Basalt-like structure intelligent stress luminescent material and preparation method thereof

Abstract

The present application belongs to the technical field of inorganic luminescent materials. The present application discloses a kind of basalt structure intelligent stress luminescent material and preparation method thereof. The chemical general formula of the stress luminescent material of the present application is Mg2SiO4:m%Cr,n%X. The stress luminescent material of the present application has stable chemical properties, high modulus and high strength mechanical properties, and high temperature resistance. The material of the present application can be prepared into fibers and used as lightweight structural materials, applied to structural elements in aerospace and automotive industry. It can also play its near-infrared stress luminescent characteristics to provide signal feedback in emergency situations and enhance safety. The material of the present application is also suitable for fire protection in high-temperature industries such as metallurgy, steel and casting. It can be used as insulation material for various heat insulation equipment in high-temperature industries. The raw materials of the material of the present application are widely available, and the preparation process is simple. It is expected to reduce the preparation cost in large-scale production, and provide strong support for the wide application of stress luminescent materials.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of inorganic luminescent materials, and particularly relates to a basalt-like structure intelligent stress luminescent material and a preparation method thereof. BACKGROUND

[0002] Mechanoluminescence is a phenomenon in which materials emit light when subjected to mechanical stress or deformation. Traditional photoluminescent materials require an external short-wave excitation light source to achieve the light-emitting process through energy level transition. Stress luminescent materials can convert mechanical signals into optical signals without the need for light or power, which makes them have broad application prospects in the field of optoelectronic applications.

[0003] Natural basalt fibers were first discovered in volcanic rocks by melting basalt ore and drawing it into fibers. The high strength, corrosion resistance, and high temperature resistance of this fiber have gradually attracted attention and are widely used in the construction, automotive, and aerospace industries. However, the preparation of natural basalt materials is limited by the source and quality of the ore. By artificially synthesizing or modifying materials to simulate the properties of basalt, more stable and controllable performance can be obtained, so the development of basalt-like materials has emerged as the times require. Basalt-like materials refer to materials with similar properties or functions to natural basalt materials. Through artificial synthesis technology, the chemical composition of the materials can be more accurately controlled to ensure performance stability and consistency. These materials can not only simulate the mechanical properties of basalt in performance, but also can be doped with different functional substances (such as nanomaterials, metal oxides, etc.) to have more characteristics. For example, the materials can be endowed with higher fire resistance, impact resistance, or self-repairing function to meet the needs of different fields. The development of basalt-like materials not only makes up for the limitations of natural basalt materials, but also expands their application scenarios, and is a new type of material with important industrial and economic value.

[0004] Magnesium disilicate (Mg2SiO4), also known as olivine, is a part of the basalt-like structure mineral and belongs to the orthorhombic system. Under high temperature and high pressure conditions in the Earth's interior, it can maintain structural stability and is a widely existing mineral in the crust and upper mantle. It is mainly composed of magnesium and silicon-oxygen tetrahedra and belongs to silicate minerals. Olivine has an orthorhombic structure, with silicon-oxygen tetrahedra closely arranged to form a three-dimensional network structure, making it relatively hard, with a Mohs hardness of about 6.5-7. This structure makes it highly strong and stable under high temperature and high pressure environments. It has good chemical stability under high temperature and dry environments and strong resistance to acid and alkali corrosion. Its melting point is about 1890°C, so magnesium disilicate has good high-temperature resistance and is often used in refractory materials. It is widely used in the lining of high-temperature industrial equipment, such as steelmaking furnaces, smelting furnaces, crucibles, and kilns in the steel industry. It is also used to produce refractory bricks that can withstand high temperatures and severe thermal shocks. Due to its low expansion coefficient, it can maintain good thermal stability, so it is often used as a casting mold material in the casting industry. It can be used for casting steel, iron, copper, and other metals, especially for castings that require high stability at high temperatures. In addition, olivine powder is used as a raw material for producing high-temperature ceramics and special ceramics, which can significantly improve the high-temperature resistance and wear resistance of ceramic products, and is commonly used in the manufacture of high-temperature equipment and parts.

[0005] Existing materials cannot simultaneously possess the high-temperature resistance, high strength and modulus mechanical properties, and self-recovery near-infrared stress luminescence performance of magnesium disilicate materials. Traditional stress luminescence materials often experience performance degradation or failure under high temperature environments, and their luminescence efficiency and stability under strong mechanical stress are difficult to guarantee, which limits their application under extreme conditions. In contrast, basalt-like structure stress luminescence materials not only have excellent high-temperature resistance and heat insulation performance, but also maintain stable luminescence characteristics under high temperature and strong mechanical stress, significantly improving the reliability and safety of materials in high-temperature industrial equipment, building fireproof layers, and other applications that require real-time monitoring and fireproof insulation.

[0006] Currently, there are relatively few silicate materials with basalt-like structure that can achieve near-infrared stress luminescence. The relevant silicate materials reported so far include CaMgSi2O6:Dy 3+ reported by Ravishankar Shukla University in India in Journal of Alloys and Compounds, 2015, 649:1329-1338, Sr2MgSi2O7:Dy 3+; and Ca2MgSi2O7:Eu reported by other institutions in Integrated Ferroelectrics, 2015, 159(1): 49-56 2+ ,Dy 3+ ; Ba2MgSi2O7:Eu reported by Luminescence, 2015, 30(8): 1207-1211 2+ ,Dy 3+ , etc.

[0007] Chromium-doped near-infrared stress luminescence materials include LiGa5O8:Cr reported by Beijing University of Science and Technology in Advanced Functional Materials, 2021, 31(19): 2010685 3+ , ZnGa2O4:Cr 3+ , Zn3Ga2GeO8:Cr 3+ , SrGa 12 O 19 :Cr 3+ ; Y3Al5O 12 : Cr reported by Kunming University of Science and Technology in Advanced Functional Materials, 2023, 33(27): 2214497 3+ ; LaAlO3:Cr reported by South China University of Technology in Advanced Powder Materials, 2024, 3(2): 100165 3+ ; Ga2O3:Cr reported by City University of Hong Kong in Matter, 2023, 6(9): 2935-2949 3+ ; SrAl2O4:Eu-Cr system developed by Japan Institute of Industrial Technology: Journal of The Electrochemical Society, 2021, 168(4): 047508; ECS Transactions, 2020, 98(11): 61; CN 105209572 A, etc. SUMMARY

[0008] The present application aims to provide a high-performance stress luminescence material and a preparation method thereof, which not only enables stress luminescence materials to be more widely applied in fields such as construction, aerospace, and industrial manufacturing, but also enables the application scenarios of basalt-like structural materials, including but not limited to strain sensing, structural detection, sensing and real-time monitoring technology in the medical field.

[0009] This invention relates to a basalt-like structure intelligent stress-luminescent material that combines high modulus, high strength, and high-temperature resistance. The material emits light directly under stress without prior illumination, with an emission wavelength ranging from 650 nm to 1000 nm and a broad emission peak around 730 nm. The light intensity is primarily distributed in the near-infrared short-wavelength band. This material exhibits high-intensity elastic stress-luminescence properties, a simple and low-cost preparation process, and stable chemical properties. It can directly respond to various forms of mechanical force signals, such as compression, tension, bending, collision, friction, and torsion, and the emitted light can be observed using an infrared camera.

[0010] This invention provides the following technical solution:

[0011] This invention provides a basalt-like structure intelligent stress-luminescent material, wherein the chemical formula of the stress-luminescent material is Mg2SiO4: m%Cr,n%X, 0.000001≤m≤10.9, 0.000001≤n≤10.9;

[0012] Where m% represents the molar percentage of Cr relative to Mg2SiO4, and n% represents the molar percentage of X relative to Mg2SiO4;

[0013] The X element includes at least one of Yb, Eu, Er, Nd, Sm, Dy, Ni, Al, and Ga.

[0014] The preparation method of the basalt-like structure intelligent stress-luminescent material of the present invention includes the following steps:

[0015] S1. Weigh the raw materials according to the stoichiometric ratio of each element in the general chemical formula of stress luminescent materials, mix the raw materials to obtain a mixed raw material; add anhydrous ethanol to the mixed raw material, grind and mix evenly, and then dry to obtain a mixed powder.

[0016] S2. Calcine the mixed powder in S1 in an air or oxygen atmosphere, and then let it cool naturally in the furnace.

[0017] S3. Grind the powder cooled in S2 to obtain a basalt-like structure intelligent stress luminescent material.

[0018] Preferably, the temperature is raised to 1300-1450°C at a heating rate of 1-100°C / min in an air or oxygen atmosphere, and calcined for 0.5-24 hours.

[0019] Preferably, anhydrous ethanol is added to the mixed raw materials, and after grinding and mixing evenly, the mixture is dried at 80~300℃ to obtain a mixed powder.

[0020] Preferably, the raw materials corresponding to the Mg element include Mg oxides, hydroxides or carbonates, and natural ores;

[0021] The natural ore includes at least one of magnesite, olivine, serpentine, and magnesia.

[0022] The raw materials corresponding to the Si element include Si oxides;

[0023] The raw materials corresponding to the Cr element include Cr oxides, chlorides, and soluble nitrates.

[0024] The raw materials corresponding to element X include oxides, chlorides, and soluble nitrates of X.

[0025] The prepared basalt-like structure intelligent stress luminescent material is ground and sieved into powder, which is then encapsulated in an optically transparent organic polymer elastic material PET to form a thin sheet. This sheet is then attached to the surface of the component to be tested. Under the action of mechanical external force, the stress on the composite is converted into light emission, achieving direct force-light conversion in the near-infrared band.

[0026] The basalt-like structure intelligent stress-luminescent material of the present invention, within the elastic limit, exhibits a stress-luminescent intensity that is positively correlated with the magnitude of the applied mechanical force.

[0027] The following are the beneficial effects of the present invention:

[0028] 1) The material of this invention is prepared by the traditional high-temperature solid-state method, which is simple and low in cost;

[0029] 2) The main elements required for the materials of this invention are oxygen, silicon and magnesium. These elements are common elements in the earth's crust, and the raw materials are abundant and easy to obtain from nature.

[0030] 3) The material of this invention has near-infrared stress luminescence characteristics. Within the elastic range, it can convert the received stress into near-infrared light emission, which can be observed using an infrared camera.

[0031] 4) The material of this invention can be widely used in many fields such as force sensing, bioimaging, anti-counterfeiting, and military applications. This type of material offers a potential solution to the current energy crisis and also broadens new horizons for multi-pathway energy conversion;

[0032] 5) The material of this invention has high temperature resistance and near-infrared stress luminescence properties, which can be used to develop high temperature resistant sensors and realize real-time stress monitoring in high temperature environments, which is crucial for the safe operation of energy, aviation and other fields.

[0033] 6) The material of this invention can be used to prepare fibers to maximize its mechanical properties and high-temperature resistance. This fiber is lightweight yet possesses high strength, making it suitable as a lightweight structural material for applications requiring materials that are both lightweight and strong, such as structural components in the aerospace and automotive industries. It can reduce weight while providing sufficient high-temperature resistance and mechanical strength, and also utilizes its near-infrared stress-luminescence properties to provide signal feedback in emergency situations, enhancing safety. Therefore, it has enormous application potential and can be used to manufacture bulletproof vests, spacesuits, etc.

[0034] 7) The fiber prepared by this invention, due to its high-temperature resistance, is commonly used in the manufacture of refractory fabrics, thermal insulation materials, and fire-resistant clothing. These materials maintain strength and structural stability at extreme high temperatures, making them suitable for fire protection in high-temperature industries such as metallurgy, steel, and casting. In terms of high-temperature insulation, the fiber can be used as refractory blankets and refractory liners, providing excellent thermal insulation protection for furnaces, boilers, and kilns. Furthermore, this fiber is an excellent thermal insulator and can be used as insulation material for various thermal insulation equipment in high-temperature industries, such as high-temperature furnace linings, pipe insulation materials, and insulation boards in heat treatment equipment.

[0035] 8) The fibers prepared by the material of this invention can also be used to manufacture high-performance composite materials, enhancing their heat resistance and strength. They can be combined with ceramics, resins, or other matrix materials to create high-temperature composite materials suitable for applications in aerospace, aviation, and automotive fields. These fiber-reinforced composite materials not only possess high strength but also exhibit excellent durability under high temperatures and harsh environments. They can be used to manufacture friction materials such as brake pads and clutch discs. Particularly in mechanical systems requiring high friction performance and thermal stability, the fibers can improve the wear resistance and service life of the materials. Attached Figure Description

[0036] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0037] Figure 1 This invention provides a schematic flowchart of a method for preparing a basalt-like structure intelligent stress-luminescent material;

[0038] Figure 2 The XRD patterns of the Mg2SiO4:0.4%Cr powder prepared in Examples 2-4 of this invention are shown.

[0039] Figure 3The stress emission spectra of the Mg2SiO4:0.4%Cr powder materials prepared in Examples 2-4 of this invention under a force of 30N are shown.

[0040] Figure 4 The XRD spectra of Mg2SiO4:m%Cr powder materials prepared by calcination at 1450℃ in Examples 4, 6-8 of the present invention and the corresponding XRD standard card of Mg2SiO4 are shown.

[0041] Figure 5 The images show the stress emission spectra of Mg2SiO4:m%Cr powder materials prepared by calcination at 1450℃ in Examples 4-9 of this invention under a force of 30N.

[0042] Figure 6 The diagram shows the stress luminescence integral intensity of the Mg2SiO4:0.4%Cr powder material prepared in Example 4 of this invention under forces of 5N, 10N, 20N, 30N, and 40N.

[0043] Figure 7 The average stress-luminescence integral intensity diagram of the Mg2SiO4:0.4%Cr powder material prepared in Example 4 of this invention was repeatedly tested under a 10N force for 10 groups, with 5 tests per group.

[0044] Figure 8 The stress emission spectra of Mg2SiO4: 0.4%Cr, n%Yb powder materials prepared by calcination at 1450℃ in Examples 10-12 of this invention are shown under a force of 30N. Detailed Implementation

[0045] To facilitate understanding of the present invention, a more comprehensive description of the invention will be provided below in conjunction with specific embodiments. Preferred embodiments of the invention are given in the specific embodiments. However, the present invention can be implemented in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided to provide a thorough and complete understanding of the disclosure of the present invention.

[0046] The application principle of the present invention will be described in detail below with reference to the accompanying drawings.

[0047] This invention provides a basalt-like structure intelligent stress-luminescent material with the chemical formula Mg2SiO4: m%Cr,n%X, where 0.000001≤m≤10.9 and 0.000001≤n≤10.9.

[0048] Where m% represents the molar percentage of Cr relative to Mg2SiO4, and n% represents the molar percentage of X relative to Mg2SiO4;

[0049] The X element includes at least one of Yb, Eu, Er, Nd, Sm, Dy, Ni, Al, and Ga. Co-doping with Yb gives the material a new stress emission peak, while other co-doped elements do not exhibit this significant phenomenon. Therefore, Yb is provided as an example below.

[0050] The basalt-like structure intelligent stress-luminescent material of this invention possesses stable chemical properties, high modulus, high strength, and high temperature resistance. This material can be prepared into fibers for use as lightweight structural materials in structural components in the aerospace and automotive industries. It can also leverage its near-infrared stress-luminescent properties to provide signal feedback in emergency situations, enhancing safety. Furthermore, this material is suitable for fire protection in high-temperature industries such as metallurgy, steel, and casting, and can be used as insulation material for various heat-insulating equipment in these industries. The raw materials for this material are widely available, and the preparation process is simple, which promises to reduce production costs in large-scale production, providing strong support for the widespread application of stress-luminescent materials.

[0051] The preparation method of the basalt-like structure intelligent stress-luminescent material of the present invention includes the following steps:

[0052] S1. Weigh the raw materials according to the stoichiometric ratio of each element in the general chemical formula of stress luminescent materials, mix the raw materials to obtain a mixed raw material; add anhydrous ethanol to the mixed raw material, grind and mix evenly, and then dry to obtain a mixed powder.

[0053] S2. Calcine the mixed powder in S1 in an air or oxygen atmosphere, and then let it cool naturally in the furnace.

[0054] S3. Grind the powder cooled in S2 to obtain a basalt-like structure intelligent stress luminescent material.

[0055] In some embodiments, the temperature is increased to 1300-1450°C at a heating rate of 1-100°C / min under an air or oxygen atmosphere, and calcined for 0.5-24 hours.

[0056] In some embodiments, anhydrous ethanol is added to the mixed raw materials, and after grinding and mixing evenly, the mixture is dried at 80~300°C to obtain a mixed powder.

[0057] In some embodiments, the raw materials corresponding to the Mg element include Mg oxides, hydroxides or carbonates, and natural ores;

[0058] Natural minerals include at least one of magnesite, peridot, serpentine, and magnesia.

[0059] The raw materials corresponding to Si include Si oxides;

[0060] The raw materials corresponding to Cr element include Cr oxides, chlorides, and soluble nitrates;

[0061] The raw materials corresponding to element X include oxides, chlorides, and soluble nitrates of X.

[0062] In some embodiments, such as Figure 1 As shown, the preparation method of the basalt-like structure intelligent stress luminescent material includes the following steps:

[0063] Step 1: The dopant element Cr is produced using its oxide Cr2O3 as raw material, the dopant element X is produced using its oxide as raw material, and the matrix is ​​produced using MgO and SiO2 as raw materials. The raw materials of each element are weighed according to the stoichiometric ratio, and then the obtained raw materials are placed in an agate mortar, and sufficient anhydrous ethanol or deionized water is added to completely submerge the raw materials. Next, the mixture is ground and mixed until it is uniformly mixed to obtain a mixed powder. Subsequently, the mixed powder is placed in an oven at 80°C to dry, and finally the mixed powder is obtained.

[0064] Step 2: Place the mixed powder obtained in Step 1 into an alumina crucible or other high-temperature resistant container, and heat it to 1300℃~1450℃ in an air or oxygen atmosphere at a heating rate of 1~100℃ / min. Calcinate for 4 hours, and then allow it to cool naturally in the furnace.

[0065] Step 3: Grind the cooled powder and pass it through a 150-mesh sieve to obtain Mg2SiO4: m%Cr,n%X powder, which is a near-infrared stress luminescent material.

[0066] The following specific embodiments further illustrate the basalt-like structure intelligent stress-luminescent material and its preparation method of the present invention. This section further illustrates the content of the present invention in conjunction with specific embodiments, but should not be construed as limiting the present invention. Unless otherwise specified, the technical means used in the embodiments are conventional means well known to those skilled in the art. Unless otherwise specified, the reagents, methods, and equipment used in the present invention are conventional reagents, methods, and equipment in the art.

[0067] Example 1

[0068] This embodiment provides a basalt-like structure intelligent stress luminescent material with the general chemical formula Mg2SiO4:0.4%Cr;

[0069] The preparation method of the above material is illustrated using Mg2SiO4:0.4%Cr at 1300℃ as an example. The specific operation steps are as follows:

[0070] Step 1: The dopant element Cr is produced using its oxide Cr2O3 as the raw material, and the matrix is ​​produced using MgO and SiO2 as raw materials. The raw materials of each element are weighed according to the stoichiometric ratio and mixed to obtain a mixed raw material. Then, the obtained mixed raw material is placed in an agate mortar and sufficient anhydrous ethanol is added to completely submerge the mixed raw material. Next, the mixed raw material is ground and mixed until it is uniformly mixed to obtain a mixed powder. Subsequently, the mixed powder is placed in an oven at 80°C to dry, and finally, the mixed powder is obtained.

[0071] Step 2: Place the mixed powder in an alumina crucible and heat it in a muffle furnace from room temperature (25°C) to 1000°C at a heating rate of 10°C / min. Then heat it from 1000°C to 1300°C at a heating rate of 5°C / min for 8 hours. Finally, allow it to cool down naturally in the furnace.

[0072] Step 3: Crush and grind the cooled powder obtained in Step 2, and pass it through a 150-mesh sieve to obtain near-infrared stress-luminescent Mg2SiO4:0.4%Cr powder.

[0073] Example 2

[0074] This embodiment provides a basalt-like structure intelligent stress luminescent material with the general chemical formula Mg2SiO4:0.4%Cr;

[0075] The preparation method of the above material is illustrated using Mg2SiO4:0.4%Cr at 1350℃ as an example. The specific operation steps are as follows:

[0076] Step 1: The dopant element Cr is produced using its oxide Cr2O3 as the raw material, and the matrix is ​​produced using MgO and SiO2 as raw materials. The raw materials of each element are weighed according to the stoichiometric ratio and mixed to obtain a mixed raw material. Then, the obtained mixed raw material is placed in an agate mortar and sufficient anhydrous ethanol is added to completely submerge the mixed raw material. Next, the mixed raw material is ground and mixed until it is uniformly mixed to obtain a mixed powder. Subsequently, the mixed powder is placed in an oven at 80°C to dry, and finally, the mixed powder is obtained.

[0077] Step 2: Place the mixed powder in an alumina crucible and heat it in a muffle furnace from room temperature (25°C) to 1000°C at a heating rate of 10°C / min. Then heat it from 1000°C to 1350°C at a heating rate of 5°C / min and calcine for 8 hours. Finally, allow it to cool down naturally in the furnace.

[0078] Step 3: Crush and grind the cooled powder obtained in Step 2, and pass it through a 150-mesh sieve to obtain near-infrared stress-luminescent Mg2SiO4:0.4%Cr powder.

[0079] Example 3

[0080] This embodiment provides a basalt-like structure intelligent stress luminescent material with the general chemical formula Mg2SiO4:0.4%Cr;

[0081] The preparation method of the above material is illustrated using Mg2SiO4:0.4%Cr at 1400℃ as an example. The specific operation steps are as follows:

[0082] Step 1: The dopant element Cr is produced using its oxide Cr2O3 as the raw material, and the matrix is ​​produced using MgO and SiO2 as raw materials. The raw materials of each element are weighed according to the stoichiometric ratio and mixed to obtain a mixed raw material. Then, the obtained mixed raw material is placed in an agate mortar and sufficient anhydrous ethanol is added to completely submerge the mixed raw material. Next, the mixed raw material is ground and mixed until it is uniformly mixed to obtain a mixed powder. Subsequently, the mixed powder is placed in an oven at 80°C to dry, and finally, the mixed powder is obtained.

[0083] Step 2: Place the mixed powder in an alumina crucible and heat it in a muffle furnace from room temperature (25°C) to 1000°C at a heating rate of 10°C / min. Then heat it from 1000°C to 1400°C at a heating rate of 5°C / min and calcine for 8 hours. Finally, allow it to cool down naturally in the furnace.

[0084] Step 3: Crush and grind the cooled powder obtained in Step 2, and pass it through a 150-mesh sieve to obtain near-infrared stress-luminescent Mg2SiO4:0.4%Cr powder.

[0085] Example 4

[0086] This embodiment provides a basalt-like structure intelligent stress luminescent material with the general chemical formula Mg2SiO4:0.4%Cr;

[0087] The preparation method of the above material is illustrated using Mg2SiO4:0.4%Cr at 1450℃ as an example. The specific operation steps are as follows:

[0088] Step 1: The dopant element Cr is produced using its oxide Cr2O3 as the raw material, and the matrix is ​​produced using MgO and SiO2 as raw materials. The raw materials of each element are weighed according to the stoichiometric ratio and mixed to obtain a mixed raw material. Then, the obtained mixed raw material is placed in an agate mortar and sufficient anhydrous ethanol is added to completely submerge the mixed raw material. Next, the mixed raw material is ground and mixed until it is uniformly mixed to obtain a mixed powder. Subsequently, the mixed powder is placed in an oven at 80°C to dry, and finally, the mixed powder is obtained.

[0089] Step 2: Place the mixed powder in an alumina crucible and heat it in a muffle furnace from room temperature (25°C) to 1000°C at a heating rate of 10°C / min. Then heat it from 1000°C to 1450°C at a heating rate of 5°C / min and calcine for 8 hours. Finally, allow it to cool down naturally in the furnace.

[0090] Step 3: Crush and grind the cooled powder obtained in Step 2, and pass it through a 150-mesh sieve to obtain near-infrared stress-luminescent Mg2SiO4:0.4%Cr powder.

[0091] Example 5

[0092] This embodiment provides a basalt-like structure intelligent stress luminescent material with the general chemical formula Mg2SiO4: 0%Cr;

[0093] The preparation method of the above material is illustrated using Mg2SiO4:0%Cr at 1450℃ as an example. The specific operation steps are as follows:

[0094] Step 1: The matrix uses MgO and SiO2 as raw materials. The raw materials of each element are weighed according to the stoichiometric ratio and mixed to obtain a mixed raw material. Then, the obtained mixed raw material is placed in an agate mortar and sufficient anhydrous ethanol is added to completely submerge the mixed raw material. Next, the mixed raw material is ground and mixed until it is uniformly mixed to obtain a mixed powder. Subsequently, the mixed powder is placed in an oven at 80°C to dry, and finally, a mixed powder is obtained.

[0095] Step 2: Place the mixed powder in an alumina crucible and heat it in a muffle furnace from room temperature (25°C) to 1000°C at a heating rate of 10°C / min. Then heat it from 1000°C to 1450°C at a heating rate of 5°C / min and calcine for 4 hours. Finally, allow it to cool down naturally in the furnace.

[0096] Step 3: Crush and grind the cooled powder obtained in Step 2, and pass it through a 150-mesh sieve to obtain near-infrared stress-luminescent Mg2SiO4:0%Cr powder.

[0097] Example 6

[0098] This embodiment provides a basalt-like structure intelligent stress luminescent material with the general chemical formula Mg2SiO4:0.1%Cr;

[0099] The preparation method of the above material is illustrated using Mg2SiO4:0.1%Cr at 1450℃ as an example. The specific operation steps are as follows:

[0100] Step 1: The dopant element Cr is produced using its oxide Cr2O3 as the raw material, and the matrix is ​​produced using MgO and SiO2 as raw materials. The raw materials of each element are weighed according to the stoichiometric ratio and mixed to obtain a mixed raw material. Then, the obtained mixed raw material is placed in an agate mortar and sufficient anhydrous ethanol is added to completely submerge the mixed raw material. Next, the mixed raw material is ground and mixed until it is uniformly mixed to obtain a mixed powder. Subsequently, the mixed powder is placed in an oven at 80°C to dry, and finally, the mixed powder is obtained.

[0101] Step 2: Place the mixed powder in an alumina crucible and heat it in a muffle furnace from room temperature (25°C) to 1000°C at a heating rate of 10°C / min. Then heat it from 1000°C to 1450°C at a heating rate of 5°C / min and calcine for 4 hours. Finally, allow it to cool down naturally in the furnace.

[0102] Step 3: Crush and grind the cooled powder obtained in Step 2, and pass it through a 150-mesh sieve to obtain near-infrared stress-luminescent Mg2SiO4:0.1%Cr powder.

[0103] Example 7

[0104] This embodiment provides a basalt-like structure intelligent stress luminescent material with the general chemical formula Mg2SiO4:0.2%Cr;

[0105] The preparation method of the above material is illustrated using Mg2SiO4:0.2%Cr at 1450℃ as an example. The specific operation steps are as follows:

[0106] Step 1: The dopant element Cr is produced using its oxide Cr2O3 as the raw material, and the matrix is ​​produced using MgO and SiO2 as raw materials. The raw materials of each element are weighed according to the stoichiometric ratio and mixed to obtain a mixed raw material. Then, the obtained mixed raw material is placed in an agate mortar and sufficient anhydrous ethanol is added to completely submerge the mixed raw material. Next, the mixed raw material is ground and mixed until it is uniformly mixed to obtain a mixed powder. Subsequently, the mixed powder is placed in an oven at 80°C to dry, and finally, the mixed powder is obtained.

[0107] Step 2: Place the mixed powder in an alumina crucible and heat it in a muffle furnace from room temperature (25°C) to 1000°C at a heating rate of 10°C / min. Then heat it from 1000°C to 1450°C at a heating rate of 5°C / min and calcine for 4 hours. Finally, allow it to cool down naturally in the furnace.

[0108] Step 3: Crush and grind the cooled powder obtained in Step 2, and pass it through a 150-mesh sieve to obtain near-infrared stress-luminescent Mg2SiO4:0.2%Cr powder.

[0109] Example 8

[0110] This embodiment provides a basalt-like structure intelligent stress luminescent material with the general chemical formula Mg2SiO4: 1%Cr;

[0111] The preparation method of the above material is illustrated using Mg2SiO4:1%Cr at 1450℃ as an example. The specific operation steps are as follows:

[0112] Step 1: The dopant element Cr is produced using its oxide Cr2O3 as the raw material, and the matrix is ​​produced using MgO and SiO2 as raw materials. The raw materials of each element are weighed according to the stoichiometric ratio and mixed to obtain a mixed raw material. Then, the obtained mixed raw material is placed in an agate mortar and sufficient anhydrous ethanol is added to completely submerge the mixed raw material. Next, the mixed raw material is ground and mixed until it is uniformly mixed to obtain a mixed powder. Subsequently, the mixed powder is placed in an oven at 80°C to dry, and finally, the mixed powder is obtained.

[0113] Step 2: Place the mixed powder in an alumina crucible and heat it in a muffle furnace from room temperature (25°C) to 1000°C at a heating rate of 10°C / min. Then heat it from 1000°C to 1450°C at a heating rate of 5°C / min and calcine for 4 hours. Finally, allow it to cool down naturally in the furnace.

[0114] Step 3: Crush and grind the cooled powder obtained in Step 2, and pass it through a 150-mesh sieve to obtain near-infrared stress-luminescent Mg2SiO4:1%Cr powder.

[0115] Example 9

[0116] This embodiment provides a basalt-like structure intelligent stress luminescent material with the general chemical formula Mg2SiO4: 2%Cr;

[0117] The preparation method of the above material is illustrated using Mg2SiO4:2%Cr at 1450℃ as an example. The specific operation steps are as follows:

[0118] Step 1: The dopant element Cr is produced using its oxide Cr2O3 as the raw material, and the matrix is ​​produced using MgO and SiO2 as raw materials. The raw materials of each element are weighed according to the stoichiometric ratio and mixed to obtain a mixed raw material. Then, the obtained mixed raw material is placed in an agate mortar and sufficient anhydrous ethanol is added to completely submerge the mixed raw material. Next, the mixed raw material is ground and mixed until it is uniformly mixed to obtain a mixed powder. Subsequently, the mixed powder is placed in an oven at 80°C to dry, and finally, the mixed powder is obtained.

[0119] Step 2: Place the mixed powder in an alumina crucible and heat it in a muffle furnace from room temperature (25°C) to 1000°C at a heating rate of 10°C / min. Then heat it from 1000°C to 1450°C at a heating rate of 5°C / min and calcine for 4 hours. Finally, allow it to cool down naturally in the furnace.

[0120] Step 3: Crush and grind the cooled powder obtained in Step 2, and pass it through a 150-mesh sieve to obtain near-infrared stress-luminescent Mg2SiO4: 2%Cr powder.

[0121] Example 10

[0122] This embodiment provides a basalt-like structure intelligent stress luminescent material with the general chemical formula Mg2SiO4:0.4%Cr,1%Yb;

[0123] The preparation method of the above material is illustrated using Mg2SiO4: 0.4%Cr, 1%Yb at 1450℃ as an example. The specific operation steps are as follows:

[0124] Step 1: The dopant element Cr is produced using its oxide Cr2O3 as the raw material, the dopant element Yb is produced using its oxide Yb2O3 as the raw material, and the matrix is ​​produced using MgO and SiO2 as raw materials. The raw materials of each element are weighed according to the stoichiometric ratio and mixed to obtain a mixed raw material. Then, the obtained mixed raw material is placed in an agate mortar and sufficient anhydrous ethanol is added to completely submerge the mixed raw material. Next, the mixed raw material is ground and mixed until it is uniformly mixed to obtain a mixed powder. Subsequently, the mixed powder is placed in an oven at 80°C to dry, and finally, the mixed powder is obtained.

[0125] Step 2: Place the mixed powder in an alumina crucible and heat it in a muffle furnace from room temperature (25°C) to 1000°C at a heating rate of 10°C / min. Then heat it from 1000°C to 1450°C at a heating rate of 5°C / min and calcine for 4 hours. Finally, allow it to cool down naturally in the furnace.

[0126] Step 3: Crush and grind the cooled powder obtained in Step 2, and pass it through a 150-mesh sieve to obtain near-infrared stress-luminescent Mg2SiO4: 0.4%Cr,1%Yb powder.

[0127] Example 11

[0128] This embodiment provides a basalt-like structure intelligent stress luminescent material with the general chemical formula Mg2SiO4:0.4%Cr,2%Yb;

[0129] The preparation method of the above material is illustrated using Mg2SiO4: 0.4%Cr, 2%Yb at 1450℃ as an example. The specific operation steps are as follows:

[0130] Step 1: The dopant element Cr is produced using its oxide Cr2O3 as the raw material, the dopant element Yb is produced using its oxide Yb2O3 as the raw material, and the matrix is ​​produced using MgO and SiO2 as raw materials. The raw materials of each element are weighed according to the stoichiometric ratio and mixed to obtain a mixed raw material. Then, the obtained mixed raw material is placed in an agate mortar and sufficient anhydrous ethanol is added to completely submerge the mixed raw material. Next, the mixed raw material is ground and mixed until it is uniformly mixed to obtain a mixed powder. Subsequently, the mixed powder is placed in an oven at 80°C to dry, and finally, the mixed powder is obtained.

[0131] Step 2: Place the mixed powder in an alumina crucible and heat it in a muffle furnace from room temperature (25°C) to 1000°C at a heating rate of 10°C / min. Then heat it from 1000°C to 1450°C at a heating rate of 5°C / min and calcine for 4 hours. Finally, allow it to cool down naturally in the furnace.

[0132] Step 3: Crush and grind the cooled powder obtained in Step 2, and pass it through a 150-mesh sieve to obtain near-infrared stress-luminescent Mg2SiO4: 0.4%Cr,2%Yb powder.

[0133] Example 12

[0134] This embodiment provides a basalt-like structure intelligent stress luminescent material with the general chemical formula Mg2SiO4:0.4%Cr,4%Yb;

[0135] The preparation method of the above material is illustrated using Mg2SiO4: 0.4%Cr, 4%Yb at 1450℃ as an example. The specific operation steps are as follows:

[0136] Step 1: The dopant element Cr is produced using its oxide Cr2O3 as the raw material, the dopant element Yb is produced using its oxide Yb2O3 as the raw material, and the matrix is ​​produced using MgO and SiO2 as raw materials. The raw materials of each element are weighed according to the stoichiometric ratio and mixed to obtain a mixed raw material. Then, the obtained mixed raw material is placed in an agate mortar and sufficient anhydrous ethanol is added to completely submerge the mixed raw material. Next, the mixed raw material is ground and mixed until it is uniformly mixed to obtain a mixed powder. Subsequently, the mixed powder is placed in an oven at 80°C to dry, and finally, the mixed powder is obtained.

[0137] Step 2: Place the mixed powder in an alumina crucible and heat it in a muffle furnace from room temperature (25°C) to 1000°C at a heating rate of 10°C / min. Then heat it from 1000°C to 1450°C at a heating rate of 5°C / min and calcine for 4 hours. Finally, allow it to cool down naturally in the furnace.

[0138] Step 3: Crush and grind the cooled powder obtained in Step 2, and pass it through a 150-mesh sieve to obtain near-infrared stress-luminescent Mg2SiO4: 0.4%Cr,4%Yb powder.

[0139] Performance Characterization

[0140] Figure 2 The images show the XRD patterns of the Mg2SiO4:0.4%Cr powder prepared in Examples 2-4 of this invention. Figure 2 The curves in the figure correspond to the XRD spectra of Mg2SiO4:0.4%Cr powder materials generated at calcination temperatures of 1350℃ (Example 2), 1400℃ (Example 3), and 1450℃ (Example 4), respectively, as well as the XRD standard card corresponding to Mg2SiO4.

[0141] from Figure 2 As can be seen from the above, the XRD spectra of the Mg2SiO4:0.4%Cr powder materials generated by the preparation method provided by the present invention at calcination temperatures of 1350℃ (Example 2), 1400℃ (Example 3), and 1450℃ (Example 4) correspond one-to-one with the diffraction peaks of the Mg2SiO4 material XRD standard card, indicating that the preparation method provided by the present invention can effectively generate the target product.

[0142] Figure 3 The images show the stress emission spectra of the Mg2SiO4:0.4%Cr powder materials prepared in Examples 2-4 of this invention under a force of 30N. Figure 3 The curves in the figure correspond to the stress emission spectra of Mg2SiO4:0.4%Cr powder materials generated under calcination conditions of 1300℃ (Example 1), 1350℃ (Example 2), 1400℃ (Example 3), and 1450℃ (Example 4), respectively. The inset is a schematic diagram of the corresponding stress emission integral intensity.

[0143] from Figure 3 As can be seen, the stress luminescence properties of powder materials are affected by the sintering temperature, and their luminescence properties increase with the increase of sintering temperature.

[0144] Figure 4 The XRD spectra of Mg2SiO4:m%Cr powder materials prepared under calcination conditions at 1450℃ in Examples 4, 6-8 of this invention are shown, along with the corresponding XRD standard card for Mg2SiO4. Figure 4 The Mg2SiO4: 1%Cr corresponds to Example 8, Mg2SiO4: 0.2%Cr corresponds to Example 7, Mg2SiO4: 0.1%Cr corresponds to Example 6, and Mg2SiO4: 0.4%Cr corresponds to Example 4.

[0145] fromFigure 4 As can be seen from the data, the XRD spectra of the Mg2SiO4:m%Cr powder material prepared by the preparation method provided by the present invention under calcination at 1450℃ correspond one-to-one with the diffraction peaks of the Mg2SiO4 material XRD standard card, indicating that the preparation method provided by the present invention can effectively generate the target product.

[0146] Figure 5 The images show the stress emission spectra of Mg2SiO4:m%Cr powder materials prepared by calcination at 1450℃ in Examples 4-9 of this invention under a force of 30N. The inset is the corresponding stress emission integral intensity diagram. Figure 5 In this context, 2%Cr corresponds to Example 9, 1%Cr corresponds to Example 8, 0.4%Cr corresponds to Example 4, 0.2%Cr corresponds to Example 7, 0.1%Cr corresponds to Example 6, and 0%Cr corresponds to Example 5.

[0147] from Figure 5 As can be seen, Mg2SiO4 material without Cr doping does not exhibit stress luminescence. As the Cr doping concentration increases, the stress luminescence performance of the material is enhanced until the optimal Cr doping concentration of 0.4% is reached. Further increases in Cr doping concentration lead to concentration quenching effect, which weakens the stress luminescence performance of the material.

[0148] Figure 6 The diagram shows the stress luminescence integral intensity of the Mg2SiO4:0.4%Cr powder material prepared in Example 4 of this invention under forces of 5N, 10N, 20N, 30N, and 40N.

[0149] from Figure 6 As can be seen, the stress luminescence properties of the Mg2SiO4:0.4%Cr powder material prepared by this invention increase with the increase of applied stress, and the relationship is approximately linear.

[0150] Figure 7 The average stress luminescence integral intensity diagram of the Mg2SiO4:0.4%Cr powder material prepared in Example 4 of this invention was repeatedly tested under a 10N force for 10 groups, with 5 tests per group.

[0151] from Figure 7 As can be seen, the Mg2SiO4:0.4%Cr powder material prepared by this invention can still maintain its stress luminescence performance under repeated stress of 10N, which verifies its stress luminescence self-recovery characteristics.

[0152] Figure 8 The stress emission spectra of Mg2SiO4: 0.4%Cr, n%Yb powder materials prepared by calcination at 1450℃ in Examples 10-12 of this invention are shown under a force of 30N.Figure 8 In the text, 0.4%Cr,1%Yb represents Example 10, 0.4%Cr,2%Yb represents Example 11, and 0.4%Cr,4%Yb represents Example 12.

[0153] from Figure 8 As can be seen, the Mg2SiO4:0.4%Cr, n%Yb powder material prepared by the method provided in this invention under calcination at 1450℃ exhibits near-infrared stress luminescence at a wavelength of 980nm. Its stress luminescence performance is affected by the Yb doping concentration. As the Yb doping concentration increases, the stress luminescence performance of the material enhances until it reaches the optimal Yb doping concentration of 2%. Further increases in Yb doping concentration lead to a concentration quenching effect, resulting in a weakening of the material's stress luminescence performance.

[0154] It is understood that the technical features of the above embodiments can be combined arbitrarily. For the sake of brevity, not all possible combinations of the technical features in the above embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0155] The above are merely preferred embodiments of this application, and only specifically describe the technical principles of this application. These descriptions are only for explaining the principles of this application and should not be construed as limiting the scope of protection of this application in any way. Based on this explanation, any modifications, equivalent substitutions, and improvements made within the spirit and principles of this application, as well as other specific embodiments of this application that can be conceived by those skilled in the art without creative effort, should be included within the scope of protection of this application.

Claims

1. A basalt-like structure intelligent stress-luminescent material, characterized in that, The chemical formula of the stress-luminescent material is Mg2SiO4: m%Cr,n%X, where m=0.4 and n=2. Where m% represents the molar percentage of Cr relative to Mg2SiO4, and n% represents the molar percentage of X relative to Mg2SiO4; Element X is Yb; The preparation method of the aforementioned basalt-like structure intelligent stress-luminescent material includes the following steps: S1. Weigh the raw materials according to the stoichiometric ratio of each element in the general chemical formula of stress luminescent materials, mix the raw materials to obtain a mixed raw material; add anhydrous ethanol to the mixed raw material, grind and mix evenly, and then dry to obtain a mixed powder. S2. Calcine the mixed powder in S1 in an air or oxygen atmosphere, and then let it cool naturally in the furnace. S3. Grind the powder cooled in S2 to obtain a basalt-like structure intelligent stress luminescent material; Step S2 specifically includes: heating from room temperature to 1000°C at a heating rate of 10°C / min in an air or oxygen atmosphere, then heating from 1000°C to 1450°C at a heating rate of 5°C / min, calcining for 4 hours, and then cooling naturally in the furnace. The raw materials for Mg include Mg oxides, hydroxides or carbonates, and natural ores; The natural ore includes at least one of magnesite, olivine, serpentine, and magnesia. The raw materials corresponding to the element Si include Si oxides; The raw materials corresponding to Cr element include Cr oxides, chlorides, and soluble nitrates; The raw materials corresponding to element X include oxides, chlorides, and soluble nitrates of X.

2. A method for preparing a basalt-like structure intelligent stress-luminescent material as described in claim 1, characterized in that, Includes the following steps: S1. Weigh the raw materials according to the stoichiometric ratio of each element in the general chemical formula of stress luminescent materials, mix the raw materials to obtain a mixed raw material; add anhydrous ethanol to the mixed raw material, grind and mix evenly, and then dry to obtain a mixed powder. S2. Calcine the mixed powder in S1 in an air or oxygen atmosphere, and then let it cool naturally in the furnace. S3. Grind the powder cooled in S2 to obtain a basalt-like structure intelligent stress luminescent material; Step S2 specifically includes: heating from room temperature to 1000°C at a heating rate of 10°C / min in an air or oxygen atmosphere, then heating from 1000°C to 1450°C at a heating rate of 5°C / min, calcining for 4 hours, and then cooling naturally in the furnace. The raw materials for Mg include Mg oxides, hydroxides or carbonates, and natural ores; The natural ore includes at least one of magnesite, olivine, serpentine, and magnesia. The raw materials corresponding to the element Si include Si oxides; The raw materials corresponding to Cr element include Cr oxides, chlorides, and soluble nitrates; The raw materials corresponding to element X include oxides, chlorides, and soluble nitrates of X.

3. The preparation method of the basalt-like structure intelligent stress-luminescent material as described in claim 2, characterized in that, Anhydrous ethanol is added to the mixed raw materials, and after grinding and mixing evenly, the mixture is dried at 80~300℃ to obtain a mixed powder.

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