Phase-regulated calcium borate-based multicolor mechanoluminescent material as well as preparation method and application of phase-regulated calcium borate-based multicolor mechanoluminescent material

Abstract

The invention belongs to the technical field of mechanoluminescent materials, and particularly discloses a phase-regulated calcium borate-based multicolor mechanoluminescent material as well as a preparation method and application thereof, the phase-regulated calcium borate-based multicolor mechanoluminescent material is manganese-doped calcium borate, and the molar ratio x of boric acid to calcium oxide is 1.00-2.00. The mechanoluminescent material is prepared from the following raw materials in mole fraction: 49.75 percent to 66.33 percent of H3BO3, 33.17 percent to 49.75 percent of CaO and 0.5 percent of MnCO3. The calcium borate-based mechanoluminescent material is prepared by taking boric acid and calcium oxide as raw materials and Mn as an activating agent, the preparation method of the mechanoluminescent material adopts a high-temperature solid-phase method, the preparation process is simple, the sintering temperature is low, the mechanoluminescent material can be sintered in air, and conditions are easy to control; no toxic gas is generated in the preparation process, and no pollution is caused to the environment; the simple, convenient, low-temperature and protective atmosphere-free synthesis of the ML material based on calcium borate is realized in a phase regulation mode.

Description

Technical Field

[0001] This invention belongs to the field of mechanoluminescent materials technology, specifically a phase-controlled calcium borate-based multicolor mechanoluminescent material, its preparation method, and its application. Background Technology

[0002] Mechanoluminescence refers to the phenomenon of a substance emitting light dynamically when subjected to external mechanical forces such as pressure, stretching, friction, vibration, and ultrasound. In recent years, due to its dynamic and stimulus-response characteristics, mechanoluminescence has attracted much attention in fields such as anti-counterfeiting, smart skin, wearable devices, and structural health monitoring.

[0003] Existing mechanoluminescent materials have the following main drawbacks in their preparation process:

[0004] (1) Uneven particle distribution: Micron-sized mechanoluminescent particles are difficult to achieve uniform distribution in polymer substrates, resulting in decreased transparency and severe light scattering, which affects the transmission efficiency of mechanoluminescence signals.

[0005] (2) Poor chemical stability: Organic polymer substrate materials are easily affected by the environment when exposed for a long time, and have poor physical and chemical stability, which may lead to performance degradation or failure in practical applications.

[0006] (3) The preparation process is complex.

[0007] The preparation of high-performance mechanoluminescent materials usually involves high-temperature solid-state sintering (typically requiring temperatures exceeding 1000°C and a protective atmosphere), and the optimization of parameters such as doping concentration and deformation frequency is necessary to balance performance.

[0008] In view of the above problems, this invention is proposed. Summary of the Invention

[0009] This invention achieves a simple, low-temperature, and atmosphere-free synthesis of calcium borate-based ML materials by adjusting the stoichiometric ratio of boric acid (H3BO3) to calcium oxide (CaO) to regulate the phase transition between Ca2B2O5 and CaB2O4. These materials contain manganese ions (Mn). 2+ The tetrahedral and octahedral coordination structures in different phases allow for tunable mechanoluminescence, ranging from green to orange (535-605 nm). When incorporated into polydimethylsiloxane elastomers, these materials exhibit excellent multicolor mechanoluminescence properties, suitable for multi-level optical encryption and motion visualization. Encrypted information hidden under sunlight or ultraviolet light can only be decrypted through mechanoluminescence activation, while the color changes induced by mechanoluminescence enable real-time monitoring of joint movements.

[0010] The first objective of this invention is to provide a phase-controlled calcium borate-based multicolor mechanoluminescent material, wherein the mechanoluminescent material is calcium borate doped with manganese, and the molar ratio of boric acid to calcium oxide raw material is x, where x = 1.00-2.00.

[0011] Preferably, the mechanoluminescent material is Ca2B2O5:Mn. 2+ (x=1.00), CaB2O4:Mn 2+ (x=2.00) and calcium borate (x=1.20, 1.25, 1.35; x=H3BO3:CaO).

[0012] Preferably, the mechanoluminescent material is Ca2B2O5:Mn 2+ (x=1.00), CaB2O4:Mn 2+ (x=2.00) and calcium borate (x=1.20, 1.25, 1.35; x=H3BO3:CaO).

[0013] Using the above technical solution, different samples were sintered according to different raw material ratios (x=H3BO3:CaO).

[0014] Preferably, the mechanoluminescent material is prepared from the following molar fractions of raw materials, based on 100% of the total content: 49.75%-66.33% H3BO3, 33.17%-49.75% CaO, and the balance MnCO3.

[0015] A second objective of this invention is to provide a method for preparing the above-mentioned phase-modulated calcium borate-based multicolor mechanoluminescent material, comprising the following steps:

[0016] S1: Grind and mix H3BO3, CaO and MnCO3 to obtain a mixture;

[0017] S2: The mixture obtained in step S1 is sintered in air at 900 °C for 6 h, and then ground to obtain a multicolor mechanoluminescent material, calcium borate doped with manganese.

[0018] Preferably, the sintering method of the mixture in step S2 is as follows: heat up to 300 °C at 20 °C / min, then heat up to 900 °C at 10 °C / min for 6 h, then cool down to 200 °C at 20 °C / min, and finally cool naturally to room temperature.

[0019] A third objective of this invention is to provide applications of the aforementioned phase-modulated calcium borate-based multicolor mechanoluminescent materials.

[0020] Preferably, the application is in the preparation of mechanoluminescent thin films and mechanoluminescence visualization.

[0021] Preferably, the method for preparing the mechanoluminescent thin film is as follows: the mechanoluminescent material and PDMS colloid are mixed evenly to obtain a mixed liquid, the mixed liquid is evenly coated in a mold, sealed and covered, and then heated to cure the colloid to obtain multicolor calcium borate mechanoluminescent thin films with different raw material ratios.

[0022] Preferably, the metronome material comprises 35%-45% by mass in the mixed liquid.

[0023] Preferably, the heating and curing temperature is 80 ℃ and the curing time is 0.5-1.5 h.

[0024] The beneficial effects of this invention are:

[0025] (1) This invention uses boric acid (H3BO3) and calcium oxide (CaO) as raw materials and Mn as an activator to prepare calcium borate-based mechanoluminescent materials. The preparation method of the mechanoluminescent materials of this invention adopts a high-temperature solid-state method, which is simple to prepare, has a low sintering temperature, and can be sintered in air, and the conditions are easy to control. No toxic gases are generated during the preparation process, and there is no pollution to the environment. Through phase regulation, the simple, low-temperature synthesis of calcium borate-based ML materials without the need for a protective atmosphere is realized.

[0026] (2) Based on the rich phase structure of calcium borate (Ca2B2O5, CaB2O4) and the different coordination forms of manganese ions (tetracoordinate, octacoordinate), the present invention synthesizes calcium borate mechanoluminescent materials with different mechanoluminescent colors by adjusting the stoichiometric ratio of boric acid and calcium oxide in the synthesis raw materials.

[0027] (3) The phase-controlled calcium borate (x=1.00-2.00) multicolor mechanoluminescent material of the present invention does not require prior ultraviolet irradiation. After mixing and curing calcium borate (x=1.00-2.00) with PDMS colloid, the prepared mechanoluminescent film exhibits multicolor mechanoluminescence within the elastic limit of the material (e.g., Figure 6 As shown), it exhibits strong mechanoluminescence under mechanical action (such as stretching, friction, etc.). Figure 9 As shown), it can be directly observed with the naked eye in a dark environment, and is used in the field of visualization sensing (such as...). Figure 6 and Figure 9 It has a wide range of applications. Attached Figure Description

[0028] Figure 1 The XRD pattern of calcium borate (x=1.00-2.00), a mechanoluminescent material.

[0029] Figure 2 PL excitation-emission spectral mapping of Ca2B2O5:0.5%Mn prepared in Example 1.

[0030] Figure 3 PL excitation-emission spectral mapping of CaB2O4:0.5%Mn prepared in Example 5.

[0031] Figure 4 The mechanoluminescence spectrum of calcium borate (x=1.20), a mechanoluminescent material prepared in Example 2.

[0032] Figure 5 The mechanoluminescence spectra of calcium borate (x=1.00-2.00), the mechanoluminescent material prepared in Examples 1-5.

[0033] Figure 6 Mechanoluminescent photographs of calcium borate (x=1.00-2.00), the mechanoluminescent material prepared in Examples 1-5.

[0034] Figure 7 CIE diagrams of calcium borate (x=1.00-2.00), the mechanoluminescent material prepared in Examples 1-5.

[0035] Figure 8 The images show the mechanoluminescence spectra of the mechanoluminescent material prepared in Example 1 with different ratios of PDMS.

[0036] Figure 9 The images show the luminescence of the mechanoluminescent material prepared in Example 2 under different stimuli. Detailed Implementation

[0037] To make the technical means, creative features, objectives and effects of this invention easier to understand, the invention will be further described below in conjunction with specific embodiments.

[0038] H3BO3, CaO, and MnCO3 were selected as raw materials, and the corresponding elements of H3BO3, CaO, and MnCO3 were weighed according to their composition and proportion. The raw materials of H3BO3, CaO, and MnCO3 were manually ground and mixed to obtain a mixture. The mixture was sintered in air at 900 °C for 6 h. Grinding was then carried out to obtain calcium borate-doped manganese mechanoluminescent materials with different raw material ratios. These materials were mixed evenly with PDMS colloid to obtain a mixed liquid. The mixed liquid was evenly coated in a polytetrafluoroethylene mold, covered with plastic wrap, and then heated to cure the colloid, thus obtaining a phase-modulated calcium borate-based multicolor mechanoluminescent film.

[0039] Furthermore, the phase-controlled calcium borate-based multicolor mechanoluminescent material is prepared from the following raw materials in the following molar fractions: 1 mol H3BO3, 1 mol CaO and 0.5% mol MnCO3.

[0040] Furthermore, the phase-modulated calcium borate-based multicolor mechanoluminescent material is prepared from the following raw materials in the following molar fractions: 1.2 mol H3BO3, 1 mol CaO and 0.5% mol MnCO3.

[0041] Furthermore, the phase-controlled calcium borate-based multicolor mechanoluminescent material is prepared from the following raw materials in the following molar fractions: 1.25 mol H3BO3, 1 mol CaO and 0.5% mol MnCO3.

[0042] Furthermore, the phase-modulated calcium borate-based multicolor mechanoluminescent material is prepared from the following raw materials in the following molar fractions: 1.35 mol H3BO3, 1 mol CaO and 0.5% mol MnCO3.

[0043] Furthermore, the phase-controlled calcium borate-based multicolor mechanoluminescent material is prepared from the following raw materials in the following molar fractions: 2 mol H3BO3, 1 mol CaO and 0.5% mol MnCO3.

[0044] The following detailed description is provided in conjunction with specific embodiments.

[0045] Example 1: Ca2B2O5:0.5%Mn 2+ (x=1.00) as an example

[0046] A method for preparing a phase-controlled calcium borate mechanoluminescent material includes the following steps:

[0047] S1: H3BO3, CaO, and MnCO3 with a purity of 99.8wt% were ground and mixed to obtain a mixed powder; based on the molar fraction of the mixed powder as 100%, H3BO3 accounted for 49.75%, CaO accounted for 49.75%, and MnCO3 accounted for 0.5%;

[0048] S2: The mixture powder obtained in step S1 is sintered in air at 900 ℃ for 6 h, then ground to obtain the phase-controlled calcium borate mechanoluminescent material Ca2B2O5:0.5%Mn. 2+ .

[0049] Preparation method of metronidized thin film: The Ca2B2O5:0.5%Mn obtained in step S2 is used... 2+ Methimilastic material and PDMS colloid were mixed evenly to obtain a mixed liquid with a mass percentage of 30%-35%. The mixed liquid was uniformly coated into a mold, covered with plastic wrap, and cured at 80 °C for 50 min to obtain Ca2B2O5:0.5%Mn. 2+ Methluminescent thin films.

[0050] Example 2: Taking calcium borate (x=1.20) as an example

[0051] A method for preparing a phase-controlled calcium borate mechanoluminescent material includes the following steps:

[0052] S1: High-purity H3BO3, CaO, and MnCO3 are ground and mixed to obtain a mixed powder; based on the molar fraction of the mixed powder as 100%, H3BO3 accounts for 54.27%, CaO accounts for 45.23%, and MnCO3 accounts for 0.5%;

[0053] S2: The mixture powder obtained in step S1 is placed in air at a temperature of 900 ℃ for high-temperature sintering for 6 h, and then ground to obtain phase-controlled calcium borate metronome material calcium borate (x=1.20).

[0054] Preparation method of mechanoluminescent film: The calcium borate (x=1.20) mechanoluminescent material obtained in step S2 is mixed with PDMS colloid to obtain a mixed liquid with a mass percentage of 30%-35%. The mixed liquid is uniformly coated in a mold, covered with plastic wrap, and heated to 80 ℃ for 50 min to obtain calcium borate (x=1.20) mechanoluminescent film.

[0055] Example 3: Taking calcium borate (x=1.25) as an example

[0056] A method for preparing a phase-controlled calcium borate mechanoluminescent material includes the following steps:

[0057] S1: High-purity H3BO3, CaO, and MnCO3 are ground and mixed to obtain a mixed powder; based on the molar fraction of the mixed powder as 100%, H3BO3 accounts for 55.28%, CaO accounts for 44.22%, and MnCO3 accounts for 0.5%;

[0058] S2: The mixture powder from step S1 is placed in air at a temperature of 900 ℃ for 6 h for high-temperature sintering, and then ground to obtain phase-controlled calcium borate mechanoluminescent material calcium borate (x=1.25).

[0059] Preparation method of mechanoluminescent film: The calcium borate (x=1.25) mechanoluminescent material obtained in step S2 is mixed evenly with PDMS colloid to obtain a mixed liquid with a mass percentage of 30%-35%. The mixed liquid is evenly coated in a mold, covered with plastic wrap, and heated to 80 ℃ for 50 min to obtain calcium borate (x=1.25) mechanoluminescent film.

[0060] Example 4: Taking calcium borate (x=1.35) as an example

[0061] A method for preparing a phase-controlled calcium borate mechanoluminescent material includes the following steps:

[0062] S1: High-purity H3BO3, CaO, and MnCO3 are ground and mixed to obtain a mixed powder; based on the molar fraction of the mixed powder as 100%, H3BO3 accounts for 57.16%, CaO accounts for 42.34%, and MnCO3 accounts for 0.5%;

[0063] S2: The mixture powder obtained in step S1 is placed in air at a temperature of 900 ℃ for high-temperature sintering for 6 h, and then ground to obtain phase-controlled calcium borate metronome material calcium borate (x=1.35).

[0064] Preparation method of mechanoluminescent film: The calcium borate (x=1.35) mechanoluminescent material obtained in step S2 is mixed evenly with PDMS colloid to obtain a mixed liquid with a mass percentage of 30%-35%. The mixed liquid is evenly coated in a mold, covered with plastic wrap, and heated to 80 ℃ for 50 min to obtain calcium borate (x=1.35) mechanoluminescent film.

[0065] Example 5: CaB2O4:0.5%Mn 2+ (x=2.00) as an example

[0066] A method for preparing a phase-controlled calcium borate mechanoluminescent material includes the following steps:

[0067] S1: High-purity H3BO3, CaO, and MnCO3 are ground and mixed to obtain a mixed powder; based on the molar fraction of the mixed powder as 100%, H3BO3 accounts for 66.33%, CaO accounts for 33.17%, and MnCO3 accounts for 0.5%;

[0068] S2: The mixture powder obtained in step S1 is sintered in air at 900 ℃ for 6 h, then ground to obtain the phase-controlled calcium borate mechanoluminescent material CaB2O4:0.5%Mn. 2+ .

[0069] Method for preparing metronic light-emitting thin films: The CaB2O4:0.5%Mn obtained in step S2 is used... 2+ Methimilastic material and PDMS colloid were mixed evenly to obtain a mixed liquid with a mass percentage of 30%-35%. The mixed liquid was evenly coated into a mold, covered with plastic wrap, and cured at 80 °C for 50 min to obtain CaB2O4:0.5%Mn. 2+ Methluminescent thin films.

[0070] Figure 1 The XRD patterns are of the mechanoluminescent materials calcium borate doped with manganese (x=1.00-2.00) prepared in Examples 1-5. Figure 1The XRD pattern matched well with the PDF standard card (JCDP#22-0139), but as the stoichiometric ratio increased from 1.00 to 2.00, the XRD pattern changed, and peaks from the standard card (JCDP#32-0155) appeared, which matched well with the PDF standard card (JCDP#32-0155).

[0071] Figure 2 The PL excitation-emission spectrum mapping of the mechanoluminescent material Ca2B2O5:0.5%Mn prepared in Example 1 shows that the optimal excitation wavelength is 340nm, which exhibits excitation dependence. It also demonstrates that Ca2B2O5:0.5%Mn emits light at 605nm.

[0072] Figure 3 The PL excitation-emission spectral mapping of the mechanoluminescent material CaB2O4:0.5%Mn prepared in Example 5 shows that the optimal excitation wavelength is 320 nm, and excitation dependence is observed. These results further demonstrate that phase modulation can achieve different Mn values. 2+ The coordination environment enables multicolor emission, and the luminescence of CaB2O4:0.5%Mn at 535 nm is demonstrated.

[0073] Figure 4 The image shows the mechanoluminescence of the calcium borate-doped manganese (x=1.20) material prepared in Example 2. As can be seen from the image, when the stretching test is performed using a linear motor, the mechanoluminescence intensity of the calcium borate-doped manganese increases with the increase of strain from 20% to 100%.

[0074] Figure 5 The images show the mechanoluminescence of calcium borate (x=1.00-2.00) prepared in Examples 1-5. As can be seen from the images, the mechanoluminescence color gradually changes from orange-red to green as the raw material ratio x increases from 1.00 to 2.00.

[0075] Figure 6 Photographs showing the mechanoluminescent color changes of calcium borate (x=1.00-2.00), the mechanoluminescent material prepared in Examples 1-5.

[0076] Figure 7 The CIE coordinates are the corresponding values ​​for the mechanoluminescent color changes of calcium borate (x=1.00-2.00) prepared in Examples 1-5.

[0077] Figure 8The images show the mechanoluminescence spectra of the mechanoluminescent material prepared in Example 1 with different ratios of PDMS. As the ratio of powder to PDMS increased from 1:5 to 1:2, the mechanoluminescence (ML) intensity of the composite elastomer significantly increased. However, when the ratio was further increased to 1:1, the ML intensity decreased. This can be explained by the fact that the enhanced ML of the composite elastomer originates from the increase in sample content (calcium borate), but when the sample content exceeds a certain limit, the effective contact between the sample (calcium borate) and PDMS decreases, leading to a weakening of interfacial interactions within the composite elastomer, thus reducing luminescence.

[0078] Figure 9 The images shown are mechanoluminescence photographs of Example 2 under different stimuli, demonstrating that the sample can exhibit mechanoluminescence under both stretching and friction stimuli.

[0079] The foregoing has shown and described the basic principles, main features, and advantages of the present invention. It will be apparent to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above, and that the invention can be implemented in other specific forms without departing from its spirit or basic characteristics. Therefore, the embodiments should be considered exemplary and non-limiting in all respects, and the scope of the invention is defined by the appended claims rather than the foregoing description. Thus, it is intended that all variations falling within the meaning and scope of equivalents of the claims be included within the present invention.

[0080] Furthermore, it should be understood that although this specification describes embodiments, not every embodiment contains only one independent technical solution. This narrative style is merely for clarity. Those skilled in the art should consider the specification as a whole, and the technical solutions in each embodiment can also be appropriately combined to form other embodiments that can be understood by those skilled in the art.

Claims

1. A phase-controlled calcium borate-based multicolor mechanoluminescent material, characterized in that, The mechanoluminescent material is calcium borate doped with manganese, and the molar ratio of boric acid to calcium oxide raw material is x, where x = 1.00-2.

00.

2. The phase-controlled calcium borate-based multicolor mechanoluminescent material according to claim 1, characterized in that, The mechanoluminescent material is Ca2B2O5:Mn 2+ (x=1.00), CaB2O4:Mn 2+ (x=2.00) and calcium borate (x=1.20, 1.25, 1.35).

3. The phase-controlled calcium borate-based multicolor mechanoluminescent material according to claim 2, characterized in that, The mechanoluminescent material is prepared from the following molar fractions of raw materials: 49.75%-66.33% H3BO3, 33.17%-49.75% CaO and the balance MnCO3.

4. A method for preparing the phase-modulated calcium borate-based multicolor mechanoluminescent material as described in any one of claims 1-3, characterized in that, Includes the following steps: S1: Grind and mix H3BO3, CaO and MnCO3 to obtain a mixture; S2: The mixture obtained in step S1 is sintered in air at 900 °C for 6 h, and then ground to obtain a multicolor mechanoluminescent material, calcium borate doped with manganese.

5. The method for preparing a phase-controlled calcium borate-based multicolor mechanoluminescent material as described in claim 4, characterized in that, The sintering method for the mixture in step S2 is as follows: heat up to 300 ℃ at 20 ℃ / min, then heat up to 900 ℃ at 10 ℃ / min and sinter for 6 h, then cool down to 200 ℃ at 20 ℃ / min, and finally cool naturally to room temperature.

6. An application of the phase-controlled calcium borate-based multicolor mechanoluminescent material as described in claims 1-3.

7. The application of the phase-controlled calcium borate-based multicolor mechanoluminescent material as described in claim 6, characterized in that, Applications in the preparation of mechanoluminescent thin films and mechanoluminescence visualization.

8. The application of the phase-controlled calcium borate-based multicolor mechanoluminescent material as described in claim 7, characterized in that, The method for preparing the mechanoluminescent thin film is as follows: the mechanoluminescent material is mixed with PDMS colloid to obtain a mixed liquid, the mixed liquid is uniformly coated in a mold, sealed and covered, and then heated to cure the colloid to obtain multicolor calcium borate mechanoluminescent thin films with different raw material ratios.

9. The application of the phase-controlled calcium borate-based multicolor mechanoluminescent material as described in claim 8, characterized in that, In the mixed liquid, the mass percentage of the metronome is 30%-35%.

10. The application of the phase-controlled calcium borate-based multicolor mechanoluminescent material as described in claim 8, characterized in that, The heating and curing temperature is 80 ℃, and the curing time is 0.5-1.5 h.

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