A manganese-doped calcium gallium compound-based triboluminescent material and a preparation method thereof

Abstract

The application discloses a friction luminescent material based on manganese-doped calcium gallium compound, which is synthesized by a high-temperature solid-phase method 1‑ x Mn x Ga4O7 stress luminescent fluorescent powder, wherein x is a mass percentage, and 0.001<=x<=0.01; the stress luminescent material is obtained after compounding with a resin mixing solution prepared from epoxy resin and a curing agent; Ca 1‑x Mn x Ga4O7 is a single-phase structure, meanwhile, Mn 2+ replaces the position of Ca 2+ into the crystal lattice; Ca 1‑x Mn x Ga4O7 has photoluminescence performance, the optimal excitation wavelength is 250nm, and the luminescence color is yellow; the stress luminescent fluorescent powder does not have stress luminescence performance under grinding conditions; the stress luminescent material has stress luminescence performance under friction conditions. The preparation method comprises the following steps: 1, preparation of a manganese-doped calcium gallium compound CGO-Mn; 2, preparation of a stress luminescent material CGOM based on the CGO-Mn. As the application of the stress luminescent material, the stress luminescent material has stress luminescence performance under friction conditions, emits yellow light with a wavelength of 530-650nm, and the strongest emission peak is 577nm.

Description

Technical Field

[0001] This invention belongs to the field of stress-luminescent materials, specifically relating to a triboluminescent material based on manganese-doped calcium gallium compounds and its preparation method. Background Technology

[0002] Stress luminescence refers to the phenomenon where a material emits light when subjected to mechanical stress, such as tension, compression, friction, or fracture. Currently, most stress-luminescent materials are discovered based on their stress-luminescent properties under refined grinding and compression conditions. For example, existing literature 1 (CN102329612A[P].2011. High-brightness stress-luminescent materials with layered crystal structures and their preparation methods and applications) prepared stress-luminescent powder using a high-temperature solid-state method with an inert atmosphere, wherein CaZnOS:Mn 2+ It exhibits stress luminescence during both the refining and grinding stages and under compression conditions.

[0003] For example, existing literature 2 (Xu CN, Watanabe T, Akiyama M, et al. Artificial skin tosense mechanical stress by visible light emission[J]. Applied Physics Letters, 1999, 74(9): 1236-1238.) prepared stress-luminescent material ZnS:Mn by introducing an inert atmosphere through a high-temperature solid-state method. 2+ It exhibits stress luminescence during both the refining and grinding stage and under compression conditions.

[0004] For example, existing literature 3 (Chen C, Zhuang Y, Tu D, et al. Creating visible-to-near-infrared mechanoluminescence in mixed-anion compounds SrZn2S2O and SrZnSO[J]. Nano Energy, 2020, 68: 104329.) prepared a series of SrZnSO doped with rare earth ions stress luminescence materials under inert atmosphere conditions by high-temperature solid-state method, which exhibited stress luminescence phenomena during the refining and grinding stage and under compression conditions.

[0005] As can be seen from the existing literature 1-3 above, all three materials exhibit stress luminescence under fine grinding and compression conditions.

[0006] However, some special stress-luminescent materials do not exhibit stress luminescence under the aforementioned grinding and compression conditions. Instead, stress luminescence only occurs when the powder of the stress-luminescent material is composited into PDMS and then stretched. For example, existing literature 4 (Bai Y, Wang F, Zhang L, et al. Interfacial triboelectrification-modulated self-recoverable and thermally stable mechanoluminescence in mixed-anion compounds[J]. Nano Energy,2022,96:107075.) synthesized a series of stress-luminescent materials by doping Sr3Al2O5Cl2 with rare earth ions. These materials do not exhibit stress luminescence under grinding and compression conditions. However, when the stress-luminescent powder is composited into PDMS colloid, which does not exhibit stress luminescence, and then stretched, the material exhibits stress luminescence.

[0007] A comparison of existing literature 1-3 with existing literature 4 shows that determining whether a material exhibits stress luminescence properties after being doped with ions that can serve as luminescent centers cannot be based solely on whether it exhibits stress luminescence properties under grinding and compression conditions. This is because the relationship between the stress-luminescent material and the composite matrix material directly affects the stress luminescence properties.

[0008] In addition, the aforementioned existing documents still have some technical problems.

[0009] For example, the matrix in existing literature 1-3 is a sulfur-containing compound, which directly leads to two technical problems: first, the preparation of sulfur-containing compounds is environmentally unfriendly; second, the preparation process requires sintering in an inert atmosphere. Therefore, an environmentally friendly matrix that can be prepared under air conditions is required.

[0010] For example, the matrix in existing literature 4 is an aluminate. Such materials are prone to deliquescence and have unstable physical and chemical properties. Therefore, the matrix material needs to have high physical and chemical stability.

[0011] According to the inventors' research, gallates, especially calcium gallium compounds, have the advantages of being environmentally friendly, having simple processing methods, and having stable physical and chemical properties. However, stress luminescent materials prepared using calcium gallium compound CaGa4O7 as a matrix have not yet been successfully developed. Summary of the Invention

[0012] The purpose of this invention is to provide a triboluminescent material based on manganese-doped calcium gallium compounds and its preparation method. The basic idea is to dope the calcium gallium compound with ions possessing stress-luminescent properties, such as Mn. 2+ Eu 3+ Pr 3+ 、Sm 3+ This allows us to obtain stress-luminescent materials that are stable, environmentally friendly, and easy to prepare.

[0013] However, during the preparation process, the inventors found that the powder of the prepared stress-luminescent material did not have stress-luminescent properties under grinding conditions. Therefore, based on existing literature and conventional practices in the field, the prepared stress-luminescent powder was compounded with epoxy resin mixture into a block for compression stress luminescence testing, but stress luminescence phenomenon was still not observed.

[0014] To solve the above problems, the inventors discovered through research that only manganese-doped calcium gallium compounds, when combined with epoxy resin to form a bulk, possess triboluminescence properties, while other ions with stress luminescence properties still do not possess stress luminescence properties.

[0015] To achieve the above-mentioned objectives, the technical solution of the present invention is as follows:

[0016] A triboluminescent material based on manganese-doped calcium gallium compounds was synthesized via a high-temperature solid-state method, using monoclinic Ca... 1-x Mn x A stress-luminescent phosphor of Ga4O7, wherein x is the molar percentage and 0.001 ≤ x ≤ 0.01, is compounded with a resin mixture prepared from epoxy resin and a curing agent to obtain a stress-luminescent material; the Ca 1-x Mn x Ga4O7 has a single-phase structure, while Mn 2+ Replace Ca 2+ The position of Ca enters the lattice; 1-x Mn x Ga4O7 exhibits photoluminescence properties, with an optimal excitation wavelength of 250 nm and a yellow emission color.

[0017] The stress-luminescent phosphor does not possess stress-luminescent properties under grinding and compression conditions; however, the stress-luminescent material possesses stress-luminescent properties under friction conditions.

[0018] A method for preparing a triboluminescent material based on a manganese-doped calcium gallium compound includes the following steps:

[0019] Step 1, based on the preparation of manganese-doped calcium gallium compounds, firstly, using the chemical formula Ca... 1-x Mn xGa4O7 is obtained by placing CaCO3, Ga2O3 and MnCO3 in a mortar, adding anhydrous ethanol, and mixing and grinding under certain conditions. Then, the mixture is sintered under certain conditions. After sintering and natural cooling, the sintered product is refined and ground under certain conditions to obtain a manganese-doped calcium gallium compound, abbreviated as CGO-Mn.

[0020] In step 1, the conditions for mixing and grinding are that the mixing and grinding time is 0.5-1 hour; the conditions for refining and grinding are that the refining and grinding time is 5-10 minutes.

[0021] In step 1, the sintering conditions are as follows: under air conditions, the heating rate is 3-10℃ / min, the reaction sintering temperature is 1100-1300℃, and the sintering time is 4-6h.

[0022] Step 2, preparation of CGO-Mn-based stress luminescent material: First, epoxy resin and curing agent are mixed evenly without bubble generation to achieve a certain mass ratio, resulting in a resin mixture. Then, petrolatum is evenly applied to the inner wall of a polytetrafluoroethylene mold. Next, CGO-Mn obtained in Step 1 is evenly spread at the bottom of the mold to achieve a certain mass ratio with the resin mixture. Then, the resin mixture is added to the mold. After addition, the mold is allowed to stand under certain conditions. Finally, the mold is dried under certain conditions. After drying, the mold is demolded to obtain a block-shaped stress luminescent material based on manganese-doped calcium gallium compound, abbreviated as CGOM.

[0023] In step 2, the mass ratio of epoxy resin to curing agent is 10:1-3:1, and the mass ratio of CGO-Mn to resin mixture is 1:1-1:5.

[0024] In step 2, the conditions for settling are: settling temperature at room temperature and settling time of 5-30 minutes; the conditions for drying are: drying temperature of 60-80℃ and drying time of 2-4 hours.

[0025] An application of a triboluminescent material based on manganese-doped calcium gallium compound exhibits stress luminescence properties under friction conditions, emitting yellow light with a wavelength of 530-650 nm, and the strongest emission peak is at 577 nm.

[0026] The technical effects of this invention have been verified as follows:

[0027] XRD analysis revealed that the main phase of the manganese-doped calcium gallium compound triboluminescent material is CaGa4O7. The doping of manganese ions did not alter the crystal lattice structure. 1-x Mn 2+x Ga4O7 is a pure phase, with no second phase introduced.

[0028] SEM and EDS tests show that Ca 1-x Mn 2+ x Ga4O7 contains Ca, Ga, O, and Mn elements, and all elements are uniformly distributed and it is a single phase.

[0029] PLE and PL tests show that Ca 1-x Mn 2+ x Ga4O7 emits yellow light with wavelengths of 530nm-650nm, which is Mn 2+ of 4 T1(6S)- 6 A1 (4G) transition.

[0030] ML testing shows that Ca 1-x Mn 2+ x Ga4O7 exhibits no stress luminescence phenomenon in grinding stress luminescence tests and compressive stress luminescence tests, but it displays stress luminescence properties when the composite material is obtained by compounding it into an epoxy resin mixture and then subjected to tribo-stress luminescence tests.

[0031] Therefore, the present invention has the following advantages over the prior art:

[0032] 1. It has unique stress luminescence properties. Compared with references 1-4, it does not exhibit stress luminescence during grinding and compression, but it has high-brightness stress luminescence properties when rubbed after the composite epoxy resin mixture.

[0033] 2. The process is simple. Compared with the literature 1-3 in the background technology, there is no need to introduce an inert atmosphere during the preparation process. It can be obtained by direct sintering in an air atmosphere.

[0034] 3. Environmentally friendly: Compared with the sulfur-containing compound materials in references 1-3, calcium gallium compounds are environmentally friendly materials;

[0035] 4. Stable physical and chemical properties: Compared with the aluminate materials in reference 4, the calcium gallium compound has more stable physical and chemical properties and is less prone to deliquescence. Attached Figure Description

[0036] Figure 1 The XRD patterns of CGO-0.002Mn in Example 1, CGO-0.001Mn in Example 2, CGO-0.003Mn in Example 3, CGO-0.005Mn in Example 4, and CGO-0.01Mn in Example 5 are shown.

[0037] Figure 2 The images shown are SEM and EDS images of CGO-0.002Mn in Example 1.

[0038] Figure 3 The PLE and PL plots after normalization to CGO-0.002Mn are shown in Example 1.

[0039] Figure 4 The images show the stress-luminescence and photoluminescence patterns of CGOM-0.002 and CGO-0.002Mn after normalization in Example 1.

[0040] Figure 5 The image shows the luminescence test result of CGO-0.002Mn under grinding stress in Example 1.

[0041] Figure 6 These are the compressive stress luminescence test images for Example 1, Comparative Example 1, Comparative Example 2, and Comparative Example 3;

[0042] Figure 7 These are triboluminescence test images of Example 1, Comparative Example 1, Comparative Example 2, and Comparative Example 3;

[0043] Figure 8 These are triboelectric stress luminescence test images from Examples 2, 3, 4, and 5. Detailed Implementation

[0044] The present invention will be further described below with reference to specific embodiments and accompanying drawings, but this should not be construed as limiting the scope of protection of the present invention.

[0045] Example 1

[0046] A method for preparing a triboluminescent material based on a manganese-doped calcium gallium compound includes the following steps:

[0047] Step 1, based on the preparation of manganese-doped calcium gallium compounds, firstly, using the chemical formula Ca... 0.998 Mn 0.002 Ga4O7: 1.1589g CaCO3, 4.3495g Ga2O3 and 0.0027g MnCO3 were placed in a mortar, and 30mL of anhydrous ethanol was added. The mixture was then ground for 1 hour to obtain a mixed raw material. Then, the mixed raw material was sintered under air conditions with a heating rate of 3℃ / min, a reaction sintering temperature of 1200℃ and a sintering time of 6 hours. After sintering and natural cooling, the sintered product was ground for 10 minutes to obtain a manganese-doped calcium gallium compound, abbreviated as CGO-Mn. The product obtained in Example 1 was named CGO-0.002Mn.

[0048] To confirm the obtained CGO-0.002Mn phase, XRD analysis was performed. Test results... Figure 1 As shown, the characteristic peaks of CGO-0.002Mn are consistent with the standard peaks of CaGa4O7. The test results lead to the following two conclusions:

[0049] 1. The doping of manganese ions does not change the crystal lattice structure. The principle is based on the substitution principle of similar ionic radii. In the CaGa4O7 compound synthesized in this invention, Ca... 2+ With 5 O 2- The connection occupies a C2-symmetric 5-recombination site, while Ga 3+ With 4 O 2- The connection is distributed across two independent tetrahedral sites, Mn 2+ The ionic radii of each coordination site are (r = 0.75, CN = 5; r = 4, CN = 0.66), Ca 2+ The ionic radius is CN=5, Ga 2+ The ionic radius is CN = 4, therefore, Mn 2+ Replace Ca 2+ The position enters the lattice;

[0050] 2. The prepared CGO-0.002Mn is a pure phase, without the introduction of a second phase.

[0051] To further demonstrate the phase composition and single-phase structure of CGO-0.002Mn, SEM and EDS tests were performed. The test results are as follows: Figure 2 As shown, CGO-0.002Mn contains Ca, Ga, O and Mn elements, and all elements are uniformly distributed, which means it is a single phase.

[0052] To demonstrate the photoluminescence properties of CGO-0.002Mn, photoluminescence emission (PLE) and photoluminescence (PL) tests were performed. The test results are as follows: Figure 3 As shown, the excitation spectrum of CGO-0.002Mn was measured at a monitoring wavelength of 577 nm. Selecting the optimal excitation wavelength of 250 nm, the emission spectrum with wavelengths of 530-650 nm was obtained, which is the Mn... 2+ of 4 T1(6S)- 6 The A1 (4G) transition emits a yellow light.

[0053] To demonstrate the stress luminescence properties of CGO-0.002Mn, a grinding stress luminescence test was conducted. The specific test method involved placing CGO-0.002Mn in a mortar and subjecting it to pre-irradiation with a 254nm ultraviolet lamp for 2 minutes, followed by grinding to test its stress luminescence properties. The test results are as follows: Figure 5 As shown, CGO-0.002Mn did not exhibit stress luminescence during the grinding process. The test results indicate that CGO-0.002Mn does not possess stress luminescence properties under grinding conditions.

[0054] Step 2, preparation of CGO-Mn-based triboluminescent material: First, epoxy resin and curing agent are mixed evenly at a mass ratio of 3:1, without the generation of bubbles, to obtain a resin mixture. Then, petrolatum is evenly applied to the inner wall of a polytetrafluoroethylene mold. Next, at a mass ratio of 1:4 between CGO-0.002Mn obtained in Step 1 and the resin mixture, 1.5g of CGO-0.002Mn is evenly spread at the bottom of the mold, and then 6g of the resin mixture is added to the mold. After the addition is complete, the mold is allowed to stand at room temperature for 5 minutes. Finally, the mold is dried at 60℃ for 4 hours. After drying, the mold is demolded to obtain a block-shaped triboluminescent material based on manganese-doped calcium gallium compound, abbreviated as CGOM-0.002.

[0055] To demonstrate the stress-luminescence properties of CGOM-0.002, a conventional compressive stress-luminescence test was conducted. Specifically, after pre-radiation under the same conditions, CGOM-0.002 was compressed under a force of 2000 N to test its stress-luminescence properties. The test results are as follows: Figure 6 As shown, CGOM-0.002 did not exhibit stress luminescence during compression. The test results indicate that CGOM-0.002 does not possess stress luminescence properties under compression conditions.

[0056] To demonstrate that CGOM-0.002 possesses stress-induced luminescence properties, a tribo-stress luminescence test was conducted. The specific test method involved pre-irradiating CGOM-0.002 under the same conditions, followed by rubbing it with a frictional force of 10 N to test its stress-induced luminescence properties. The test results are as follows: Figure 7 As shown, the stress-luminescence spectrum of CGOM-0.002 is a broadband emission spectrum, and it shares the same luminescence center as photoluminescence. The test results indicate that CGOM-0.002 possesses stress-luminescence properties.

[0057] Further comparison with the results of the grinding stress luminescence performance test of CGO-0.002Mn obtained in step 1 and the compressive stress luminescence test of CGOM-0.002 obtained in step 2 shows that the test results are as follows: Figure 5As shown in Figure 6, under grinding conditions, CGO-0.002Mn, as a powder of stress-luminescent material (hereinafter referred to as powder), does not possess stress-luminescent properties. When combined with an epoxy resin matrix (which itself does not possess stress-luminescent properties), the resulting CGOM-0.002, as a bulk stress-luminescent material (hereinafter referred to as bulk), exhibits stress-luminescent properties under compression testing conditions, as shown in Figure 6. This can be simply summarized as the powder exhibiting stress-luminescence under frictional conditions after being combined into a bulk. In other words, there is an inconsistency between the powder and the bulk when stress-luminescent.

[0058] According to reference 1 (Zhou Y, Yang YL, Fan YT, et al. Intense red photoluminescence and mechanoluminescence from Mn 2+ -activated SrZnSO with alayered structure[J].Journal of Materials Chemistry C,2019,7(26):8070-8078.) Previous results from our research group indicate that conventional stress-luminescent materials SrZnSO with alayered structure... 2+ Powders, under grinding and compression conditions, also exhibit stress luminescence. This phenomenon serves as a criterion in the field for determining whether a new material possesses stress luminescence properties.

[0059] The inconsistency between the powder and bulk materials in stress luminescence indicates that the material of this invention differs substantially from the prior art in terms of stress luminescence mechanism.

[0060] To demonstrate the effect of manganese doping on the properties of stress-luminescent materials, Comparative Examples 1, 2, and 3 are provided. Based on the dopant ions with stress-luminescent properties described in existing literature in Table 1, Eu was used for doping. 3+ Pr 3+ and Sm 3+ The resulting composite material.

[0061] Table 1 Summary of doped ions with stress luminescence properties

[0062] compound Doped ions Stress-emitting color References SrZnOS <![CDATA[Mn 2+ ]]> red [1] <![CDATA[Ca2Al2SiO7]]> <![CDATA[Eu 3+ ]]> red [2] <![CDATA[LiNbO3]]> <![CDATA[Pr 3+ ]]> red [3] <![CDATA[Sr3Sn2O7]]> <![CDATA[Sm 3+ ]]> Orange [4]

[0063] in:

[0064] Reference 1 (Zhou Y, Yang Y L, Fan Y T, et al. Intense red photoluminescenceand mechanoluminescence from Mn 2+ -activated SrZnSO with a layered structure[J]. Journal of Materials Chemistry C, 2019, 7(26): 8070 - 8078.)

[0065] Reference 2 (Tiwari G, Brahme N, Sharma R, et al. Fracto - mechanoluminescenceand thermoluminescence properties of orange - red emitting Eu 3+ doped Ca2Al2SiO7 phosphors[J]. Journal of Luminescence, 2017, 183: 89 - 96.)

[0066] Reference 3 (Tu D, Xu C N, Yoshida A, et al. LiNbO3: Pr 3+ : a multipiezomaterial with simultaneous piezoelectricity and sensitive piezoluminescence[J]. Advanced Materials, 2017, 29(22): 1606914.)

[0067] Reference 4 (Kamimura S, Yamada H, Xu C N. Strong reddish - orange lightemission from stress - activated Sr n+1 Sn n O 3n+1 : Sm 3+ (n = 1, 2, ∞) with perovskite - related structures[J]. Applied Physics Letters, 2012, 101(9).)

[0068] Comparative Example 1

[0069] A method for preparing a composite material based on europium-doped calcium gallium compound, wherein the steps not specifically described are the same as the preparation method described in Example 1, except that the chemical formula of step 1 is Ca 0.998 Eu 0.002 The composite material obtained by adding Ga4O7, i.e., 1.1584g CaCO3, 4.3476g Ga2O3, and 0.0041g Eu2O3, is named CGOE-0.002.

[0070] To verify whether CGOE-0.002 possesses compressive stress luminescence properties, a compressive stress luminescence test was conducted. The test results are as follows: Figure 6 As shown, CGOE-0.002 did not exhibit stress luminescence during compression. The test results indicate that CGOP-0.002 does not possess compressive stress luminescence properties under compression conditions.

[0071] To further verify whether CGOE-0.002 possesses triboluminescence properties, triboluminescence tests were conducted. The test results are as follows: Figure 7 As shown, CGOE-0.002 does not exhibit stress luminescence. The test results indicate that CGOP-0.002 does not possess compressive stress luminescence properties under compression conditions.

[0072] In summary, doping calcium gallium compounds with Eu exhibiting stress luminescence properties... 3+ Stress-induced luminescence properties could not be obtained.

[0073] Comparative Example 2

[0074] A method for preparing a composite material based on praseodymium-doped calcium gallium compound, wherein the steps not specifically described are the same as the preparation method described in Example 1, except that the chemical formula of step 1 is Ca 0.998 Pr 0.002 Ga4O7, meaning the amounts of each raw material added are 1.1584g CaCO3, 4.3478g Ga2O3, and 0.0039g Pr6O. 11 The resulting composite material was named CGOP-0.002.

[0075] To verify whether CGOP-0.002 possesses compressive stress luminescence properties, a compressive stress luminescence test was conducted. The test results are as follows: Figure 6 As shown, CGOP-0.002 did not exhibit stress luminescence during compression. The test results indicate that CGOP-0.002 does not possess compressive stress luminescence properties under compression conditions.

[0076] To further verify whether CGOP-0.002 possesses triboluminescence properties, a triboluminescence test was conducted. The test results are as follows: Figure 7As shown, CGOP-0.002 does not exhibit stress luminescence. The test results indicate that CGOP-0.002 does not possess compressive stress luminescence properties under compression conditions.

[0077] In summary, doping calcium gallium compounds with Pr exhibiting stress luminescence properties... 3+ Stress-induced luminescence properties could not be obtained.

[0078] Comparative Example 3

[0079] A method for preparing a composite material based on samarium-doped calcium gallium compound, wherein the steps not specifically described are the same as the preparation method described in Example 1, except that the chemical formula of step 1 is Ca 0.998 Sm 0.002 The composite material obtained by adding Ga4O7, i.e., 1.1584g CaCO3, 4.3476g Ga2O3 and 0.0040g Sm2O3, is named CGOS-0.002.

[0080] To verify whether CGOS-0.002 possesses compressive stress luminescence properties, a compressive stress luminescence test was conducted. The test results are as follows: Figure 6 As shown, CGOS-0.002 did not exhibit stress luminescence during compression. The test results indicate that CGOS-0.002 does not possess compressive stress luminescence properties under compression conditions.

[0081] To further verify whether CGOS-0.002 possesses triboluminescence properties, triboluminescence tests were conducted. The test results are as follows: Figure 7 As shown, CGOS-0.002 does not exhibit stress luminescence. The test results indicate that CGOS-0.002 does not possess compressive stress luminescence properties under compression conditions.

[0082] In summary, doping calcium gallium compounds with Sm exhibits stress luminescence properties... 3+ Stress-induced luminescence properties could not be obtained.

[0083] By comparing Example 1 with Comparative Examples 1, 2, and 3, it can be seen that CGOE-0.002, CGOP-0.002, and CGOS-0.002, prepared by introducing ions with the same stress luminescence properties, cannot achieve stress luminescence properties. Only the present invention, through Mn doping, achieves this property. 2+ Only the prepared CGOM-0.002 exhibits stress luminescence properties, meaning that in calcium gallium compounds, not all doped ions that can act as luminescent centers can achieve stress luminescence. The principle is that Mn... 2+ ionic radius and Eu 3+ Pr 3+ 、Sm 3+The ionic radii differ significantly, resulting in a large difference in the optical band gap of the material after entering the crystal lattice, ultimately achieving stress luminescence properties.

[0084] To demonstrate the effect of manganese doping on the performance of stress-luminescent materials, Examples 2, 3, 4, and 5 are provided, with the chemical formula Ca... 0.999 Mn 0.001 Ga4O7, Ca 0.997 Mn 0.003 Ga4O7, Ca 0.995 Mn 0.005 Ga4O7 and Ca 0.99 Mn 0.010 Ga4O7.

[0085] Example 2

[0086] A method for preparing a triboluminescent material based on a manganese-doped calcium gallium compound, wherein the steps unless otherwise specified are the same as those described in Example 1, the difference being that the chemical formula of step 1 is Ca 0.999 Mn 0.001 Ga4O7, i.e., the amount of each raw material added is 1.1601g CaCO3, 4.3497g Ga2O3, and 0.0013g MnCO3, the product is named CGO-0.001Mn, and the stress luminescent material obtained in step 2 is named CGOM-0.001.

[0087] XRD test results of CGO-0.001Mn Figure 1 As shown, the characteristic peak of CGO-0.001Mn is consistent with the standard peak of CaGa4O7, meaning the test results are the same as in Example 1.

[0088] The triboluminescence test results of CGOM-0.001 are as follows: Figure 8 As shown, it is the same as CGOM-0.002 obtained in Example 1. Test results show that CGOM-0.001 possesses stress luminescence properties.

[0089] Example 3

[0090] A method for preparing a triboluminescent material based on a manganese-doped calcium gallium compound, wherein the steps unless otherwise specified are the same as those described in Example 1, the difference being that the chemical formula of step 1 is Ca 0.997 Mn 0.003 Ga4O7, i.e., the amount of each raw material added is 1.1577g CaCO3, 4.3494g Ga2O3, and 0.0040g MnCO3, the product is named CGO-0.003Mn, and the stress luminescent material obtained in step 2 is named CGOM-0.003.

[0091] XRD test results of CGO-0.003Mn Figure 1 As shown, the characteristic peak of CGO-0.003Mn is consistent with the standard peak of CaGa4O7, meaning the test results are the same as in Example 1.

[0092] The triboluminescence test results of CGOM-0.003 are as follows: Figure 8 As shown, it is the same as CGOM-0.002 obtained in Example 1. Test results show that CGOM-0.003 possesses stress luminescence properties.

[0093] Example 4

[0094] A method for preparing a triboluminescent material based on a manganese-doped calcium gallium compound, wherein the steps unless otherwise specified are the same as those described in Example 1, the difference being that the chemical formula of step 1 is Ca 0.995 Mn 0.005 Ga4O7, i.e., the amount of each raw material added is 1.1553g CaCO3, 4.3491g Ga2O3, and 0.0067g MnCO3, the product is named CGO-0.005Mn, and the stress luminescent material obtained in step 2 is named CGOM-0.005.

[0095] XRD test results of CGO-0.005Mn Figure 1 As shown, the characteristic peak of CGO-0.005Mn is consistent with the standard peak of CaGa4O7, meaning the test results are the same as in Example 1.

[0096] The triboluminescence test results of CGOM-0.005 are as follows: Figure 8 As shown, it is the same as CGOM-0.002 obtained in Example 1. Test results show that CGOM-0.005 possesses stress luminescence properties.

[0097] Example 5

[0098] A method for preparing a triboluminescent material based on a manganese-doped calcium gallium compound, wherein the steps unless otherwise specified are the same as those described in Example 1, the difference being that the chemical formula of step 1 is Ca 0.99 Mn 0.010 Ga4O7, i.e., the amount of each raw material added is 1.1493g CaCO3, 4.3483g Ga2O3, and 0.0133g MnCO3, the product is named CGO-0.010Mn, and the stress luminescent material obtained in step 2 is named CGOM-0.010.

[0099] XRD test results of CGO-0.010Mn Figure 1As shown, the characteristic peak of CGO-0.010Mn is consistent with the standard peak of CaGa4O7, meaning the test results are the same as in Example 1.

[0100] The triboluminescence test results of CGOM-0.01 are as follows: Figure 7 As shown, it is the same as CGOM-0.002 obtained in Example 1. Test results show that CGOM-0.010 possesses stress luminescence properties.

[0101] Examples 1-5 demonstrate that stress-luminescent materials based on manganese-doped calcium gallium compounds can achieve stress-luminescence properties within the range of manganese ion doping concentration of 0.001-0.010 mol.

Claims

1. A triboluminescent material based on a manganese-doped calcium gallium compound, characterized in that: Ca 1-x Mn x Ga4O7 stress luminescence fluorescent powder, wherein x is the percentage of substance by amount, and 0.001<=x<=0.01, and the stress luminescence material is obtained after compounding with a resin mixing solution made of epoxy resin and curing agent. The Ca 1-x Mn x Ga4O7 is a single phase structure, and at the same time, Mn 2+ instead of Ca 2+ enters the lattice The Ca 1-x Mn x Ga4O7 has photoluminescence performance, the optimal excitation wavelength is 250 nm, and the light emission color is yellow. The stress luminescence phosphor does not have stress luminescence performance under grinding conditions; the stress luminescence material has stress luminescence performance under friction conditions.

2. The manganese-doped calcium gallium compound-based triboluminescent material according to claim 1, characterized in that: The stress luminescence material has stress luminescence performance under friction conditions, emits yellow light with a wavelength of 530-650 nm, and has a strongest emission peak of 577 nm.

3. A method for producing the manganese-doped calcium gallium compound-based triboluminescent material according to claim 1, characterized by: The method comprises the following steps: Step 1, preparation of manganese-doped calcium gallate compound, first, Ca 1-x Mn x Ga4O7, CaCO3, Ga2O3 and MnCO3 are placed in a mortar, mixed and ground after adding anhydrous ethanol dropwise, to obtain a mixed raw material, then the mixed raw material is sintered, and after sintering and natural cooling, the obtained sintered product is finely ground to obtain a manganese-doped calcium gallate compound, referred to as CGO-Mn; In the step 1, the mixing and grinding conditions are that the mixing and grinding time is 0.5-1 h; and the refining grinding conditions are that the refining grinding time is 5-10 min. In the step 1, the sintering conditions are that the heating rate is 3-10℃ / min under air conditions, the reaction sintering temperature is 1100-1300℃, and the sintering time is 4-6 h; In step 2, the preparation of the stress luminescence material based on CGO-Mn, first, the epoxy resin and the curing agent are mixed uniformly and no air bubbles are generated, to obtain a resin mixture, then, the Vaseline is uniformly applied to the inner wall of a polytetrafluoroethylene mold, then, the CGO-Mn is uniformly laid on the bottom of the mold, then, the resin mixture is added to the mold, after the addition is completed, the mold is placed, finally, the mold is dried, after the drying is completed, the mold is demolded, to obtain a block-shaped stress luminescence material based on manganese-doped calcium gallium compound, which is referred to as CGOM for short; In the step 2, the mass ratio of the epoxy resin to the curing agent is 10:1-3:1, and the mass ratio of the CGO-Mn to the resin mixture is 1:1-1:5; In the step 2, the standing conditions are that the standing temperature is under room temperature conditions, and the standing time is 5-30 min; the drying conditions are that the drying temperature is 60-80℃, and the drying time is 2-4 h.

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