Rod-like crystal type mechanoluminescence powder and mechanoluminescence elastic composite material and preparation method thereof

Abstract

The application provides a rod crystal type mechanoluminescence powder and a mechanoluminescence elastic composite material and a preparation method thereof, and relates to the technical field of mechanoluminescence materials. 0.6 Sr 0.4 Al2Si2O8:xEu 2+ (0.005<=x<=0.025) stoichiometric ratio, CaCO3, SrCO3, HNTs and Eu2O3 are weighed and mixed to obtain a mixture; the mixture is sequentially subjected to pre-burning, first grinding, sintering and second grinding to obtain the mechanoluminescence powder. 0.6 Sr 0.4 Al2Si2O8:Eu 2+ The application uses HNTs with a nanotube structure as an Al / Si matrix to prepare Ca The confined effect of the HNTs structure and the increase of oxygen vacancies in the material preparation process are used to improve the photoluminescence and mechanoluminescence performance of the mechanoluminescence powder.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of mechanoluminescence materials, and particularly relates to a rod crystal type mechanoluminescence powder and a mechanoluminescence elastic composite material and a preparation method thereof. BACKGROUND

[0002] Long persistent luminescence (LPL) materials, as a special photoluminescence energy-saving material, have a wide range of applications in the fields of display, biomedical, energy and environmental engineering. Silicates are generally considered as the main candidate for the matrix material in LPL materials, and aluminum matrix as the matrix material of LPL has excellent chemical stability and high excitation efficiency. Therefore, researchers combine the advantages of silicate and aluminate matrix, integrate the beneficial properties of the two materials, and finally further optimize the overall performance of the LPL system. For example, SrAl2Si2O8:Eu 2+ ,Dy 3+ ,CaAl2Si2O8:Eu 2+ , etc.

[0003] Chemical substitution is an important concept for designing new materials and improving the functional properties of known compounds. Mechanoluminescence (ML) is a luminescence behavior of materials under mechanical force stimulation, which can directly convert mechanical energy into light energy, and bridge the microstructure and macroscopic material performance through photons. In the field of mechanoluminescence, partial substitution of cations can change the crystal structure and adjust the luminescence properties in a predictable way. By partially substituting Sr 2+ for Ca 2+ , the degree of disorder of atoms in the crystal lattice is enhanced, which can improve the mechanoluminescence intensity of CaAl2Si2O8:Eu 2+ , and the local change of crystal symmetry caused by Sr 2+ substitution is the key to the enhancement of luminescence. However, the photoluminescence and mechanoluminescence performance of the mechanoluminescence material obtained by this doping method is still low. SUMMARY

[0004] Therefore, the purpose of the present application is to provide a rod crystal type mechanoluminescence powder and a mechanoluminescence elastic composite material and a preparation method thereof. The present application uses halloysite nanotubes as Al / Si matrix, and the photoluminescence and mechanoluminescence performance of the obtained mechanoluminescence powder is obviously improved.

[0005] In order to achieve the above-mentioned application purposes, the present application provides the following technical solutions:

[0006] The present application provides a preparation method of a rod crystal type mechanoluminescence powder, comprising the following steps:

[0007] According to the chemical formula Ca 0.6 Sr 0.4 Al2Si2O8:xEu2+ CaCO3, SrCO3, halloysite nanotubes and Eu2O3 in stoichiometric ratio, to obtain a mixture; the chemical formula of the Ca 0.6 Sr 0.4 Al2Si2O8:xEu 2+ 0.005≤x≤0.025, and the halloysite nanotubes are calculated based on Al2O3 and SiO2;

[0008] The mixture is sequentially pre-fired, first ground, sintered and second ground to obtain the rod crystal type piezoluminescent powder; and the sintering is performed in a mixed atmosphere of hydrogen and inert gas.

[0009] Preferably, the halloysite nanotubes are pretreated before the mixing, and the pretreatment method is: the halloysite nanotubes are mixed with ethanol, subjected to microwave treatment and then dried.

[0010] Preferably, the mixing method is: the CaCO3, SrCO3, halloysite nanotubes and Eu2O3 are wet ground and then dried.

[0011] Preferably, the pre-firing temperature is 600-900℃, and the time is 3-5h.

[0012] Preferably, the inert gas is nitrogen, the volume ratio of nitrogen to hydrogen in the mixed atmosphere is 9:1, the sintering temperature is 1000-1400℃, and the time is 3-5h.

[0013] The application provides a rod crystal type piezoluminescent powder prepared by the preparation method.

[0014] The application further provides a piezoluminescent elastic composite material, which comprises an organic polymer elastic carrier and a piezoluminescent powder compounded in the organic polymer elastic carrier, and the piezoluminescent powder is the rod crystal type piezoluminescent powder.

[0015] Preferably, the organic polymer elastic carrier comprises polydimethylsiloxane, polyurethane or silica gel.

[0016] Preferably, the mass ratio of the piezoluminescent powder to the organic polymer elastic carrier is (0.5-2):1.

[0017] The application provides a preparation method of the piezoluminescent elastic composite material.

[0018] The prepolymer of the organic polymer elastic carrier, a curing agent and the piezoluminescent powder are mixed, and the mixture is heated and cured to obtain the piezoluminescent elastic composite material.

[0019] The application provides a preparation method of a rod crystal type mechanoluminescent powder, comprising the following steps: weighing CaCO3, SrCO3, halloysite nanotubes (HNTs) and Eu2O3 according to a stoichiometric ratio shown in a chemical formula Ca 0.6 Sr 0.4 Al2Si2O8:xEu 2+ (0.005≤x≤0.025), mixing to obtain a mixture; the halloysite nanotubes are calculated according to Al2O3 and SiO2; and the mixture is sequentially subjected to pre-sintering, first grinding, sintering and second grinding to obtain the rod crystal type mechanoluminescent powder. 0.6 Sr 0.4 Al2Si2O8:Eu 2+ The application uses HNTs with a nanotube structure as an Al / Si matrix to prepare the Ca 0.6 Sr 0.4 Al2Si2O8:Eu 2+ The application improves the photoluminescence and mechanoluminescence performance of the mechanoluminescent powder by utilizing the confinement effect of the structure of the HNTs and the increase of oxygen vacancies in the material preparation process. 0.6 Sr 0.4 Al2Si2O8:0.015Eu 2+ The application also provides a new idea for improving the photoluminescence of silicate luminescent materials; and on the other hand, the application applies the HNTs to the field of mechanoluminescence, which greatly expands the material category of the mechanoluminescence application.

[0020] The application provides a mechanoluminescent elastic composite material, which comprises an organic polymer elastic carrier and a mechanoluminescent powder which is compounded in the organic polymer elastic carrier, and the mechanoluminescent powder is the rod crystal type mechanoluminescent powder in the above technical solution. BRIEF DESCRIPTION OF DRAWINGS

[0021] Figure 1 Ca 0.6 Sr 0.4 Al2Si2O8:0.015Eu 2+ / PDMS prepared in Example 1 and Ca 0.6 Sr 0.4 Al2Si2O8:0.015Eu 2+ / PDMS prepared in Comparative Example 1 under the same conditions;

[0022] Figure 2 Ca 0.6 Sr 0.4 Al2Si2O8:0.015Eu 2+ / PDMS(a) and Ca 0.6 Sr 0.4 Al2Si2O8:0.015Eu 2+ / PDMS(H)(b) under the same conditions;

[0023] Figure 3 X-ray diffraction spectra of CSASE(H) prepared in Example 1 and CSASE prepared in Comparative Example 1;

[0024] Figure 4 SEM images of CSASE prepared in Comparative Example 1 (a) and CSASE(H) prepared in Example 1 (b);

[0025] Figure 5 Ca 0.6 Sr 0.4 Al2Si2O8:xEu 2+ / PDMS(H)(x = 0.005, 0.010, 0.015, 0.020, 0.025) under the same conditions;

[0026] Figure 6 O1s XPS fine spectra of CSASE(H) prepared in Example 1 and CSASE prepared in Comparative Example 1. DETAILED DESCRIPTION

[0027] The present application provides a preparation method of a rod crystal type piezoluminescent powder, comprising the following steps:

[0028] Ca 0.6 Sr 0.4 Al2Si2O8:xEu 2+ CaCO3, SrCO3, halloysite nanotubes and Eu2O3 are weighed according to the stoichiometric ratio of the chemical formula Ca 0.6 Sr 0.4 Al2Si2O8:xEu 2+ 0.005≤x≤0.025, and the halloysite nanotubes are calculated based on Al2O3 and SiO2.

[0029] The mixture is sequentially subjected to pre-sintering, first grinding, sintering and second grinding to obtain the rod crystal type piezoluminescent powder; and the sintering is performed in a mixed atmosphere of hydrogen and inert gas.

[0030] In the present application, the raw materials involved are all commercially available products well known in the art, unless otherwise specified.

[0031] The present application is according to the chemical formula Ca 0.6 Sr 0.4 Al2Si2O8:xEu 2+ The CaCO3, SrCO3, halloysite nanotubes and Eu2O3 are weighed and mixed according to the stoichiometric ratio to obtain a mixture. In the present application, the chemical formula Ca 0.6 Sr 0.4 Al2Si2O8:xEu 2+ 0.005≤x≤0.025 (x is the doping molar ratio of Eu 2+ The doping molar ratio or the doping molar percentage of Eu 0.6 Sr 0.4 Al2Si2O8:xEu 2+ The molar amount of Eu 2+ is x), and the x can be specifically 0.005, 0.010, 0.015, 0.020, 0.025, and preferably 0.015. In the present application, the halloysite nanotubes are calculated based on Al2O3 and SiO2. In the present application, the chemical formula Ca 0.6 Sr 0.4 Al2Si2O8:xEu 2+ The stoichiometric ratio, i.e. the molar ratio of Ca:Sr:Al:Si:Eu 2+ =0.6:0.4:2:2:x. In the embodiments of the present application, the purity of the CaCO3 is 99.9%, the purity of the SrCO3 and Eu2O3 is 99.99% respectively, and the purity of the halloysite nanotubes is preferably >99%.

[0032] The halloysite nanotubes (Al2O3·2SiO2·4H2O, HNTs) are 1:1 type layered aluminosilicate minerals, which are composed of silicon oxygen tetrahedral layers and aluminum oxygen octahedral layers. Among them, the oxygen atom shared by each silicon oxygen tetrahedron and aluminum oxygen octahedron is the apex oxygen, and the other three oxygen atoms are the basal oxygen. Adjacent silicon oxygen tetrahedrons share basal oxygen atoms and are connected to each other at a specific angle to form a silicon oxygen tetrahedral layer. Each aluminum oxygen octahedron is composed of four hydroxyl groups, one aluminum atom, and two silicon oxygen tetrahedral apex oxygen atoms, wherein the hydroxyl groups are shared with adjacent aluminum oxygen octahedrons, and they are connected to each other to form a unique tubular structure. The special Al2O3 / SiO2 component and structure of the halloysite nanotubes provide the Ca 0.6 Sr 0.4 Al2Si2O8:Eu 2+The enhancement of mechanoluminescence provides the basis. 0.6 Sr 0.4 Al2Si2O8:Eu 2+ The enhancement of mechanoluminescence provides the basis.

[0033] In the present application, the halloysite nanotubes are preferably pretreated before mixing, and the method of the pretreatment is preferably: the halloysite nanotubes are mixed with ethanol, subjected to microwave treatment, and then dried. In the present application, the ratio of the amount of the halloysite nanotubes to the amount of ethanol is preferably 5 g:50 mL. In the present application, the time of the microwave treatment is preferably 30 min, and the drying is preferably carried out at 100°C. In the present application, the halloysite nanotubes are mixed with ethanol and subjected to microwave treatment, so that the halloysite nanotubes are dispersed, and the subsequent reaction can be fully carried out. Since the HNTs lose the adsorbed water (two molecules of water in the HNTs are adsorbed water, which is lost during drying, which is a characteristic of HNTs) during drying, the weight of the HNTs is calculated according to the molecular formula Al2O3·2SiO2·2H2O to ensure the accuracy of the weighing.

[0034] In the present application, the method of the mixing is preferably: the CaCO3, SrCO3, halloysite nanotubes and Eu2O3 are wet ground and then dried. In the present application, the grinding medium added in the wet grinding is preferably ethanol; and the specific operation of the mixing is preferably: the CaCO3, SrCO3, halloysite nanotubes and Eu2O3 are mixed and placed in an agate mortar, ethanol is added, and then the mixture is ground thoroughly. The present application does not have special requirements for the conditions of the drying.

[0035] After the mixture is obtained, the mixture is sequentially pre-sintered, first ground, sintered and second ground to obtain the rod crystal type piezoluminescent powder.

[0036] In the present application, the sintering is carried out in a mixed atmosphere of hydrogen and inert gas, and the inert gas is preferably nitrogen, and the volume ratio of nitrogen to hydrogen in the mixed atmosphere is preferably 9:1. In the present application, the sintering temperature is preferably 1000-1400℃, which can be 1000, 1100, 1200, 1300 or 1400℃, and the sintering time is preferably 3-5h, which can be 3, 4 or 5h, and the heating rate from room temperature to the sintering temperature is preferably 4.5-5.5℃ / min, which can be 4.5, 5 or 5.5℃ / min. In the present application, the sintering is preferably carried out in a tube furnace. During the sintering process, the material gradually crystallizes to form a Ca 0.6 Sr 0.4 Al2Si2O8 phase with a relatively complete crystal structure. This process involves rearrangement and combination of elements in the raw materials to form a stable crystal structure. After sintering, the sintered sample is first ground into powder to obtain the rod crystal type piezoluminescent powder. In the present application, the piezoluminescent powder is represented as CSASE(H) luminescent powder.

[0037] The present application uses a high-temperature solid-phase method to prepare piezoluminescent powder, which is simple to operate and easy to industrialize.

[0038] The present application provides a rod crystal type piezoluminescent powder prepared by the preparation method described in the above technical solution. In the present application, the piezoluminescent powder has a rod crystal morphology, which is caused by the confinement effect of HNTs. The confinement effect introduces internal stress, which improves the piezoluminescent performance.

[0039] The present application also provides a piezoluminescent elastic composite material, which comprises an organic polymer elastic carrier and a piezoluminescent powder compounded in the organic polymer elastic carrier, and the piezoluminescent powder is the rod crystal type piezoluminescent powder described in the above technical solution.

[0040] In the present application, the organic polymer elastic carrier preferably comprises polydimethylsiloxane (PDMS), polyurethane (PU, such as thermoplastic polyurethane elastomer) or silica gel, and more preferably is PDMS. The present application does not have special requirements for the PDMS, PU or silica gel, and corresponding materials well known to those skilled in the art can be used. In the present application, the mass ratio of the force luminescent powder to the organic polymer elastic carrier is preferably (0.5-2):1, and more preferably is 0.5:1, 1:1.5 or 2:1.

[0041] The force luminescent elastic composite material provided by the present application has high light-emitting efficiency, high brightness and high photoluminescence, and can meet the actual application requirements to a certain extent, and has good application prospect.

[0042] The present application provides a preparation method of the force luminescent elastic composite material described in the above technical solution, which comprises the following steps:

[0043] The prepolymer, curing agent and the force luminescent powder of the organic polymer elastic carrier are mixed, and heating is performed to cure, so as to obtain the force luminescent elastic composite material.

[0044] In the present application, the prepolymer and curing agent of the organic polymer elastic carrier are preferably the prepolymer and curing agent corresponding to the elastomers such as polydimethylsiloxane, polyurethane and silica gel. The present application does not have special requirements for the types and proportions of the prepolymer and curing agent, and corresponding prepolymer and curing agent and proportions well known to those skilled in the art can be used. In the present application, the prepolymer is a PDMS prepolymer, and the mass ratio of the PDMS prepolymer to the curing agent is 1:0.1. In the present application, the total mass ratio of the force luminescent powder to the prepolymer and curing agent of the organic polymer elastic carrier is preferably (0.5-2):1, and more preferably is 0.5:1, 1:1.5 or 2:1.

[0045] In the present application, the method for mixing the prepolymer, curing agent and the force luminescent powder of the organic polymer elastic carrier is preferably as follows: the prepolymer and curing agent of the organic polymer elastic carrier are uniformly mixed, and then the force luminescent powder is added and fully mixed by mechanical stirring. After the mixing, the present application preferably transfers the obtained mixture to a mold, and then transfers the mold to a vacuum oven for vacuum degassing treatment. The temperature of the vacuum degassing treatment is preferably room temperature, the vacuum degree is preferably 10-20 kPa, and the time is preferably 10-20 min.

[0046] The present application does not have special requirements for the curing conditions, and the curing conditions well known to those skilled in the art can be used. In the present application, the temperature of the curing is preferably 50-80℃, and the time is preferably 20-60 min. After the curing, the force luminescent elastic composite material is obtained.

[0047] To further illustrate the present application, the rod-like piezoluminescent powder and piezoluminescent elastic composite material provided by the present application and the preparation thereof are described in detail below in connection with examples, but they should not be understood as limiting the scope of protection of the present application.

[0048] In various embodiments, the composition of the piezoluminescent elastic composite material is represented as Ca 0.6 Sr 0.4 Al2Si2O8:xEu 2+ / PDMS, wherein x is the molar doping concentration of Eu ions (i.e. 1 mol of Ca 0.6 Sr 0.4 Al2Si2O8:xEu 2+ Eu 2+ with a molar amount of x).

[0049] Example 1

[0050] A preparation method of a rod-like piezoluminescent powder and a piezoluminescent elastic composite material thereof, the steps of which are as follows:

[0051] (1) Preparation of the piezoluminescent powder:

[0052] HNTs were placed in ethanol and subjected to microwave treatment for 30 min, and then dried at 100°C for use. SrCO3(99.99%), CaCO3(99.9%), HNTs (>99%) and Eu2O3(99.99%) were weighed according to the stoichiometric ratio (Ca 0.6 Sr 0.4 Al2Si2O8:0.015Eu 2+ ) and mixed in an agate mortar, and then ethanol was added and ground thoroughly. After drying, the mixture was transferred to an alumina crucible, and the raw materials were pre-sintered at 700°C for 4 h using a box-type resistance furnace. After cooling, the pre-sintered sample was ground into powder. Then, the alumina crucible containing the pre-sintered sample was placed in a tube furnace (GSL-1600X) and sintered in a nitrogen-hydrogen (volume ratio 9:1) mixed atmosphere for 4 h, with a heating rate of 5°C / min and a sintering temperature of 1200°C. After the tube furnace cooled to room temperature, the sample was removed and ground into powder again to obtain the piezoluminescent powder, which is denoted as CSASE(H).

[0053] (2) Preparation of the piezoluminescent elastic composite material:

[0054] Prepolymer polydimethylsiloxane (PDMS) and curing agent were uniformly mixed at a ratio of 1:0.1. Then, the mechanoluminescent powder (CSASE(H)) prepared in step (1) was mixed with the above mixture at a mass ratio of 1:1.5. After thorough mixing by mechanical stirring, the mixture was transferred to a mold. At room temperature, the mold was placed in a vacuum oven with a vacuum degree of 20 kPa for 10 min to degas and eliminate air bubbles. Subsequently, it was cured at 70°C for 30 min to obtain a mechanoluminescent elastic composite material, denoted as Ca. 0.6 Sr 0.4 Al2Si2O8:0.015Eu 2+ / PDMS(H).

[0055] Comparative Example 1

[0056] In step (1) of Example 1, HNTs were replaced with SiO2 (99.9%) and Al2O3 (99.9%), while the rest remained the same as in Example 1, resulting in mechanoluminescent powder (denoted as CSASE) and mechanoluminescent elastic composite material (denoted as Ca). 0.6 Sr 0.4 Al2Si2O8:0.015Eu 2+ / PDMS).

[0057] Figure 1 The mechanoluminescent elastic composite material Ca prepared in Example 1 is given. 0.6 Sr 0.4 Al2Si2O8:0.015Eu 2+ The mechanoluminescent elastic composite material Ca prepared by / PDMS(H) and Comparative Example 1 0.6 Sr 0.4 Al2Si2O8:0.015Eu 2+ Mechanoluminescence spectrum of PDMS under the same conditions (80% tensile deformation). Figure 1 It can be seen that when the tensile deformation is 80%, the mechanoluminescent elastic composite material Ca prepared in Example 1... 0.6 Sr 0.4 Al2Si2O8:0.015Eu 2+ The mechanoluminescence intensity of / PDMS(H) (curve 1) is significantly higher than that of Ca. 0.6 Sr 0.4 Al2Si2O8:0.015Eu 2+ / PDMS (Curve 2).

[0058] Figure 2 The mechanoluminescent elastic composite material Ca prepared in Example 1 is given. 0.6 Sr 0.4 Al2Si2O8:0.015Eu 2+The mechanoluminescent elastic composite material Ca prepared by / PDMS(H) and Comparative Example 1 0.6 Sr 0.4 Al2Si2O8:0.015Eu 2+ Photoperiod afterglow spectrum of PDMS under the same conditions. Figure 2 It can be seen that after 5 minutes of ultraviolet (365nm) irradiation, the mechanoluminescent elastic composite material Ca prepared in Example 1 showed improved performance. 0.6 Sr 0.4 Al2Si2O8:0.015Eu 2+ / PDMS(H)( Figure 2 (b) Photoinduced afterglow is significantly better than Ca 0.6 Sr 0.4 Al2Si2O8:0.015Eu 2+ / PDMS( Figure 2 (a)

[0059] Figure 3 X-ray diffraction patterns of CSASE(H) prepared in Example 1 and CSASE mechanoluminescent powder prepared in Comparative Example 1, measured on an Auriga / Shimadzu XRD-6100 X-ray diffractometer. Figure 3 It can be seen that the two have similar crystal structures.

[0060] Figure 4 These are scanning electron microscope (SEM) images of the metheluminescent powder CSASE(H) prepared in Example 1 and the metheluminescent powder CSASE prepared in Comparative Example 1. Figure 4 In the diagram, a corresponds to CSASE and b corresponds to CSASE(H). It can be seen that the two have different morphological characteristics. The mechanoluminescent powder of CSASE(H) has a rod-shaped morphology.

[0061] Figure 6 The images show the fine O 1s XPS spectra of CSASE(H) prepared in Example 1 and CSASE mesoluminescent powder prepared in Comparative Example 1. Figure 6 China O Ⅰ O represents lattice oxygen. Ⅱ This indicates an oxygen vacancy. (From...) Figure 6 It can be seen that the oxygen vacancy (O) in CSASE(H) Ⅱ () has increased significantly.

[0062] Example 2

[0063] A method for preparing a rod-shaped mechanoluminescent powder and its mechanoluminescent elastic composite material, comprising the following steps:

[0064] Compared to Example 1, x is 0.005, and the rest are the same as steps (1) and (2) in Example 1. The resulting mechanoluminescent elastic composite material is denoted as Ca.0.6 Sr 0.4 Al2Si2O8:0.005Eu 2+ / PDMS(H)。

[0065] Figure 5 The piezoluminescence spectrum of the piezoluminescence elastic composite material Ca 0.6 Sr 0.4 Al2Si2O8:0.015Eu 2+ / PDMS(H) prepared in Example 2 is shown in Figure 1 (curve 3), and the piezoluminescence spectrum of the piezoluminescence elastic composite material Ca 0.6 Sr 0.4 Al2Si2O8:0.005Eu 2+ / PDMS(H) prepared in Example 2 is shown in Figure 1 (curve 1), and the piezoluminescence spectrum of the piezoluminescence elastic composite material Ca Figure 5 It can be seen that the piezoluminescence elastic composite material Ca 0.6 Sr 0.4 Al2Si2O8:0.005Eu 2+ / PDMS(H) prepared in Example 2 is shown in Figure 1 (curve 1), and the piezoluminescence spectrum of the piezoluminescence elastic composite material Ca

[0066] Example 3

[0067] A rod crystal piezoluminescence powder and a preparation method of a piezoluminescence elastic composite material thereof, the steps are as follows:

[0068] Compared with Example 1, x is 0.010, and the rest is the same as steps (1) and (2) in Example 1, and the obtained piezoluminescence elastic composite material is denoted as Ca 0.6 Sr 0.4 Al2Si2O8:0.010Eu 2+ / PDMS(H).

[0069] Figure 5 The piezoluminescence spectrum of the piezoluminescence elastic composite material Ca 0.6 Sr 0.4 Al2Si2O8:0.010Eu 2+ / PDMS(H) prepared in Example 3 is shown in Figure 1 (curve 2), and the piezoluminescence spectrum of the piezoluminescence elastic composite material Ca Figure 5 It can be seen that the piezoluminescence elastic composite material Ca 0.6 Sr 0.4 Al2Si2O8:0.010Eu 2+ / PDMS(H) prepared in Example 3 is shown in Figure 1 (curve 2), and the piezoluminescence spectrum of the piezoluminescence elastic composite material Ca

[0070] Example 4

[0071] A preparation method of a rod crystal type piezoluminescent powder and a piezoluminescent elastic composite material thereof, steps as follows:

[0072] Compared with Example 1, x is 0.020, and the rest is the same as steps (1) and (2) in Example 1, and the obtained piezoluminescent elastic composite material is recorded as Ca 0.6 Sr 0.4 Al2Si2O8:0.020Eu 2+ / PDMS(H).

[0073] Figure 5 The piezoluminescent spectrum (curve 4) of the piezoluminescent elastic composite material Ca 0.6 Sr 0.4 Al2Si2O8:0.020Eu 2+ / PDMS(H) prepared in Example 4 is given, and the characterization conditions are the same as those in Example 1, and the piezoluminescent spectrum is obtained by Figure 5 It can be seen that the piezoluminescent elastic composite material Ca 0.6 Sr 0.4 Al2Si2O8:0.020Eu 2+ / PDMS(H) prepared in Example 4 has a lower piezoluminescent intensity value than curves 3 and 2, and a higher piezoluminescent intensity than curve 1.

[0074] Example 5

[0075] A preparation method of a rod crystal type piezoluminescent powder and a piezoluminescent elastic composite material thereof, steps as follows:

[0076] Compared with Example 1, x is 0.025, and the rest is the same as steps (1) and (2) in Example 1, and the obtained piezoluminescent elastic composite material is recorded as Ca 0.6 Sr 0.4 Al2Si2O8:0.025Eu 2+ / PDMS(H).

[0077] Figure 5 The piezoluminescent spectrum (curve 5) of the piezoluminescent elastic composite material Ca 0.6 Sr 0.4 Al2Si2O8:0.025Eu 2+ / PDMS(H) prepared in Example 5 is given, and the characterization conditions are the same as those in Example 1, and the piezoluminescent spectrum is obtained by Figure 5 It can be seen that the piezoluminescent elastic composite material Ca 0.6 Sr 0.4 Al2Si2O8:0.025Eu 2+The force-induced luminescence intensity of / PDMS(H) is lower than that of curve 3 and curve 2, and higher than that of curve 1.

[0078] From Figure 1 It can be seen that with the increase of the doping concentration of Eu, the force-induced luminescence intensity of the material presents a change trend of first increasing and then decreasing; from Figure 2 and ​ It can be seen that when the doping concentration of Eu is 0.015, the material Ca 0.6 Sr 0.4 Al2Si2O8:0.015Eu 2+ The photoluminescence and force-induced luminescence intensity of / PDMS(H) are better than those of Ca 0.6 Sr 0.4 Al2Si2O8:0.015Eu 2+ / PDMS.

[0079] Example 6

[0080] A preparation method of a rod crystal type force-induced luminescence powder and a force-induced luminescence elastic composite material thereof, the steps are as follows:

[0081] Compared with Example 1, x is 0.005, the polymer is silicone, the mass ratio of the prepolymer (silicone prepolymer and curing agent) and the luminescent powder CSASE(H) is 1:0.5, the curing temperature is 60℃, and the time is 60min.

[0082] Example 7

[0083] A preparation method of a rod crystal type force-induced luminescence powder and a force-induced luminescence elastic composite material thereof, the steps are as follows:

[0084] Compared with Example 1, x is 0.02, the polymer is polyurethane, the mass ratio of the prepolymer (polyurethane prepolymer and curing agent) and the luminescent powder CSASE(H) is 1:2, the curing temperature is 60℃, and the time is 50min.

[0085] The above only describes the preferred embodiments of the present application, and does not limit the present application in any form. It should be noted that for ordinary skilled persons in the art, without departing from the principles of the present application, a number of improvements and refinements can be made, and these improvements and refinements should be considered as the protection scope of the present application.

Claims

1. A method for preparing a rod-like crystalline mechanoluminescent powder, characterized in that, The method comprises the following steps: Ca 0.6 Sr 0.4 Al2Si2O8:xEu 2+ , SrCO3, halloysite nanotubes and Eu2O3 according to the stoichiometric ratio shown in the formula Ca 0.6 Sr 0.4 Al2Si2O8:xEu 2+ 0.005≤x≤0.025, and the halloysite nanotubes are calculated in terms of Al2O3 and SiO2; before the mixing, the halloysite nanotubes are pretreated by mixing the halloysite nanotubes with ethanol, microwave treatment and drying. The mixture is sequentially pre-fired, first ground, sintered and second ground to obtain the rod crystal type mechanoluminescent powder; the sintering is performed in a mixed atmosphere of hydrogen and inert gas.

2. The production method according to claim 1, characterized by, The mixing method is: wet grinding and then drying the CaCO3, SrCO3, halloysite nanotube and Eu2O3.

3. The preparation method according to claim 1, characterized in that, The pre-firing temperature is 600-900 ℃, and the time is 3-5 h.

4. The method of claim 1, wherein, The inert gas is nitrogen, and the volume ratio of nitrogen to hydrogen in the mixed atmosphere is 9:1; the sintering temperature is 1000-1400 ℃, and the time is 3-5 h.

5. The rod crystal type mechanoluminescent powder prepared by the preparation method in any one of claims 1-4.

6. A mechanoluminescent elastomeric composite, characterized in that, The organic polymer elastic carrier comprises polydimethylsiloxane, polyurethane or silica gel.

7. The elasto-optic material of claim 6, wherein, The mass ratio of the mechanoluminescent powder to the organic polymer elastic carrier is (0.5-2):

1.

8. The elasto-optic material according to claim 6 or 7, wherein The method comprises the following steps:

9. A method of producing the piezoluminescent elastic composite according to any one of claims 6 to 8, characterized in that, The prepolymer of the organic polymer elastic carrier, a curing agent and the mechanoluminescent powder are mixed and heated to be cured to obtain the mechanoluminescent elastic composite material. ​

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