X-ray fast charging stress luminescence material and preparation method thereof

Abstract

The application discloses an X-ray fast energy-charged stress luminescent material and a preparation method thereof, and belongs to the technical field of novel inorganic functional materials. 3+ A2SiO4(A=Ca, Sr or Ba) material is used as a base body, trivalent rare earth ion Dy + is used as an activator, and Li 2‑x‑y is used as a charge compensation agent, so that X-ray fast energy-charged stress luminescent powder A 3+ SiO4:xDy + (A=Ca, Sr or Ba, 0 3+ Dy + and Li 3+ are doped in the silicate to form traps in the base body, so as to capture carriers; by changing the concentration of Dy + and Li , the concentration of the carriers in the traps is adjusted, so that the material has strong afterglow and stress luminescent intensity. The material has the advantages of simple preparation, stable chemical property, short excitation time, strong afterglow and afterglow duration, strong stress luminescent phenomenon, and super-long delayed stress luminescent phenomenon.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of new inorganic functional materials, and particularly relates to an X-ray rapid energy charging stress luminescence material and a preparation method thereof. BACKGROUND

[0002] Mechanoluminescence is a phenomenon of light emission from materials under the action of various mechanical stimuli (such as friction, compression, stretching, vibration, impact, ultrasonic waves, etc.), and is a phenomenon of light emission caused by elastic deformation, plastic deformation and fracture. According to the characteristics of the material, the mechanoluminescence can be divided into self-recovery type and pre-excitation trap control type, and the trap control type mechanoluminescence material is a new type of energy storage and electron trapping material. In the sensing field of stress distribution visualization, bridge engineering structure diagnosis, signature and anti-counterfeiting encryption, the mechanoluminescence material has broad application prospects. In addition, the mechanoluminescence material is endowed with the potential of new optoelectronic materials for the new era, and is expected to realize self-driving, flexibility, multi-mode coupling and other advanced functions. Similarly, the mechanoluminescence material has gradually become one of the new research hotspots in the fields of intelligent wearable devices, mechanical driving light generators, biomedical diagnosis and treatment, artificial intelligence and electronic skin, and its potential application fields can cover medical treatment, agriculture, information, military, aviation and many other industries. The research on the mechanoluminescence material has attracted much attention in recent years, and due to its recyclable use, stress distribution image visualization and many other advantages, it has attracted worldwide attention, and the research on the mechanoluminescence material has developed rapidly.

[0003] Compared with other types of luminescent materials, the research on the mechanoluminescence material is relatively short. Since 1999, the Chaonan Xu research group of the National Institute of Industrial Technology of Japan first reported two high-brightness mechanoluminescence materials, ZnS:Mn 2+ (yellow) and SrAl2O4:Eu 2+ (green), and up to now, the types of successfully synthesized mechanoluminescence materials are still very limited, and the lack of types is one of the important factors affecting the development of the mechanoluminescence material to the practical application field. Researches show that for the development of the mechanoluminescence material, one of the most efficient ways is to select the materials with non-centrosymmetric crystal structure from the existing long afterglow luminescent materials, and the representative materials are: CaZr(PO4)2:Eu 2+ , Sr3Al2O5Cl2:Eu 2+ , Tm 3+ , BaSi2O2N2:Eu 2+ , Ca2Al2SiO7:Eu 2+ , Dy 3+etc. In addition, the pre-excitation source of most stress luminescent materials is relatively single at present, and expanding the pre-excitation source is also one of the methods to improve the performance of stress luminescent materials. Therefore, in the field, there is a great driving force to develop a stress luminescent material with stable chemical properties, non-toxic, simple preparation method and using high-energy rays (such as X-rays) as a pre-excitation source, which also has a great driving force for the research and application of stress luminescent materials. SUMMARY

[0004] The purpose of the present application is to provide an X-ray fast charging stress luminescent material and a preparation method thereof. By taking A2SiO4 (A = Ca, Sr or Ba) material as the matrix, using trivalent rare earth ion Dy 3+ as the activator, Li + as the charge compensation agent, an X-ray fast charging stress luminescent powder A 2-x-y SiO4:xDy 3+ ,yLi + (A = Ca, Sr or Ba, 0 < x < 0.08, 0 < y < 0.07) is prepared, wherein the Dy 3+ and Li + doped in the silicate form traps in the matrix to capture carriers; by changing the concentration of Dy 3+ and Li + , the concentration of carriers inside the traps is adjusted to have strong afterglow and stress luminescence intensity. The material is simple to prepare, has stable chemical properties, short excitation time, strong afterglow and afterglow duration, strong stress luminescence phenomenon, and exhibits super-long delayed stress luminescence phenomenon. The stress luminescence performance of the fluorescent powder provided by the present application lays a foundation for its practical application in intelligent wearable devices, mechanical drive light generators, biomedical diagnosis and treatment, artificial intelligence and electronic skin, stress sensing, bridge damage detection, anti-counterfeiting encryption and many other fields.

[0005] To achieve the above object, the present application provides the following technical solutions:

[0006] One of the technical solutions of the present application: an X-ray fast charging stress luminescent powder is provided, and the chemical formula of the X-ray fast charging stress luminescent powder is: A 2-x-y SiO4:xDy 3+ ,yLi + ; wherein A is Ca, Sr or Ba, 0 < x < 0.08, 0 < y < 0.07.

[0007] The second technical solution of the present application: a preparation method of the above-mentioned X-ray fast charging stress luminescent powder is provided, which is prepared by a high-temperature solid phase method.

[0008] Preferably, the specific steps of the high-temperature solid-phase method include: weighing the carbonates of A elements and Li, the oxides of Si and Dy, adding a dispersion liquid, grinding the mixture, pre-sintering under oxygen, continuing to calcine the pre-sintered product under oxygen, and obtaining the X-ray fast-charging luminescent powder.

[0009] Preferably, the dispersion liquid is anhydrous ethanol.

[0010] Preferably, the pre-sintering temperature is 800-900 DEG C, and the time is 2-4 h.

[0011] Preferably, the calcining temperature is 1200-1300 DEG C, and the time is 4-6 h.

[0012] More preferably, the heating rate of the pre-sintering and the calcining is 5-10 DEG C / min.

[0013] The third technical scheme of the present application provides an X-ray fast-charging stress luminescent material composed of the X-ray fast-charging luminescent powder dispersed in a cured epoxy resin.

[0014] The fourth technical scheme of the present application provides a preparation method of the X-ray fast-charging stress luminescent material, comprising the following steps:

[0015] Mixing the X-ray fast-charging luminescent powder with an epoxy resin and a curing agent, and obtaining the X-ray fast-charging stress luminescent material after curing.

[0016] The fifth technical scheme of the present application provides an application of the X-ray fast-charging luminescent powder in preparing a stress luminescent device.

[0017] The sixth technical scheme of the present application provides an application of the X-ray fast-charging stress luminescent material in preparing a stress luminescent device.

[0018] The present application has the following beneficial technical effects:

[0019] The X-ray fast-charging luminescent powder provided by the present application is prepared by a traditional high-temperature solid-phase method, and has the advantages of simple preparation process, easy control of conditions, low equipment requirement, low cost, no generation of toxic gas in the preparation process, and no pollution to the environment.

[0020] The X-ray fast-charging stress luminescent material prepared by the present application can emit a visible afterglow in a dark environment after a short-time X-ray pre-excitation, and the afterglow time can last for more than 8 hours; under the stimulation of an external load, a visible stress luminescent phenomenon can be observed, and the stress luminescent signal can still be detected under the action of the external load after 386 hours.

[0021] The X-ray rapid charging phosphor powder can be mixed with epoxy resin, curing agent and other organic polymers to prepare stress luminescence devices in various forms. BRIEF DESCRIPTION OF DRAWINGS

[0022] Figure 1 XRD patterns of different doped strontium silicate powders prepared in Examples 1-11 and α-strontium silicate and β-strontium silicate, wherein (a) is XRD patterns of different doped strontium silicate powders prepared in Examples 1-7 and α-strontium silicate and β-strontium silicate, and (b) is XRD patterns of different doped strontium silicate powders prepared in Examples 8-11 and α-strontium silicate and β-strontium silicate.

[0023] Figure 2 After the different doped strontium silicate powders prepared in Examples 1-11 were excited by X-ray for 10 s, the afterglow emission spectra were measured, wherein (a) is the afterglow emission spectra of the different doped strontium silicate powders prepared in Examples 1-7, and (b) is the afterglow emission spectra of the different doped strontium silicate powders prepared in Examples 6, 8-11.

[0024] Figure 3 After the different doped strontium silicate powders prepared in Example 9 were excited by X-ray for 10 s, the afterglow decay curves at 481 nm were measured.

[0025] Figure 4 After the doped strontium silicate stress luminescence materials prepared in Examples 12-18 were excited by X-ray for 10 s and interval 1 min, the stress luminescence intensity at 481 nm was measured under 1000 N load after 5 times of compression, wherein (a) is the stress curve during the 5 times of compression, (b)-(h) are the stress luminescence intensities of Examples 12-18 in turn, and (i) is the stress luminescence intensity of different Dy 3+ Stress luminescence intensity of different doping concentrations.

[0026] Figure 5 After the doped strontium silicate stress luminescence materials prepared in Examples 17, 19-22 were excited by X-ray for 10 s and interval 1 min, the stress luminescence intensity at 481 nm was measured under 1000 N load after 5 times of compression, wherein (a)-(e) are the stress luminescence intensities of Examples 17, 19-22 in turn, and (f) is the stress luminescence intensity of different Li + Stress luminescence intensity of different doping concentrations.

[0027] Figure 6 After the doped strontium silicate stress luminescence material prepared in Example 20 was excited by X-ray for 5 min and delayed for 386 h in the dark, the stress luminescence curve at 481 nm was measured by applying a cyclic compression load. DETAILED DESCRIPTION

[0028] Various exemplary embodiments of the present invention will now be described in detail. This detailed description should not be considered as a limitation of the present invention, but rather as a more detailed description of certain aspects, features, and embodiments of the present invention. It should be understood that the terminology used in this invention is merely for describing particular embodiments and is not intended to limit the present invention.

[0029] Furthermore, regarding the numerical ranges in this invention, it should be understood that each intermediate value between the upper and lower limits of the range is also specifically disclosed. Any stated value or intermediate value within a stated range, as well as each smaller range between any other stated value or intermediate value within said range, are also included in this invention. The upper and lower limits of these smaller ranges may be independently included or excluded from the range.

[0030] Unless otherwise stated, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. While only preferred methods and materials have been described herein, any methods and materials similar to or equivalent to those described herein may be used in the implementation or testing of this invention.

[0031] The terms “include,” “including,” “have,” “contain,” etc., used in this article are all open-ended terms, meaning that they include but are not limited to.

[0032] Unless otherwise specified, "room temperature" in the embodiments of this invention refers to a temperature of 20±10℃.

[0033] Examples 1-11

[0034] Preparation of doped strontium silicate powder:

[0035] According to the metal elements and silicon molar ratios in Table 1, weigh analytical grade SrCO3, SiO2, Dy2O3, and Li2CO3 (Li2CO3 was not added in Examples 1-7). Add 5 mL of anhydrous ethanol, grind thoroughly, transfer to a crucible, and place in a muffle furnace. Heat to 800°C at 5°C / min in air, pre-calcine for 2 hours, and then allow to cool naturally to room temperature. Remove the powder from the crucible, grind thoroughly in an agate mortar, transfer to the crucible, place in a muffle furnace, heat to 1300°C at 5°C / min in air, calcine for 6 hours, and then allow to cool naturally to room temperature. Remove the powder from the crucible, grind thoroughly in an agate mortar, and obtain doped strontium silicate powder.

[0036] Table 1

[0037]

[0038]

[0039] The XRD patterns of strontium silicate powders with different doping prepared in Examples 1-11, and α-strontium silicate and β-strontium silicate are shown in the figure. Figure 1 Among them, (a) are the XRD patterns of strontium silicate powders with different doping and α-strontium silicate and β-strontium silicate prepared in Examples 1 to 7, and (b) are the XRD patterns of strontium silicate powders with different doping and α-strontium silicate and β-strontium silicate prepared in Examples 6, 8 to 11. Figure 1 The results show that the doped strontium silicate powder prepared by this invention is a pure phase, and the doped ions do not disrupt the crystal structure.

[0040] The afterglow emission spectra of strontium silicate powders with different doping prepared in Examples 1-11, measured after X-ray excitation for 10 s, are shown in the figure. Figure 2 Among them, (a) is the afterglow emission spectrum of strontium silicate powders with different doping prepared in Examples 1 to 7, and (b) is the afterglow emission spectrum of strontium silicate powders with different doping prepared in Examples 6, 8 to 11. Figure 2 The emission peaks of the afterglow spectrum are located at approximately 481, 574, 663, and 752 nm, appearing white, and are Dy. 3+ It exhibits characteristic transitions and possesses a strong afterglow emission intensity.

[0041] Figure 1 and Figure 2 0Li in + This is the sample from Example 6.

[0042] The afterglow decay curves at 481 nm of the strontium silicate powders with different doping prepared in Example 9 after X-ray excitation for 10 s are shown in the figure. Figure 3 . Figure 3 The Sr prepared in Example 8 shows 1.9 SiO4:0.07Dy 3+ 0.03Li + After being excited by X-rays for 10 seconds, the afterglow decay time can last for more than 8 hours.

[0043] Examples 12-22

[0044] Preparation of doped strontium silicate stress-luminescent materials:

[0045] A mixed solution of epoxy resin and curing agent was prepared at a volume ratio of 2:1. 0.5 mL of this mixed solution was taken, and 0.5 g of the doped strontium silicate powder prepared in Examples 1-11 was added to each solution and mixed into a mold (25 mm in diameter and 15 mm in depth). After stirring evenly, the mixture was allowed to stand for 4 hours. Another 5.5 mL of the mixed solution was added to the mold, and the mixture was allowed to stand for 24 hours to obtain the doped strontium silicate stress-luminescent material.

[0046] The doped strontium silicate stress luminescent materials of Examples 12-22 correspond to the doped strontium silicate powders of Examples 1-11, respectively.

[0047] The stress luminescence intensity at 481 nm of the doped strontium silicate stress luminescent materials prepared in Examples 12-18 after X-ray excitation for 10 s followed by a 1 min interval and 5 cycles of compression under a 1000 N load is shown in the figure. Figure 4 Wherein, (a) is the stress curve during five cycles of compression, (b) to (h) are the stress luminescence intensities of Examples 12 to 18 respectively, and (i) is the luminescence intensity of different Dy values. 3+ Stress luminescence intensity at doping concentration.

[0048] The stress luminescence intensity at 481 nm of the doped strontium silicate stress luminescent materials prepared in Examples 17, 19-22, after X-ray excitation for 10 s followed by a 1 min interval and 5 cycles of compression under a 1000 N load, is shown in the figures. Figure 5 Wherein, (a) to (e) are the stress luminescence intensities of Examples 17, 19 to 22, respectively, and (f) are the intensities of different Li... + Stress luminescence intensity at doping concentration.

[0049] Figure 5 0Li in + This is the sample from Example 17.

[0050] Figure 4 and Figure 5 The results show that, even under low light conditions, after the excitation source is removed, the doped strontium silicate stress-luminescent materials prepared in Examples 19-22 still exhibit good stress-luminescent properties.

[0051] The stress emission curve at 481 nm of the doped strontium silicate stress-luminescent material prepared in Example 20, after X-ray excitation for 5 min and delay in darkness for 386 h, followed by cyclic compression loading, is shown in the figure. Figure 6 . Figure 6 The results show that, after a brief X-ray charging, under the influence of external mechanical stimulation, the doped strontium silicate stress-luminescent material prepared in Example 20 exhibits an ultralong delayed stress luminescence phenomenon.

[0052] The embodiments described above are merely preferred embodiments of the present invention and are not intended to limit the scope of the present invention. Various modifications and improvements made by those skilled in the art to the technical solutions of the present invention without departing from the spirit of the present invention should fall within the protection scope defined by the claims of the present invention.

Claims

1. The application of an X-ray rapidly charged phosphorescent powder in the fabrication of stress-emitting devices, characterized in that, The chemical formula for the X-ray fast-charging bioluminescent powder is: A 2-x-y SiO4:xDy 3+ ,yLi + Where A is Sr, 0 < x ≤ 0.08, 0 < y ≤ 0.

07.

2. The application of the X-ray fast-charging phosphorescent powder according to claim 1 in the fabrication of stress-emitting devices, characterized in that, The X-ray fast-charged bioluminescent powder was prepared by a high-temperature solid-state method.

3. The application of the X-ray fast-charging bioluminescent powder according to claim 2 in the fabrication of stress-emitting devices, characterized in that, The specific steps of the high-temperature solid-state method preparation include: weighing A element and Li carbonate, Si and Dy oxides according to the proportion, adding them to the dispersion, grinding and mixing them, and then pre-calcining them under aerobic conditions. After grinding the pre-calcined product, it is further calcined under aerobic conditions to obtain the X-ray rapid charging power fluorescent powder.

4. The application of the X-ray fast-charging bioluminescent powder according to claim 3 in the fabrication of stress-emitting devices, characterized in that, The dispersion is anhydrous ethanol.

5. The application of the X-ray fast-charging bioluminescent powder according to claim 3 in the fabrication of stress-emitting devices, characterized in that, The pre-calcination temperature is 800-900℃ and the time is 2-4h; and / or the calcination temperature is 1200-1300℃ and the time is 4-6h.

6. The application of the X-ray fast-charging bioluminescent powder according to claim 5 in the fabrication of stress-emitting devices, characterized in that, The heating rates for both the pre-firing and calcination are 5-10℃ / min.

7. The application of an X-ray fast-charged stress-luminescent material in the fabrication of stress-luminescent devices, characterized in that, The X-ray fast-charge stress luminescent material is composed of X-ray fast-charge stress luminescent powder of claim 1 dispersed in a cured epoxy resin.

8. The application of the X-ray fast-charged stress-luminescent material according to claim 7 in the fabrication of stress-luminescent devices, characterized in that, The preparation method of the X-ray fast-charge stress-luminescent material includes the following steps: The X-ray fast-charged stress-luminescent powder is mixed with epoxy resin and a curing agent, and after curing, an X-ray fast-charged stress-luminescent material is obtained.

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