CN107828414B - Silicozirconate elastic stress luminescent material and preparation method and application thereof - Google Patents
Silicozirconate elastic stress luminescent material and preparation method and application thereof Download PDFInfo
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7783—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals one of which being europium
- C09K11/7792—Aluminates
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
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Abstract
The invention discloses a silicozirconate elastic stress luminescent material and a preparation method and application thereof, wherein the luminescent material uses rare earth element Eu2+Is an activator and has a chemical structure represented by Ba2‑x‑ yZr2Si3O12：xEu2+And yRe, wherein x is more than or equal to 0 and less than or equal to 0.10, y is more than or equal to 0 and less than or equal to 0.10: x and y respectively represent the mole percentage content; re represents a trivalent rare earth ion selected from La3+、Ce3+、Pr3+、Nd3+、Sm3+、Dy3+、Gd3+、Tb3+、Ho3+、Yb3+、Lu3+Or Er3+One or more of the above. The material is simple to prepare, stable in chemical property, strong in afterglow and stress luminescence intensity, and can be used as a stress luminescence light source to excite other color luminescent materials while monitoring stress, so that a full-color stress luminescent material is developed.
Description
Technical Field
The invention belongs to the technical field of novel inorganic functional materials, and particularly relates to a silicozirconate elastic stress luminescent material and a preparation method thereof.
Background
The stress luminescence (mechanoluminescence) refers to luminescence generated by a luminous body under the action of various stress stimuli (such as compression, stretching, bending, collision, friction, torsion, ultrasound and the like), and a stress luminescent material is a solid material for realizing light-force conversion under the action of external force, namely, the material luminesces according to the deformation degree caused by the external force. The stress luminescent material may be classified into a destructive stress luminescent material, a plastic stress luminescent material, and an elastic stress luminescent material. The elastic stress luminescent material has the characteristics of repeatability, quick response, high luminous intensity, wide stress range and the like. In addition, in the elastic deformation range, the stress luminous intensity of the elastic stress luminous material is in direct proportion to the deformation size thereof, and the stress distribution condition can be visually displayed in real time, so that the deformation of the detected object under various forces can be reflected by combining the stress luminous material and the coatable material. These properties make it possible for the stress luminescent material to be used as a sensor for detecting the degree of damage to an object. In recent years, with the improvement of stress luminescent material synthesis and development technologies, high-sensitivity CCD cameras and optical fiber technologies are rapidly developed, and in the process of stress luminescent detection, a photographic sensing technology can be used to visualize large-area deformation and conveniently search hidden danger parts for timely repair, so as to achieve the effect of preventing accidents.
To date, over ten kinds of elastic stress luminescent materials capable of emitting light of different colors have been developed. For example, SrMgSi206:Ce3+(purple), SrAl204:Eu2+，Dy3+(Green), ZnS: Mn2+(yellow), SrAl204:Eu2+(yellow-green), Ca2Al2Si07:Ce3+(blue), Sr3SnO7：Sm3+(red). Of these, the two most excellent materials are SrAl204:Eu2+，Dy3+And ZnS: Mn2+Can respond to various stresses and can generate strong luminescence for slight stress, and the response sensitivity is high. However, the disadvantages are also evident, SrAl204:Eu2+，Dy3+The chemical property is not stable enough in the air atmosphere, the hydrolysis is easy to occur, ZnS is Mn2+Corrosive and toxic.
Therefore, the development of an elastic stress luminescent material which is stable in chemical property, non-toxic and simple in preparation method in the field has great driving force for research and application of the material. The present inventors have further studied and developed a silicozirconate elastic stress luminescent material and a method for preparing the same for application, and the present invention has been made based on the results.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a silicozirconate elastic stress luminescent material, a preparation method and application thereof.
In order to solve the technical problems, the technical solution of the invention is as follows:
a silicozirconate elastic stress luminescent material is prepared from rare-earth element Eu2+Is an activator and has a chemical structure represented by Ba2-x-yZr2Si3O12：xEu2+And yRe, wherein x is more than or equal to 0 and less than or equal to 0.10, y is more than or equal to 0 and less than or equal to 0.10: x and y respectively represent the mole percentage content; re represents a trivalent rare earth ion selected from La3+、Ce3+、Pr3+、Nd3+、Sm3+、Dy3+、Gd3+、Tb3+、Ho3+、Yb3+、Lu3+Or Er3+One or more of the above.
Preferably, Ba is selected from its oxide, nitrate or carbonate, Zr is selected from its oxide, and Eu is selected as a divalent rare earth ion activator2+And co-doped trivalent rare earth ion La3+、Ce3+、Pr3+、Nd3+、Sm3+、Dy3+、Gd3+、Tb3+、Ho3+、Yb3+、Lu3+Or Er3+Using its oxides or nitrates.
A method for preparing a silicozirconate elastic stress luminescent material comprises the following steps:
step (1): weighing the raw materials according to the stoichiometric ratio of the elements, wherein Ba adopts the oxide, nitrate or carbonate raw material, Zr adopts the oxide raw material, and the divalent rare earth ion activator Eu2+And co-doped trivalent rare earth ion La3+、Ce3+、Pr3+、Nd3+、Sm3+、Dy3+、Gd3+、Tb3+、Ho3+、Yb3+、Lu3+Or Er3+Adopting the oxide or nitrate raw material;
step (2): adding a proper amount of absolute ethyl alcohol or deionized water into the mixed raw materials, grinding the mixture in an agate mortar for 1-4 hours, drying the mixture in a baking oven at 50-100 ℃ to obtain uniformly ground powder, heating the powder to 700-1000 ℃ at a heating rate of 1-10 ℃/min in an atmospheric environment, and firing the powder for 3-6 hours to obtain a pre-sintered sample;
and (3): fully grinding the powder obtained in the step (2), heating to 1200-1500 ℃ at a heating rate of 1-10 ℃/min in a reducing atmosphere of 5-10% hydrogen, firing for 3-8 hours, and naturally cooling to room temperature along with the furnace;
and (4): fully grinding the powder obtained in the step (3), and sieving the powder by a sieve of 20-50 meshes to obtain the elastic stress luminescent material Ba of the barium silicozirconate cyan long afterglow2-x-yZr2Si3O12：xEu2+And yRe powder.
Preferably, the temperature in step (2) is 800 ℃ and the temperature in step (3) is 1450 ℃.
The application of elastic stress luminescent silicate material is characterized by that the prepared elastic stress luminescent material powder material and optically-transparent organic high-molecular elastic material are mixed, and made into thin sheet or cylindrical resin body or coated on the surface of component to be tested, and the mechanical stress applied on the component can be converted into optical energy so as to implement stress distribution detection.
Preferably, the organic polymer elastic material is one of ABS resin, polyacetal, polycarbonate, polyethylene, polystyrene, polypropylene, polymethyl methacrylate, polyurethane resin, polyester, epoxy resin, or silicone rubber.
After the scheme is adopted, the elastic stress luminescent material of the invention uses divalent europium ions to activate barium zirconate silicate Ba2-x-yZr2Si3O12：xEu2+As matrix, trivalent rare earth ion La is adopted3+、Ce3+、Pr3+、Nd3+、Sm3+、Dy3+、Gd3+、Tb3+、Ho3+、Yb3+、Lu3+Or Er3+One or more of the above-mentioned materials and divalent rare earth ion activator Eu2+Codoping, increasing in host materials by doping with different elementsThe number of carrier traps enhances the elastic stress luminescence intensity, thereby realizing the silicon zirconate luminescent material with long afterglow and stress luminescence properties. Ba2-x-yZr2Si3O12：xEu2+yRe (Re is selected from La)3+、Ce3+、Pr3+、Nd3+、Sm3+、Dy3+、Gd3+、Tb3+、Ho3+、Yb3+、Lu3+Or Er3+One or more of) can generate macroscopic light emission even responding to an external force signal, and is a cyan long-afterglow elastic stress luminescent material Ba2-x-yZr2Si3O12：xEu2+And the practical application of yRe in the fields of elastic stress light-emitting devices and the like lays a foundation. The method has wide application prospect in various fields of production and life in stress detection and monitoring of artificial skin, identity authentication, mechanical parts, building facilities and the like.
The invention has the beneficial effects that:
(1) the material preparation adopts the traditional solid phase method, the preparation process is simple, the conditions are easy to control, the equipment requirement is low, the cost is low, no toxic gas is generated in the preparation process, and no pollution is caused to the environment;
(2) the prepared elastic stress luminescent material and an optically transparent high-molecular elastic material are mixed to prepare a sheet or a cylindrical resin body, or are coated on the surface of a component to be tested, and various external forces (compression, stretching, bending, shearing, friction, ultrasound and the like) can be converted into light energy to be emitted;
(3) the cyan long afterglow elastic stress luminescent material Ba2-x-yZr2Si3O12 prepared by the invention: the actual elastic stress luminescence intensity of xEu2+ and yRe can be seen by naked eyes in a bright environment;
(4) the invention relates to a cyan long afterglow elastic stress luminescent material Ba2-x-yZr2Si3O 12: the luminous intensity of xEu2+, yRe and the composite material thereof depends on the mechanical energy of the excitation source in the elastic stress range. The luminous intensity of the material is increased along with the increase of mechanical acting force, so that the material generates stress luminescence. The cyan long afterglow elastic stress luminescent material and the composite material thereof have a direct proportion relation between the luminous intensity and the stress intensity in the elastic deformation range, and can realize stress distribution detection.
Drawings
FIG. 1 is an X-ray diffraction pattern of a cyan long persistence elastic stress luminescent material prepared in examples 1-5 of the present invention;
FIG. 2 is a graph of the stress luminescence intensity at 1500N cyclic pressure for a stress luminescence sample prepared by mixing example 4 of the material of the present invention with an optically transparent polymeric elastomer;
FIG. 3 is a gray-scale photograph of a stress luminescence sample prepared by mixing example 4 of the material of the present invention with an optically transparent polymer elastic material.
Detailed Description
The invention discloses a silicozirconate elastic stress luminescent material, which uses rare earth element Eu2+Is an activator and has a chemical structure represented by Ba2-x-yZr2Si3O12：xEu2+And yRe, wherein x is more than or equal to 0 and less than or equal to 0.100 and less than or equal to 0.10: x and y respectively represent the mole percentage content; re represents a trivalent rare earth ion selected from La3+、Ce3+、Pr3+、Nd3+、Sm3+、Dy3 +、Gd3+、Tb3+、Ho3+、Yb3+、Lu3+Or Er3+One or more of the above.
The invention is described in further detail below with reference to the figures and specific examples.
Taking example 1 as an example, synthesis was performed by a typical high temperature solid phase method, comprising the following steps:
step (1): weighing the raw materials according to the stoichiometric ratio of each elementI.e. analytically pure BaCO3、ZrO2、SiO2、Eu2O3、Dy2O3Weighing (BaCO) according to molar ratio3＝0.5314，ZrO2＝0.3352，SiO2＝0.2451，Eu2O3＝0.00239，Dy2O3＝0.00254)。
Step (2): and then adding a proper amount of absolute ethyl alcohol into the mixed raw materials, grinding the mixture in an agate mortar for 1-4 hours, drying the mixture in a 50-100 ℃ drying oven to obtain uniformly ground powder, heating the uniformly ground powder to 800 ℃ at a heating rate of 1-10 ℃/min in an atmospheric environment, and firing the powder for 3 hours to obtain a pre-sintered sample.
And (3): and (3) fully grinding the powder obtained in the step (2), heating to 1450 ℃ at a heating rate of 1-10 ℃/min in a reducing atmosphere of 5-10% hydrogen, firing for 4 hours, and naturally cooling to room temperature along with the furnace.
And (4): fully grinding the powder obtained in the step (3), and sieving the powder by a 20-mesh sieve to obtain the elastic stress luminescent material Ba of the barium silicozirconate cyan long afterglow1.98Zr2Si3O12:Eu0.01,Dy0.01And (3) powder.
And (3) mixing the elastic stress luminescent material powder obtained after sieving in the step (4) with an optically transparent organic polymer elastic material (such as ABS resin, Polyacetal (PA), Polycarbonate (PC), Polyethylene (PE), Polystyrene (PS), polypropylene (PP), polymethyl methacrylate (PMMA), polyurethane resin, polyester, epoxy resin, silicon rubber and the like), and then preparing the mixture into a sheet or cylindrical resin body or coating the sheet or cylindrical resin body on the surface of a part to be detected, so that the mechanical stress borne by the part can be converted into optical energy, and the stress distribution detection is realized. The stress luminous intensity of the material can be observed by naked eyes; within the elastic limit of the material, the stress luminous intensity is in direct proportion to the applied stress intensity, and the elastic stress luminous intensity can be seen by naked eyes in dark.
The other implementation is the same as the preparation method of the implementation 1, except that the raw material proportion is different, as shown in figure 1, the X-ray diffraction pattern of the cyan long-afterglow elastic stress luminescent material prepared in the examples 1-5 of the invention shows that the prepared powder is pure phase, and the rare earth ions are doped without disturbing the crystal. As shown in fig. 2, it is a stress luminescence intensity graph of a stress luminescence sample prepared by mixing example 4 of the material of the present invention with an optically transparent polymer elastic material under a cyclic pressure of 1500N, which shows that the stress luminescence intensity has a good linear relationship with stress, excellent repeatability and slow decay of the stress luminescence intensity. Fig. 3 shows a gray-scale photograph of a stress luminescence sample prepared by mixing example 4 of the material of the present invention with an optically transparent polymer elastic material, which shows that the sample emits light visible to the naked eye when pressure is applied in a dark room environment.
Doped in the embodiment of the invention is Pr3+And Dy3+Ions, but other trivalent rare earths, e.g. La3+、Ce3+、Nd3+、Sm3+、Gd3+、Tb3+、Ho3+、Yb3+、Lu3+Or Er3+And can be codoped to achieve the aim and the effect of the invention.
Embodiment 6 a method for preparing a silicozirconate elastic stress luminescent material comprises the following steps: step (1): weighing the raw materials according to the stoichiometric ratio of the elements, wherein Ba adopts the oxide raw material, Zr adopts the oxide raw material, and the divalent rare earth ion activator Eu2+And co-doped trivalent rare earth ion La3+Adopting nitrate raw materials; step (2): adding a proper amount of absolute ethyl alcohol or deionized water into the mixed raw materials, grinding the mixture in an agate mortar for 1-4 hours, drying the mixture in an oven at the temperature of 80 ℃ to obtain uniformly ground powder, heating the powder to 700 ℃ at the heating rate of 1-10 ℃/min in the atmospheric environment, and firing the powder for 6 hours to obtain a pre-sintered sample; and (3): fully grinding the powder obtained in the step (2), heating to 1500 ℃ at a heating rate of 1-10 ℃/min in a reducing atmosphere of 5-10% hydrogen, firing for 3 hours, and naturally cooling to room temperature along with the furnace; and (4): and (4) fully grinding the powder obtained in the step (3), and sieving the powder by using a 50-mesh sieve to obtain the barium silicozirconate cyan long-afterglow elastic stress luminescent material powder.
Example 7A silicozirconate bombThe preparation method of the stress luminescent material comprises the following steps: step (1): weighing the raw materials according to the stoichiometric ratio of the elements, wherein Ba adopts nitrate raw material, Zr adopts oxide raw material, and divalent rare earth ion activator Eu2+And co-doped trivalent rare earth ion Er3+Adopting the oxide raw material; step (2): adding a proper amount of absolute ethyl alcohol or deionized water into the mixed raw materials, grinding the mixture in an agate mortar for 1 to 4 hours, drying the mixture in a baking oven at the temperature of between 50 and 100 ℃ to obtain uniformly ground powder, heating the powder to 1000 ℃ at the heating rate of 1 to 10 ℃/min in the atmospheric environment, and firing the powder for 3 hours to obtain a pre-sintered sample; and (3): fully grinding the powder obtained in the step (2), heating to 1200 ℃ at a heating rate of 1-10 ℃/min in a reducing atmosphere of 5-10% hydrogen, firing for 8 hours, and naturally cooling to room temperature along with the furnace; and (4): and (4) fully grinding the powder obtained in the step (3), and sieving the powder by using a 40-mesh sieve to obtain the barium silicozirconate cyan long-afterglow elastic stress luminescent material powder.
Embodiment 8 a method for preparing a silicozirconate elastic stress luminescent material comprises the following steps: step (1): weighing the raw materials according to the stoichiometric ratio of the elements, wherein Ba adopts the oxide raw material, Zr adopts the oxide raw material, and the divalent rare earth ion activator Eu2+Adopts the oxide raw material and co-doped trivalent rare earth ion Ce3+、Sm3+And Nd3+Adopting the oxide raw material; step (2): adding a proper amount of absolute ethyl alcohol or deionized water into the mixed raw materials, grinding the mixture in an agate mortar for 1-4 hours, drying the mixture in a drying oven at 100 ℃ to obtain uniformly ground powder, heating the powder to 1000 ℃ at a heating rate of 1-10 ℃/min in an atmospheric environment, and firing the powder for 5 hours to obtain a pre-sintered sample; and (3): fully grinding the powder obtained in the step (2), heating to 1200 ℃ at a heating rate of 1-10 ℃/min in a reducing atmosphere of 5-10% hydrogen, firing for 6 hours, and naturally cooling to room temperature along with the furnace; and (4): and (4) fully grinding the powder obtained in the step (3), and sieving the powder by using a 30-mesh sieve to obtain the barium silicozirconate cyan long-afterglow elastic stress luminescent material powder.
The above-mentioned embodiments are only preferred embodiments of the present invention, and do not limit the technical scope of the present invention, so that the changes and modifications made by the claims and the specification of the present invention should fall within the scope of the present invention.
Claims (6)
1. A silicozirconate elastic stress luminescent material is characterized in that: the luminescent material is made of rare earth element Eu2+Is an activator and has a chemical structure expression Ba2-x-yZr2Si3O12：xEu2+yRe wherein 0<x≤0.10，0<y is less than or equal to 0.10; x and y respectively represent the mole percentage content; re represents trivalent rare earth ion Dy3+。
2. The elastic stress luminescent material of silicate as claimed in claim 1, wherein: ba is oxide, nitrate or carbonate thereof, Zr is oxide thereof, divalent rare earth ion activator Eu2+And co-doped trivalent rare earth ion Dy3+Using its oxides or nitrates.
3. A method for preparing a silicozirconate elastic stress luminescent material according to claim 1, wherein: the method comprises the following steps: step (1): weighing the raw materials according to the stoichiometric ratio of the elements, wherein Ba adopts the oxide, nitrate or carbonate raw material, Zr adopts the oxide raw material, and the divalent rare earth ion activator Eu2+And co-doped trivalent rare earth ion Dy3+Adopting the oxide or nitrate raw material; step (2): adding a proper amount of absolute ethyl alcohol or deionized water into the mixed raw materials, grinding the mixture in an agate mortar for 1-4 hours, drying the mixture in a drying oven at 50-100 ℃ to obtain uniformly ground powder, heating the powder to 700-1000 ℃ at a heating rate of 1-10 ℃/min in an atmospheric environment, and firing the powder for 3-6 hours to obtain a pre-sintered sample; and (3): fully grinding the powder obtained in the step (2), heating to 1200-1500 ℃ at a heating rate of 1-10 ℃/min in a reducing atmosphere of 5-10% hydrogen, firing for 3-8 hours, and naturally cooling to room temperature along with the furnace; and (4): obtained in the step (3)The obtained powder is fully ground and sieved by a 20-50 mesh screen to obtain the elastic stress luminescent material Ba of barium silicozirconate cyan long afterglow2-x-yZr2Si3O12：xEu2+And yRe powder.
4. The method of claim 3, wherein the steps of preparing the elastic stress luminescent silicate material are as follows: the temperature in step (2) is 800 ℃ and the temperature in step (3) is 1450 ℃.
5. Use of the elastic stress silicate phosphor according to claim 2, wherein: the prepared elastic stress luminescent material powder is mixed with an optically transparent organic polymer elastic material to prepare a sheet or cylindrical resin body or coat the surface of a component to be detected, and the mechanical stress borne by the component can be converted into light energy to realize stress distribution detection.
6. The elastic stress luminescent material of silicate according to claim 5, wherein: the organic polymer elastic material is one of ABS resin, polyacetal, polycarbonate, polyethylene, polystyrene, polypropylene, polymethyl methacrylate, polyurethane resin, polyester, epoxy resin or silicon rubber.
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| CN105670615A (en) * | 2016-03-08 | 2016-06-15 | 浙江大学 | Bivalent europium ion-doped strontium aluminate cage type microsphere light-emitting material and preparation method thereof |
| CN107129805A (en) * | 2017-04-17 | 2017-09-05 | 南昌大学 | A kind of europium ion-doped silicate white fluorescent material and preparation method thereof |
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| CN107129805A (en) * | 2017-04-17 | 2017-09-05 | 南昌大学 | A kind of europium ion-doped silicate white fluorescent material and preparation method thereof |
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| Interplay between local environments and photoluminescence of Eu2+ in Ba2Zr2Si3O12:blue shift emission, optimal bond valence and luminescence mechanisms;Yang Zhang et al.;《Journal of Materials Chemistry C》;20151231;第3卷;第3294-3303页 * |
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