material, recorded as ZnS:0.002Mn.0.01Li2CO3 / PU;

[0077] The elastic stress luminescent composite material prepared in Example 1 was tested and characterized using a QE-Pro photon receiver connected to a push-pull force gauge (the push-pull force gauge model is Edberg HP-100), the applied load was set to 10N, and the effective contact area of ​​the sample was 1cm.

[0078] The stress luminescence intensity of the elastic stress luminescence composite material in Example 1 under the sliding stress of 10N load is much higher than that of the commercial powder.

[0079] Comparative Example 1

[0080] Compared with Example 1, x=0.004 was changed, and the rest was the same as Example 1. The finally obtained elastic polymer stress luminescent composite material was recorded as ZnS:0.004Mn.0.01Li2CO3 / PU.

[0081] Comparative Example 1 and the stress luminescence spectrum of the elastic stress luminescence composite material prepared when x=0.002 under the same force, under the same test conditions, as x increases, the luminescence intensity shows an increasing trend.

[0082] Comparative Example 2

[0083] Compared with Example 1, x=0.006 is changed, and the rest is the same as Example 1. The obtained elastic polymer stress luminescent composite material is recorded as ZnS:0.006Mn.0.01Li2CO3 / PU.

[0084] The stress luminescence spectrum of the elastic stress luminescence composite material prepared in Comparative Example 2 under the same force shows an increasing trend of luminescence intensity as x increases under the same test conditions.

[0085] Comparative Example 3

[0086] Compared with Example 1, x=0.008 is changed, and the rest is the same as Example 1. The obtained elastic polymer stress luminescent composite material is recorded as ZnS:0.008Mn.0.01Li2CO3 / PU.

[0087] The stress luminescence spectrum corresponding to the elastic stress luminescence composite material prepared in Comparative Example 3 under the same force shows an increasing trend of luminescence intensity as x increases under the same test conditions.

[0088] Comparative Example 4

[0089] Compared with Example 1, x=0.01 was changed, and the rest was the same as Example 1. The obtained elastic polymer stress luminescent composite material was recorded as ZnS:0.01Mn.0.01Li2CO3 / PU.

[0090] The stress luminescence spectrum corresponding to the elastic stress luminescence composite material prepared in Comparative Example 4 under the same force shows an increasing trend of luminescence intensity as x increases under the same test conditions.

[0091] Comparative Example 5

[0092] Compared with Example 1, x=0.02 was changed, and the rest was the same as Example 1. The obtained elastic polymer stress luminescent composite material was recorded as ZnS:0.02Mn.0.01Li2CO3 / PU.

[0093] The stress luminescence spectrum corresponding to the elastic stress luminescence composite material prepared in Comparative Example 5 under the same force shows an increasing trend of luminescence intensity as x increases under the same test conditions.

[0094] Comparative Example 6

[0095] Compared with Example 1, x=0.03 was changed, and the rest was the same as Example 1. The obtained elastic polymer stress luminescent composite material was recorded as ZnS:0.03Mn.0.01Li2CO3 / PU.

[0096] The stress luminescence spectrum of the elastic stress luminescence composite material prepared in Comparative Example 6 under the same force shows that, under the same test conditions, the luminescence intensity decreases significantly as x increases.

[0097] Comparative Example 7

[0098] Compared with Example 1, x=0.04 was changed, and the rest was the same as Example 1. The obtained elastic polymer stress luminescent composite material was recorded as ZnS:0.04Mn.0.01Li2CO3 / PU.

[0099] The stress luminescence spectrum of the elastic stress luminescence composite material prepared in Comparative Example 7 under the same force shows that, under the same test conditions, as x increases, the luminescence intensity continues to decrease.

[0100] Combining Example 1 and Comparative Examples 1 to 7, it is found that when x is in the range of 0.002 to 0.02, as x increases, the luminescence intensity of the elastic polymer stress luminescent composite material increases; however, when x>0.02, as x increases, the luminescence intensity of the elastic polymer stress luminescent composite material begins to drop sharply. This shows that x=0.02 in Comparative Example 5 can be used as a preferred value for subsequent experiments.

[0101] Example 2

[0102] (1) Compared with Example 1, nanoparticles were added to modify the surface of the stress luminescent powder. ZnS, MnCO3, Li2CO3, and Al2O3 were weighed according to the stoichiometric ratio (ZnS:xMn.yLi2CO3.zAl2O3; x=0.02, y=0.01, z=0.1). The weighed raw materials were placed in an agate mortar, and an appropriate amount of anhydrous ethanol was added. The raw materials were continuously ground until uniformly mixed, and then placed in an oven for drying and then transferred to a corundum crucible;

[0103] (2) The corundum crucible containing the sample is placed in a porcelain boat, and the porcelain boat is placed in a tube furnace of model GSL-1600X for sintering. It is calcined at a constant temperature of 1150°C for 3 hours (heating rate of 5°C / min), and a protective atmosphere of nitrogen is passed throughout the calcination process with a gas flow rate of 0.15L / min. After the tube furnace program is completed and the tube cools to room temperature, the corundum crucible is taken out, and the sample is moved back into an agate mortar and ground into powder to obtain the ZnS:Mn-based stress luminescent material, recorded as ZnS:0.02Mn.0.01Li2CO3.0.1Al2O3 stress luminescent material.

[0104] (3) The ZnS:0.02Mn.0.01Li2CO3.0.1Al2O3 stress luminescent material is used to prepare an elastic stress luminescent composite material, which is recorded as ZnS:0.02Mn.0.01Li2CO3.0.1Al2O3 / PU.

[0105] The SEM results of the ZnS:0.02Mn.0.01Li2CO3.0.1Al2O3 stress luminescent material prepared in this example are shown in FIG. Figure 2 As shown in the figure, it can be seen that the sample surface maintains a uniform granular structure, the particle size distribution is relatively consistent, and the particle diameter is still at the submicron level. 2+ A uniform nanoscale coating is formed on the surface of the particles, which further improves the dispersion of the particles. This uniform dispersion helps to more effectively transfer and distribute energy under stress, thereby improving the stress luminescence performance of the material. In addition, no obvious particle agglomeration phenomenon is still observed in the sample, which shows that the modification process of Al2O3 not only maintains the original particle dispersion, but also further enhances the stability of the particles.

[0106] Figure 3 A schematic diagram of the stress luminescent composite material of the present invention is provided. The stress luminescent composite material shown is prepared by a high temperature solid phase method. 2+ Particles are introduced to enhance performance through nanoparticles, and are formed by wrapping and curing an elastic polymer matrix. This material has efficient stress luminescence performance and excellent mechanical properties, and is suitable for a variety of flexible application scenarios.

[0107] Example 3

[0108] Compared with Example 2, except that the nanoparticles are replaced with silicon dioxide, the rest is the same as Example 1, and the obtained elastic stress luminescent composite material is recorded as ZnS: 0.02Mn.0.01Li2CO3.0.1SiO2 / PU.

[0109] Example 4

[0110] Compared with Example 2, except that the nanoparticles are replaced with zirconium dioxide, the rest is the same as Example 1, and the obtained elastic stress luminescent composite material is recorded as ZnS: 0.02Mn.0.01Li2CO3.0.1ZrO2 / PU.

[0111] Figure 4 The stress luminescence spectra of the elastic stress luminescence composite materials in Examples 2, 3, and 4 under the sliding stress of 10N load are shown. It is found that the stress luminescence performance of the stress luminescence powder modified by adding nanoparticles is improved. The luminescence curves of the elastic stress luminescence composite materials prepared in Examples 2, 3, and 4 at 600nm have intensities higher than those of the elastic stress luminescence composite materials when z=0 (the elastic polymer stress luminescence composite materials provided in Comparative Example 5). In addition, after adding several different nanoparticles, the performance is compared: ZnS: 0.02Mn. 0.01Li2CO3. 0.1Al2O3 / PU> ZnS: 0.02Mn. 0.01Li2CO3. 0.1SiO2 / PU> ZnS: 0.02Mn. 0.01Li2CO3. 0.1ZrO2 / PU.

[0112] Figure 5 The X-ray diffraction spectra of ZnS:Mn based stress luminescent materials prepared in Examples 1, 2, 3, and 4 are provided. From the results, it can be seen that the main diffraction peaks of all samples are consistent with the standard card of ZnS (JCPDS#36-1450). After the addition of nanoparticles, the diffraction peak intensity is significantly reduced, and the peak width is increased, indicating that the introduction of nanoparticles may lead to a decrease in crystal size or lattice distortion. In addition, no obvious impurity phase is observed, indicating that the sample purity is high. In summary, the addition of nanoparticles has a significant effect on the ZnS:Mn 2+ The crystal structure of the nanostructured samples was significantly affected, which also had a positive impact on the stress luminescence properties.

[0113] Example 5

[0114] According to steps (1) and (2) in Example 2, a ZnS: 0.02Mn. 0.01Li2CO3. 0.1Al2O3 stress luminescent material was prepared, and the material was used as stress luminescent powder to prepare a transparent self-healing polymer elastomer stress luminescent composite material, and the material was recorded as ZnS: 0.02Mn. 0.01Li2CO3. 0.1Al2O3 / PEG. The preparation method is as follows:

[0115] (1) Weighing an appropriate amount of choline chloride ChCl and placing it in an oven to dry at a drying temperature of 60°C for 2 hours; mixing the dried choline chloride ChCl and acrylic acid AA in a molar ratio of 1:2 to obtain ChCl-AA PDES (polymerizable low eutectic solvent Polymerizable DES, PDES); transferring the ChCl-AA PDES to a sealed flask, placing it on a heating table and heating and stirring until a uniform colorless solution is formed, the heating temperature is 90°C, and the stirring time is 4 hours;

[0116] (2) adding the PA solution to the ChCl-AA PDES at a molar ratio of 1:1000, mixing and stirring to obtain ChCl-AA-PA PDES;

[0117] (3) adding a crosslinker PEG(200)DA and a photoinitiator 2959 to ChCl-AA-PA PDES at a molar ratio of 1:1000, respectively, and mixing and stirring to form a polymer precursor solution;

[0118] (4) Add ZnS: 0.02Mn. 0.01Li2CO3. 0.1Al2O3 stress luminescent material to the polymer precursor solution, and continue stirring until it is uniform to obtain a mixed slurry of ZnS: 0.02Mn. 0.01Li2CO3. 0.1Al2O3 stress luminescent material and ChCl-AA-PA PDES, and move the mixed slurry into an ultrasonic cleaner for degassing (40kHz, 15min), or use a vacuum pump to extract and degas (room temperature, vacuum degree 200Pa, 10min); place the mixed slurry in a rectangular polytetrafluoroethylene mold (size 10cm x2cm x 1cm);

[0119] (5) At room temperature, irradiate with a UV light source (365 nm) for 2 minutes to initiate a polymerization reaction and cure; after the curing, the transparent self-healing polymer elastomer stress luminescent composite material ZnS: 0.02Mn.0.01Li2CO3.0.1Al2O3 / PEG is obtained.

[0120] Example 6

[0121] Compared with Example 5, except that the nanoparticles are replaced with silicon dioxide SiO2, the rest is the same as Example 5, and the obtained transparent self-healing polymer elastomer stress luminescent composite material is recorded as ZnS:0.02Mn.0.01Li2CO3.0.1SiO2 / PEG.

[0122] Example 7

[0123] Compared with Example 5, except that the nanoparticles are replaced with zirconium dioxide ZrO2, the rest is the same as Example 5, and the obtained transparent self-healing polymer elastomer stress luminescent composite material is recorded as ZnS:0.02Mn.0.01Li2CO3.0.1ZrO2 / PEG.

[0124] Comparative Example 8

[0125] Compared with Example 5, no nanoparticles are added, and the rest is the same as Example 5. The obtained transparent self-healing polymer elastomer stress luminescent composite material is recorded as ZnS:0.02Mn.0.01Li2CO3 / PEG.

[0126] Figure 6 These are the stress luminescence spectra corresponding to the elastic stress luminescence force under the sliding stress of 10N load for the transparent self-healing polymer elastomer stress luminescence composite materials prepared in Examples 5, 6, 7 and Comparative Example 8. It can be seen that the luminescence intensity of the three samples with surface modification is stronger than that of the unmodified stress luminescence sample, and the luminescence intensity of the sample modified by Al2O3 is the highest.

[0127] It can be seen from the above embodiments and comparative examples that the ZnS:Mn-based stress luminescent material prepared by the method of the present invention has high brightness, a luminescent intensity higher than that of commercial manganese-doped ZnS-based luminescent material, and high luminescent efficiency.

[0128] The above description of the embodiments is to facilitate the understanding and use of the invention by those skilled in the art. It is obvious that those skilled in the art can easily make various modifications to these embodiments and apply the general principles described herein to other embodiments without creative work. Therefore, the present invention is not limited to the above embodiments, and improvements and modifications made by those skilled in the art based on the disclosure of the present invention without departing from the scope of the present invention should be within the scope of protection of the present invention.

Claims

1. A method for preparing a ZnS:Mn-based stress luminescent material, characterized in that: The following steps are involved: ZnS, MnCO3, flux and nanoparticles are mixed to obtain a mixture, the mixture is sintered by a high-temperature solid phase method under a protective atmosphere, the sintered product is cooled to room temperature and ground into powder, and the ZnS:Mn-based stress luminescent material is obtained.

2. The method for preparing a ZnS:Mn-based stress luminescent material according to claim 1, characterized in that: The flux is any one of Li2CO3, NaCl, B2O3, and Li2O; The nanoparticles are any one of Al2O3, SiO2, and ZrO2; The particle size of the nanoparticles is 100-300 nm; The purity of the ZnS is 99.99% or more, the purity of the MnCO3 is 99.95% or more, the purity of the flux is 99% or more, and the purity of the nanoparticles is 99% or more; The molar ratio of the ZnS, MnCO3, flux and nanoparticles is 1:(0.002-0.04):(0.01-0.04):(0-0.3); the addition ratio of the nanoparticles can be 0.

3. The method for preparing a ZnS:Mn-based stress luminescent material according to claim 1, characterized in that: The method of mixing ZnS, MnCO3, flux and nanoparticles is: The ZnS, MnCO3, nanoparticles and flux are placed in a mortar, a grinding medium is added to uniformly mix, and the resulting mixed system is dried at 40 to 60° C. for 10 to 30 minutes to obtain a mixture; The grinding medium is anhydrous ethanol, and the grinding time is 20 to 30 minutes.

4. The method for preparing a ZnS:Mn-based stress luminescent material according to claim 1, characterized in that: The protective atmosphere is an inert gas or nitrogen; The sintering temperature is 1050-1200°C, the time is 3-6h, and the pressure is 0.015-0.03MPa; The heating rate from room temperature to the sintering temperature is 4-6°C / min.

5. A ZnS:Mn-based stress luminescent material, characterized in that: It is prepared by the preparation method according to any one of claims 1 to 4.

6. Application of a ZnS:Mn-based stress luminescent material, characterized in that: In the application, the ZnS:Mn-based stress luminescent material is used as a raw material to prepare a stress luminescent composite material; The stress luminescent composite material includes an elastic polymer stress luminescent composite material and / or a transparent self-healing polymer elastomer stress luminescent composite material.

7. An elastic polymer stress luminescent composite material, characterized in that: The raw materials for preparing the elastic polymer stress luminescent composite material include an elastic polymer material and a stress luminescent material; the elastic polymer material is made of a polymer material and a curing agent, and the stress luminescent material is the ZnS:Mn-based stress luminescent material as described in claim 5; The elastic polymer material is any one of transparent PU potting glue, transparent silicone potting glue, addition-cured silicone rubber resin RTV-2, epoxy resin potting glue, and transparent PMDS elastic potting glue; The elastic polymer material is made by mixing glue A and glue B, wherein the glue A is a polymer material used for bonding and fixing, and the glue B is a curing agent used for accelerating the curing process of glue A; In the transparent PU potting glue, the ratio of A glue to B glue is (0.4-0.6): (0.4-0.6); in the transparent silicone potting glue, the ratio of A glue to B glue is (0.4-0.6): (0.4-0.6); in the addition-cured silicone rubber resin RTV-2, the ratio of A glue to B glue is (8-10): 1; in the epoxy resin potting glue, the ratio of A glue to B glue is (0.4-0.6): (0.4-0.6); in the transparent PMDS elastic potting glue, the ratio of A glue to B glue is (9-11): 1; The mass ratio of the elastic polymer material to the stress luminescent material is 1:(0.4-1).

8. The elastic polymer stress luminescent composite material according to claim 7, characterized in that: The preparation method comprises the following steps: (1) Mixing the polymer material and the curing agent to form a precursor solution and removing bubbles; (2) adding ZnS:Mn-based stress luminescent material to the above-mentioned precursor solution, stirring continuously until uniform, obtaining a mixed slurry of ZnS:Mn-based stress luminescent material and precursor solution, and removing bubbles; The bubbles are removed in steps (1) and (2) by ultrasonic debubbling or vacuum pump debubbling; the ultrasonic debubbling time is 15 to 20 minutes, and the vacuum pump extraction time is 10 to 30 minutes; the vacuum degree of the vacuum pump is 5 to 20 kPa; (3) pouring the mixed slurry evenly into a mold, drying and curing the mixture to obtain an elastic polymer stress luminescent composite material; The drying and curing temperature in step (3) is 60-80° C. and the time is 2-3 hours.

9. A transparent self-healing polymer elastomer stress luminescent composite material, characterized in that: The raw materials of the transparent self-healing polymer elastomer stress luminescent composite material include polymer material, stress luminescent material, crosslinking agent and photoinitiator; the stress luminescent material is the ZnS:Mn-based stress luminescent material as described in claim 5; The polymer material is a polymer ChCl-AA-PA made of acrylic acid AA, choline chloride ChCl and phytic acid PA, wherein the molar ratio of acrylic acid to choline chloride is 1:(1-3), and the molar ratio of the total amount of acrylic acid and choline chloride to phytic acid is (500-5000):1; the purity of the ChCl is above 98%, the purity of the AA is above 99%, and the purity of the PA is above 50%; The crosslinking agent is polyethylene glycol diacrylate PEG (200) DA, and the photoinitiator is 2-hydroxy-4-(2-hydroxyethoxy)-2-methylacetophenone; the mass ratio of the crosslinking agent and the photoinitiator to the mass ratio of the acrylic acid is 1: (500-1500); The mass ratio of the total mass of the polymer material, the crosslinking agent and the photoinitiator to the stress luminescent material is (1-4):

10.

10. The transparent self-healing polymer elastomer stress luminescent composite material according to claim 9, characterized in that: The preparation method of ChCl-AA-PA comprises the following steps: (1) Mixing dried ChCl and AA, heating and stirring to obtain a ChCl-AA PDES polymerizable low eutectic solvent; The heating and stirring temperature in step (1) is 60 to 90° C., and the stirring time is 4 to 6 hours; (2) adding the PA solution to the above-mentioned ChCl-AA PDES, mixing and stirring to obtain ChCl-AA-PA PDES; (3) adding a crosslinking agent and a photoinitiator to ChCl-AA-PA PDES and mixing and stirring to form a polymer precursor solution, and removing bubbles; (4) adding ZnS:Mn-based stress luminescent material to the polymer precursor solution, stirring evenly to obtain a mixed slurry of ZnS:Mn-based stress luminescent material and polymer, and removing bubbles; The bubbles are removed in steps (3) and (4) by ultrasonic debubbling or vacuum pump debubbling; the ultrasonic debubbling time is 15 to 20 minutes, and the vacuum pump extraction time is 10 to 30 minutes; the vacuum degree of the vacuum pump is 5 to 20 kPa; (5) placing the mixed slurry in a mold; irradiating the mixture with a UV light source at room temperature to initiate a polymerization reaction and solidify the mixture to obtain the transparent self-healing polymer elastomer stress luminescent composite material ChCl-AA-PA; The wavelength of the UV light source in step (5) is 365 nm, and the irradiation time is 1 to 10 min.

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