X-ray excited stress luminescent material and preparation method thereof

Abstract

The invention discloses an X-ray excited stress luminescent material and a preparation method thereof, and belongs to the technical field of novel inorganic functional materials. The X-ray excited force-induced fluorescent powder ALa1-xAl3O7: xPr < 3 + > (A is Ca, Ba or Sr, and x is more than or equal to 0.1% and less than or equal to 3%) is prepared by taking an ALaAl3O7 (A is Ca, Ba or Sr) material as a matrix and adopting a trivalent rare earth ion Pr < 3 + > as an activating agent. The stress luminescent material prepared from the powder has good afterglow luminescence performance and stress luminescence performance at room temperature, has a good linear relationship between stress luminescence intensity and load, and is expected to be prepared into a stress luminescence sensor.

Description

Technical Field

[0001] The invention belongs to the technical field of novel inorganic functional materials, and in particular relates to an X-ray excited stress luminescent material and a preparation method thereof. Background Art

[0002] Stress luminescence refers to the phenomenon that a substance produces light under the action of mechanical stimulation. Since stress luminescent materials can convert mechanical energy into light energy, and mechanical energy is ubiquitous in our lives, stress luminescence has received widespread attention. So far, the wavelengths of stress luminescent materials developed have covered the ultraviolet, visible and near-infrared regions. For example, SrAl2O4:Eu 2+ (green emission), ZnS:Cu (green and blue emission), SrZnSO:Mn 2+ (red emission), Y3Al5O 12 :Ce 3+ (yellow emission), etc., are typical visible light stress luminescent materials; CaZnOS:Nd 3+ , SrGa 12 O 19 :Cr 3+ Phosphors such as LiYGeO4:Bi 3+ , Ca9Bi(PO4)7:Ce 3+ Ultraviolet stress luminescent materials such as (dual-band emission) have also been developed one after another. Even in the same matrix (CaZnOS material), multi-color stress luminescence (covering from the ultraviolet region to the near-infrared region) has been achieved by doping different lanthanide ions. It is the diversity of the wavelength of stress luminescent materials that has expanded its application range. Studies have found that it has shown great application potential in the fields of anti-counterfeiting, traffic safety, building health testing, biomechanical testing, etc.

[0003] Stress luminescent materials are a potential stock that cannot be ignored in many fields due to their special luminescence phenomenon, but there are not many materials that can meet the conditions for actual application. This is because the performance of different stress luminescent materials varies greatly. Studies have found that about half of inorganic solids and more than a quarter of organic crystals have stress luminescence properties, but only a few materials have a good linear relationship between the luminescence intensity and the load. This is because the above-mentioned few materials can emit light within the elastic limit of the external mechanical stimulus applied to them, while most materials will undergo plastic deformation or even fracture under the action of force, resulting in a poor correlation between their luminescence intensity and the applied force. The linear relationship between force and stress luminescence intensity is the guarantee for the preparation of stress luminescent materials into stress luminescence sensors and then their application. Therefore, the development of a material with excellent correlation between stress luminescence intensity and load, non-toxicity and simple preparation method has a great driving force for the research and application of materials. Summary of the invention

[0004] The present invention aims to provide an X-ray excited stress luminescent material and a preparation method thereof. 3+ As an activator, the X-ray excited force-induced fluorescent powder ALa was prepared 1-x Al3O7:xPr 3+ (A = Ca, Ba or Sr, 0.1% ≤ x ≤ 3%). The stress luminescent material prepared using the powder has good afterglow luminescence performance and stress luminescence performance at room temperature, and there is a good linear relationship between the stress luminescence intensity and the load, and it is expected to be prepared into a stress luminescence sensor.

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

[0006] One of the technical solutions of the present invention is to provide an X-ray excited mechanoluminescent powder, wherein the chemical expression of the X-ray excited mechanoluminescent powder is: ALa 1-x Al3O7:xPr 3+ ; Wherein, A is Ca, Ba or Sr, 0.1%≤x≤3%.

[0007] The second technical solution of the present invention is to provide a method for preparing the above-mentioned X-ray excited mechanoluminescent powder by a high temperature solid phase method.

[0008] Preferably, the specific steps of the high-temperature solid-phase preparation method include: weighing the carbonate of element A, the oxides of La, Al and Pr in proportion, adding a dispersion containing a solvent, grinding and mixing, and then calcining under aerobic conditions, and grinding the calcined product to obtain the X-ray-excited mechanoluminescent powder.

[0009] Preferably, the co-solvent is boric acid.

[0010] Preferably, the dispersion liquid is anhydrous ethanol.

[0011] Preferably, the burning temperature is 1350-1600° C. and the burning time is 5-6 hours.

[0012] More preferably, the heating rate of the burning is 5-10°C / min.

[0013] The third technical solution of the present invention is to provide an X-ray excited stress luminescent material, which is composed of the above-mentioned X-ray excited stress luminescent powder dispersed in a cured epoxy resin.

[0014] A fourth technical solution of the present invention is to provide a method for preparing the above-mentioned X-ray excited stress luminescent material, comprising the following steps:

[0015] The X-ray excited stress luminescent powder is mixed with epoxy resin and curing agent, and after curing, the X-ray excited stress luminescent material is obtained.

[0016] The fifth technical solution of the present invention is to provide an application of the above-mentioned X-ray excited force-induced fluorescent powder in the preparation of stress luminescence sensors.

[0017] Technical solution six of the present invention: provides an application of the above-mentioned X-ray excited stress luminescence material in the preparation of a stress luminescence sensor.

[0018] The beneficial technical effects of the present invention are as follows:

[0019] The X-ray excited mechanoluminescent powder provided by the present invention is prepared by a traditional high temperature solid phase method, and has a simple preparation process, easy control of conditions, low equipment requirements, and low cost. No toxic gas is generated during the preparation process, and there is no pollution to the environment.

[0020] The X-ray excited force-induced fluorescent powder provided by the present invention can be observed with naked eyes to have an orange-red afterglow in a weak light environment after being excited by X-rays for 1 minute and the excitation source is removed, and the afterglow is relatively strong.

[0021] The X-ray excited stress luminescent material prepared by the present invention has a strong stress luminescent effect, and there is a good linear relationship between its luminescent intensity and load. It is expected to be prepared into a stress luminescent sensor, which can be applied to the fields of building health detection, anti-counterfeiting, traffic safety, aerospace, biomechanics, etc. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] Figure 1 The different Pr prepared in Examples 1 to 5 3+ XRD patterns of lanthanum calcium aluminate powder and lanthanum calcium aluminate with different doping concentrations.

[0023] Figure 2 The different Pr prepared in Examples 1 to 5 3+ Afterglow emission spectrum of lanthanum calcium aluminate powder with doped concentration measured after X-ray excitation for 1 minute.

[0024] Figure 3 The different Pr prepared in Examples 1 to 5 3+ The afterglow decay curve of lanthanum calcium aluminate powder with doped concentration was measured at 490nm after X-ray excitation for 1min.

[0025] Figure 4 Pr prepared in Example 7 3+ The stress luminescence intensity of the calcium lanthanum aluminate-doped stress luminescent material after being excited by X-rays for 1 minute and then applying different loads after an interval of 5 minutes.

[0026] Figure 5The different Pr prepared in Examples 6 to 10 3+ The stress luminescence intensity of the lanthanum calcium aluminate stress luminescent material with a doping concentration after being excited by X-rays for 1 minute and then applying a load of 2000N after an interval of 5 minutes. DETAILED DESCRIPTION

[0027] Now, various exemplary embodiments of the present invention are described in detail, and this detailed description should not be considered as a limitation of the present invention, but should be understood as a more detailed description of certain aspects, characteristics and embodiments of the present invention. It should be understood that the terms described in the present invention are only for describing specific embodiments and are not used to limit the present invention.

[0028] In addition, for the numerical range in the present invention, it is understood that each intermediate value between the upper and lower limits of the range is also specifically disclosed. The intermediate value in any stated value or stated range, and each smaller range between any other stated value or intermediate value in the range is also included in the present invention. The upper and lower limits of these smaller ranges can be independently included or excluded in the scope.

[0029] Unless otherwise specified, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the art to which the invention pertains. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein may also be used in the practice or testing of the present invention.

[0030] The words “include,” “including,” “have,” “contain,” etc. used in this document are open-ended terms, meaning including but not limited to.

[0031] Unless otherwise specified, the "room temperature" in the embodiments of the present invention refers to a temperature of 20±10°C.

[0032] Examples 1 to 5

[0033] Pr 3+ Preparation of doped lanthanum calcium aluminate powder:

[0034] According to the molar ratio of metal elements in Table 1, weigh analytically pure CaCO3, La2O3, Al2O3 and Pr6O 11 , add 0.8mmol H3BO3 and 5mL anhydrous ethanol, grind thoroughly, transfer to a crucible and place in a muffle furnace, heat to 1350℃ at 5℃ / min in air environment, burn for 5h and then cool naturally to room temperature in the furnace. Take out the powder in the crucible and grind it thoroughly in an agate mortar for 15min to obtain Pr 3+ Doped lanthanum calcium aluminate powder.

[0035] Table 1

[0036]

[0037]

[0038] Different Pr prepared in Examples 1 to 5 3+ The XRD patterns of lanthanum calcium aluminate powder and lanthanum calcium aluminate with different doping concentrations are shown in Figure 1 . Figure 1 It shows that the Pr prepared by the present invention 3+ The doped calcium lanthanum aluminate powder is pure phase, and the doped rare earth ions do not disturb the crystal structure.

[0039] Different Pr prepared in Examples 1 to 5 3+ The afterglow emission spectrum of the lanthanum calcium aluminate powder with a doping concentration measured after X-ray excitation for 1 minute is shown in Figure 2 . Figure 2 It is shown that each sample forms a green emission centered at 490 nm and a red emission centered at 616 nm, which is due to the Pr 3+ due to the electron transition.

[0040] Different Pr prepared in Examples 1 to 5 3+ The afterglow decay curve of the lanthanum calcium aluminate powder with a doping concentration at 490nm was measured after 1 minute of X-ray excitation. Figure 3 . Figure 3 Show, when Pr 3+ When the doping concentration is 1%, the afterglow performance of the material reaches the best. The afterglow intensity of materials with different doping concentrations is visible to the naked eye, and the afterglow duration is relatively long, which has application prospects in optical devices, emergency lighting displays and other fields.

[0041] Embodiments 6 to 10

[0042] Pr 3+ Preparation of calcium lanthanum aluminate-doped stress luminescent materials:

[0043] A mixed solution of epoxy resin and curing agent was prepared with a volume ratio of epoxy resin to curing agent of 2:1. 0.5 mL of the mixed solution was taken and 0.5 g of Pr prepared in Examples 1 to 5 was added respectively. 3+ The doped lanthanum calcium aluminate powder was mixed in a mold (25 mm in diameter and 15 mm in depth), stirred evenly and left to stand for 4 h. 5.5 mL of the mixed solution was added to the mold again and left to stand for 24 h to obtain Pr 3+ Doped lanthanum calcium aluminate stress luminescent material.

[0044] Pr of Examples 6 to 10 3+ The doped calcium lanthanum aluminate stress luminescent materials correspond to Pr in Examples 1 to 5 in sequence. 3+ Doped lanthanum calcium aluminate powder.

[0045] Example 7 Preparation of Pr 3+ The stress luminescence intensity of the doped calcium aluminate lanthanum stress luminescent material after X-ray excitation for 1 minute and then applying different loads after an interval of 5 minutes is shown in the figure. Figure 4 . Figure 4 It shows that the Pr prepared in Example 7 3+ After X-ray excitation of the lanthanum calcium aluminate stress luminescent material, a load of 0 to 2000N is applied, and the stress luminescent intensity is linear with the load size.

[0046] Different Pr prepared in Examples 6 to 10 3+ The stress luminescence intensity of the lanthanum calcium aluminate stress luminescent material with a doping concentration is shown in Figure 2 after being excited by X-rays for 1 minute and then subjected to a load of 2000N after a 5-minute interval. Figure 5 . Figure 5 It shows that the CaLa prepared in Example 3 0.99 Al3O7:1%Pr 3+ The stress luminescence intensity of the stress luminescence material prepared by powder is the highest.

[0047] The embodiments described above are only descriptions of the preferred modes of the present invention, and are not intended to limit the scope of the present invention. Without departing from the design spirit of the present invention, various modifications and improvements made to the technical solutions of the present invention by ordinary technicians in this field should all fall within the protection scope determined by the claims of the present invention.

Claims

1. An X-ray excited mesoluminescent powder, characterized in that: The chemical expression of the X-ray excited mesoluminescent powder is: ALa 1-x Al3O7:xPr 3+ ; Wherein, A is Ca, Ba or Sr, 0.1%≤x≤3%.

2. A method for preparing the X-ray excited mesoluminescent powder according to claim 1, characterized in that: Prepared by high temperature solid phase method.

3. The method for preparing X-ray excited mesoluminescent powder according to claim 2, characterized in that: The specific steps of the high-temperature solid phase method preparation include: weighing the carbonate of element A, the oxides of La, Al and Pr in proportion, adding a dispersion containing a solvent, grinding and mixing, and then calcining under aerobic conditions, and grinding the calcined product to obtain the X-ray excited mechanoluminescent powder.

4. The method for preparing X-ray excited mesoluminescent powder according to claim 3, characterized in that: The co-solvent is boric acid; and / or the dispersion liquid is anhydrous ethanol.

5. The method for preparing X-ray excited mesoluminescent powder according to claim 3, characterized in that: The burning temperature is 1350-1600° C. and the burning time is 5-6 hours.

6. The method for preparing X-ray excited mesoluminescent powder according to claim 5, characterized in that: The heating rate of the burning is 5-10°C / min.

7. An X-ray excited stress luminescent material, characterized in that: The X-ray excited mechanoluminescent powder according to claim 1 is dispersed in a cured epoxy resin.

8. A method for preparing the X-ray excited stress luminescent material according to claim 7, characterized in that: The following steps are involved: The X-ray excited stress luminescent powder is mixed with epoxy resin and curing agent, and after curing, the X-ray excited stress luminescent material is obtained.

9. Use of the X-ray excited mesoluminescent powder according to claim 1 in the preparation of a stress luminescence sensor.

10. Use of the X-ray excited stress luminescence material according to claim 7 in preparing a stress luminescence sensor.

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