Intelligent stress luminescent material with basalt-like structure and preparation method of intelligent stress luminescent material

Abstract

The invention belongs to the technical field of inorganic luminescent materials. The invention discloses an intelligent stress luminescent material with a basalt-like structure and a preparation method of the intelligent stress luminescent material. The general chemical formula of the stress luminescent material is Mg2SiO4: m% of Cr, n% of X, the stress luminescent material disclosed by the invention is stable in chemical property, has mechanical properties of high modulus and high strength, and also has the characteristic of high temperature resistance. The material disclosed by the invention can be used for preparing fibers, is used as a light structural material, is applied to structural elements in aerospace and automobile industries, can exert the near-infrared stress luminescence characteristic of the material, and can provide signal feedback and enhance safety in emergency; the material is also suitable for fireproof protection in metallurgy, steel, casting and other high-temperature industries, and can be used as a thermal insulation material for various thermal insulation equipment in the high-temperature industries. The material is wide in raw material source and simple in preparation process, the preparation cost is expected to be reduced in large-scale production, and powerful support is provided for wide application of the stress luminescent material.

Description

Technical Field

[0001] The present invention relates to the technical field of inorganic luminescent materials, and in particular to a basalt-like structure intelligent stress luminescent material and a preparation method thereof. Background Art

[0002] Mechanoluminescence is the phenomenon in which a material emits light when subjected to mechanical stress or deformation. Traditional photoluminescent materials rely on external short-wavelength excitation light sources to achieve luminescence through energy level transitions. However, mechanoluminescent materials can convert mechanical signals into optical signals without the need for illumination or electrical current. This property makes mechanoluminescent materials promising for broad applications in optoelectronics.

[0003] Natural basalt fiber was first discovered in volcanic rocks. It is formed by melting and drawing basalt ore into fibers. The fiber's high strength, corrosion resistance, and high-temperature resistance have gradually attracted attention and are widely used in industries such as construction, automotive, and aviation. However, the preparation of natural basalt materials is limited by the availability and quality of the ore. Therefore, the development of basalt-like materials has emerged, mimicking the properties of basalt through artificial synthesis or modification to achieve more stable and controllable performance. Basalt-like materials are materials with similar properties or functions to natural basalt. Through artificial synthesis, the chemical composition of the materials can be more precisely controlled to ensure stable and consistent performance. These materials can not only mimic the mechanical properties of basalt but also, through the doping of various functional substances (such as nanomaterials and metal oxides), possess additional properties. For example, they can impart enhanced fire resistance, impact resistance, or self-healing capabilities to meet the needs of various applications. The development of basalt-like materials not only makes up for the limitations of natural basalt materials, but also expands their application scenarios. It is a new type of material with important industrial and economic value.

[0004] Dimagnesium silicate (Mg2SiO4), also known as olivine, is a mineral with a basaltic structure and belongs to the orthorhombic crystal system. It maintains its structural stability under the high temperatures and pressures found within the Earth's interior. It is a mineral found throughout the Earth's crust and upper mantle. Composed primarily of magnesium and silicon-oxygen tetrahedrons, it belongs to the silicate mineral family. Olivine has an orthorhombic crystal structure, with silicon-oxygen tetrahedrons closely arranged to form a three-dimensional network, making it extremely hard, with a Mohs hardness of approximately 6.5-7. This structure imparts high strength and stability under high temperatures and high pressures. In dry, high-temperature environments, it exhibits excellent chemical stability and strong resistance to acid and alkali corrosion. With a melting point of approximately 1890°C, dimagnesium silicate exhibits excellent high-temperature resistance, making it a popular refractory material. It is widely used in the linings of high-temperature industrial equipment, such as steelmaking furnaces, furnace linings, crucibles, and kilns in the steel industry. It is also used in the production of refractory bricks, which can withstand high temperatures and severe thermal shock. Due to its low coefficient of expansion and excellent thermal stability, dimagnesium silicate is often used as a mold material in the foundry industry. It can be used in the casting of metals such as steel, iron, and copper, and is particularly suitable for castings that require high stability at high temperatures. Additionally, olivine powder is used as a raw material in the production of high-temperature ceramics and specialty ceramics, significantly improving the heat resistance and wear resistance of ceramic products. It is commonly used in the manufacture of high-temperature equipment and components.

[0005] Existing materials are unable to combine the high-temperature resistance, high-strength and high-modulus mechanical properties, and self-recovering near-infrared stress luminescence properties inherent in magnesium silicate materials. Traditional stress luminescent materials often experience performance degradation or failure in high-temperature environments, and their luminescence efficiency and stability under strong mechanical stress are difficult to guarantee, all of which limit the application of stress luminescent materials under extreme conditions. In contrast, basalt-like structured stress luminescent materials not only have excellent high-temperature resistance and thermal insulation properties, but also maintain stable luminescence properties under high temperature and strong mechanical stress, significantly improving the reliability and safety of the material in high-temperature industrial equipment, building fireproofing layers, and other applications requiring real-time monitoring and fire protection and insulation.

[0006] At present, there is a lack of silicate materials with basalt-like structures that can achieve near-infrared stress luminescence. The relevant silicate materials reported so far include: CaMgSi2O6:Dy reported by Ravishankar Shukla University in India in Journal of Alloys and Compounds, 2015, 649:1329-1338 3+ 、Sr2MgSi2O7:Dy reported in Displays, 2014, 35(5):279-286 3+; Other institutions reported Ca2MgSi2O7:Eu in Integrated Ferroelectrics, 2015, 159(1):49-56 2+ ,Dy 3+ ;Luminescence,2015,30(8):1207-1211 reported Ba2MgSi2O7:Eu 2+ ,Dy 3+ wait.

[0007] Chromium-doped near-infrared stress luminescent 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 reported by Kunming University of Science and Technology, China in Advanced Functional Materials, 2023, 33(27): 2214497 12 :Cr 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, China in Matter, 2023, 6(9): 2935-2949 3+ ; SrAl2O4:Eu-Cr system developed by the National Institute of Advanced Industrial Science and Technology of Japan: Journal of The Electrochemical Society, 2021, 168(4):047508; ECS Transactions, 2020, 98(11):61; CN105209572 A et al.

[0008] This patented material has the following advantages: First, compared with other high-performance composite materials such as carbon fiber, it is low in cost, and the raw materials are widely distributed natural minerals, which has obvious advantages in large-scale preparation; Second, it has high-strength and high-modulus mechanical properties and high-temperature resistance that traditional stress luminescent materials do not have, so it can still maintain its stable luminescence characteristics in some extreme environments; Third, most of the reported near-infrared stress luminescent materials require the use of rare earth element doping, while this patented material uses chromium doping, which has diverse acquisition methods and lower costs; Fourth, compared with systems that react in a reducing atmosphere or systems that require organic acid-assisted reactions, the preparation method of this patented material is simpler. Summary of the Invention

[0009] The present invention aims to provide a high-performance stress luminescent material and its preparation method, which will not only enable stress luminescent materials to be more widely used in fields such as construction, aerospace, and industrial manufacturing, but also enable 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.

[0010] The present invention is a basalt-like intelligent stress luminescent material with a high modulus and high strength mechanical properties and high temperature resistance. The material emits light directly when subjected to stress, without the need for prior illumination. The wavelength of the light is in the 650nm to 1000nm range, with a broad peak located near 730nm, and the light intensity is mainly distributed in the near-infrared short-wave band. The material has high-intensity elastic stress luminescence properties, a simple preparation process, low cost, and stable chemical properties. It can directly respond to different forms of mechanical force signals, such as compression, tension, bending, collision, friction, torsion, etc., and the emitted light can be observed using an infrared camera.

[0011] The present invention provides the following technical solutions:

[0012] The present 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;

[0013] Wherein, m% represents the molar percentage of Cr element relative to Mg2SiO4, and n% represents the molar percentage of X relative to Mg2SiO4;

[0014] The X element includes at least one of Yb, Eu, Er, Nd, Sm, Dy, Ni, Al, and Ga.

[0015] The method for preparing the basalt-like structure intelligent stress luminescent material of the present invention comprises the following steps:

[0016] S1. Weighing raw materials according to the stoichiometric ratio of each element in the chemical formula of the stress luminescent material, mixing the raw materials to obtain a mixed raw material; adding anhydrous ethanol to the mixed raw material, grinding and mixing uniformly, and drying to obtain a mixed powder;

[0017] S2, calcining the mixed powder in S1 in air or oxygen atmosphere, and cooling the furnace naturally;

[0018] S3. Grind the powder cooled in S2 to obtain a basalt-like structured intelligent stress luminescent material.

[0019] Preferably, the temperature is raised to 1300-1450° C. at a heating rate of 1-100° C. / min in air or oxygen atmosphere, and calcined for 0.5-24 h.

[0020] Preferably, anhydrous ethanol is added to the mixed raw materials, ground and mixed evenly, and then dried at 80-300° C. to obtain a mixed powder.

[0021] Preferably, the raw materials corresponding to the Mg element include Mg oxides, hydroxides or carbonates, and natural ores;

[0022] The natural ore includes at least one of magnesite, olivine, serpentine and stevensite;

[0023] The raw materials corresponding to the Si element include Si oxides;

[0024] The raw materials corresponding to the Cr element include Cr oxides, chlorides and soluble nitrates;

[0025] The raw materials corresponding to the X element include X oxides, chlorides and soluble nitrates.

[0026] The prepared basalt-like structured intelligent stress luminescent material is ground and sieved into powder and encapsulated in optically transparent organic polymer elastic material PET, made into a thin sheet and attached to the surface of the component to be tested. Under the action of external mechanical force, the stress exerted on the composite is converted into light emission, realizing direct force-light conversion in the near-infrared band.

[0027] The basalt-like structured intelligent stress luminescent material of the present invention has a stress luminescent intensity that is positively correlated with the magnitude of the applied mechanical force within the elastic limit.

[0028] The following are the beneficial effects of the present invention:

[0029] 1) The material of the present invention is prepared by a traditional high-temperature solid-phase method, which is simple and low-cost;

[0030] 2) The main elements required for the material of the present invention are oxygen, silicon and magnesium, which are common elements in the earth's crust, have abundant raw material sources and are easy to obtain from nature;

[0031] 3) The material of the present invention has near-infrared stress luminescence properties, and can convert the stress received within the elastic range into near-infrared light emission, which can be observed using an infrared camera;

[0032] 4) The materials of the present invention can be widely used in many fields such as force sensing, bioimaging, anti-counterfeiting, and military. This type of material provides a potential solution to the current energy crisis and also opens up new horizons for multi-path energy conversion;

[0033] 5) The material of the present invention has high-temperature resistance and near-infrared stress luminescence properties, and can be used to develop high-temperature sensing and achieve real-time stress monitoring in high-temperature environments, which is crucial for safe operation in energy, aviation and other fields.

[0034] 6) The material of the present invention can be used to prepare fibers to maximize its mechanical properties and high-temperature resistance. This fiber is lightweight and high-strength, making it suitable for use as a lightweight structural material in applications requiring both lightness and strength, such as structural components in the aerospace and automotive industries. It reduces weight while providing sufficient high-temperature resistance and mechanical strength. Its near-infrared stress luminescence properties can also provide signal feedback in emergency situations, enhancing safety. Therefore, it has enormous potential for applications such as bulletproof clothing and space suits.

[0035] 7) Fibers made from the materials of this invention are commonly used in the manufacture of fire-resistant fabrics, thermal insulation materials, and fire-resistant clothing due to their high-temperature resistance. These materials can maintain strength and structural stability even at extremely high temperatures, making them suitable for fire protection in high-temperature industries such as metallurgy, steel, and foundry. For high-temperature insulation, the fibers can be used as refractory blankets and refractory linings, providing excellent thermal insulation for furnaces, boilers, and kilns. Furthermore, the fibers are excellent thermal insulators and can be used as insulation materials for various insulation equipment in high-temperature industries, such as high-temperature furnace linings, pipeline insulation materials, and insulation panels in heat treatment equipment.

[0036] 8) Fibers made from this material can also be used to manufacture high-performance composites, enhancing their heat resistance and strength. They can be combined with ceramics, resins, or other matrix materials to create high-temperature composites suitable for applications in aviation, aerospace, and automotive fields. These fiber-reinforced composites not only possess high strength but also exhibit exceptional durability under high temperatures and harsh environments. They can be used in friction materials such as brake linings and clutch plates. In particular, in mechanical systems requiring high friction performance and thermal stability, the fibers can improve the material's wear resistance and service life. BRIEF DESCRIPTION OF THE DRAWINGS

[0037] To more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the following briefly introduces the drawings required for use in the embodiments or the description of the prior art. Obviously, the drawings described below are only some embodiments of the present invention. Those skilled in the art can also derive other drawings based on these drawings without inventive effort.

[0038] Figure 1 The present invention provides a schematic flow chart of a method for preparing a basalt-like structure intelligent stress luminescent material;

[0039] Figure 2 The XRD patterns of the Mg2SiO4:0.4%Cr powders prepared in Examples 2 to 4 of the present invention are as follows;

[0040] Figure 3 This is a stress luminescence spectrum of the Mg2SiO4:0.4%Cr powder material prepared in Examples 2 to 4 of the present invention under a force of 30N;

[0041] Figure 4 XRD spectra of Mg2SiO4:m%Cr powder materials prepared by calcining at 1450°C in Examples 4, 6-8 of the present invention and the corresponding XRD standard card of Mg2SiO4;

[0042] Figure 5 This is a stress luminescence spectrum of the Mg2SiO4:m%Cr powder material prepared under calcination conditions of 1450°C in Examples 4 to 9 of the present invention under a force of 30N.

[0043] Figure 6 Schematic diagram of the stress luminescence integrated intensity corresponding to the Mg2SiO4:0.4%Cr powder material prepared in Example 4 of the present invention under forces of 5N, 10N, 20N, 30N, and 40N respectively;

[0044] Figure 7 The Mg2SiO4:0.4%Cr powder material prepared in Example 4 of the present invention was repeatedly tested under a force of 10N for 10 groups, with each group undergoing 5 times of stress-luminescence integrated intensity.

[0045] Figure 8 This is a stress luminescence spectrum of the Mg2SiO4:0.4%Cr,n%Yb powder material prepared under calcination conditions of 1450°C in Examples 10 to 12 of the present invention under a force of 30N. DETAILED DESCRIPTION

[0046] To facilitate understanding of the present invention, the present invention will be described more fully below in conjunction with the specific embodiments. Preferred embodiments of the present invention are provided in the specific embodiments. However, the present invention can be implemented in many different forms and is not limited to the embodiments described herein. On the contrary, the purpose of providing these embodiments is to provide a more thorough and comprehensive understanding of the disclosure of the present invention.

[0047] The application principle of the present invention is described in detail below with reference to the accompanying drawings.

[0048] The present invention provides a basalt-like structure intelligent stress luminescent material, the general chemical formula of which is Mg2SiO4: m% Cr, n% X, 0.000001≤m≤10.9, 0.000001≤n≤10.9;

[0049] Wherein, m% represents the molar percentage of Cr element relative to Mg2SiO4, and n% represents the molar percentage of X relative to Mg2SiO4;

[0050] The X element includes at least one of Yb, Eu, Er, Nd, Sm, Dy, Ni, Al, and Ga. The co-doping of the Yb element enables the material to obtain a new stress luminescence peak. Other co-doped elements do not have this significant phenomenon, so the Yb element is provided as an example below.

[0051] The basalt-like structured intelligent stress luminescent material of the present invention has stable chemical properties, high modulus and high strength mechanical properties, and high temperature resistance. The material of the present invention can be used to prepare fibers, used as lightweight structural materials, and applied to structural components in the aerospace and automotive industries. It can also exert its near-infrared stress luminescence properties to provide signal feedback in emergency situations and enhance safety. The invented material is also suitable for fire protection in high-temperature industries such as metallurgy, steel, and casting, and can be used as a thermal insulation material for various insulation equipment in high-temperature industries. The raw materials of the material of the present invention are widely available and the preparation process is simple. It is expected to reduce the preparation cost in large-scale production, providing strong support for the widespread application of stress luminescent materials.

[0052] The method for preparing the basalt-like structure intelligent stress luminescent material of the present invention comprises the following steps:

[0053] S1. Weighing raw materials according to the stoichiometric ratio of each element in the chemical formula of the stress luminescent material, mixing the raw materials to obtain a mixed raw material; adding anhydrous ethanol to the mixed raw material, grinding and mixing uniformly, and drying to obtain a mixed powder;

[0054] S2, calcining the mixed powder in S1 in air or oxygen atmosphere, and cooling the furnace naturally;

[0055] S3. Grind the powder cooled in S2 to obtain a basalt-like structured intelligent stress luminescent material.

[0056] In some embodiments, the temperature is increased to 1300-1450° C. at a heating rate of 1-100° C. / min in air or oxygen atmosphere, and calcined for 0.5-24 h.

[0057] In some embodiments, anhydrous ethanol is added to the mixed raw materials, and after grinding and mixing, the raw materials are dried at 80-300° C. to obtain a mixed powder.

[0058] In some embodiments, the raw materials corresponding to the Mg element include Mg oxides, hydroxides or carbonates, and natural ores;

[0059] The natural ore includes at least one of magnesite, olivine, serpentine and stevensite;

[0060] The raw materials corresponding to the Si element include Si oxides;

[0061] The raw materials corresponding to the Cr element include Cr oxides, chlorides and soluble nitrates;

[0062] The raw materials corresponding to element X include oxides, chlorides and soluble nitrates of X.

[0063] In some embodiments, as Figure 1 As shown, the preparation method of the basalt-like structure intelligent stress luminescent material includes the following steps:

[0064] Step 1: The doping element Cr uses its oxide Cr2O3 as a raw material, the doping element X uses its oxide as a raw material, and the matrix uses MgO and SiO2 as raw materials; the raw materials of each element are weighed according to the stoichiometric ratio, and then the resulting raw materials are placed in an agate bowl, and sufficient anhydrous ethanol or deionized water is added to completely immerse the raw materials; then the mixture is ground and mixed until it is uniformly mixed to obtain a mixed powder; then, the mixed powder is placed in an oven at 80°C to dry, and finally a mixed powder is obtained.

[0065] Step 2: Place the mixed powder obtained in step 1 in an alumina crucible or other high-temperature resistant container, heat it to 1300°C to 1450°C at a heating rate of 1 to 100°C / min in air or oxygen atmosphere, burn it for 4 hours, and cool it down naturally with the furnace.

[0066] Step 3: Grind the cooled powder and pass it through a 150-mesh sieve to obtain Mg2SiO4: m% Cr, n% X powder having near-infrared stress luminescence material.

[0067] The following further illustrates the basalt-like structured intelligent stress-luminescent material and its preparation method using specific examples. This section further illustrates the present invention with reference to specific examples, but should not be construed as limiting the present invention. Unless otherwise specified, the techniques employed in the examples are conventional techniques well known to those skilled in the art. Unless otherwise noted, the reagents, methods, and equipment employed in the present invention are conventional in the art.

[0068] Example 1

[0069] This embodiment provides a basalt-like structure intelligent stress luminescent material, the chemical formula of which is Mg2SiO4:0.4%Cr;

[0070] The preparation method of the above material is described using Mg2SiO4:0.4%Cr at 1300℃ as an example. The specific steps are as follows:

[0071] Step 1: The doping element Cr is prepared using its oxide Cr2O3 as a raw material, and the matrix is ​​prepared using MgO and SiO2 as raw materials; the raw materials of each element are weighed according to a stoichiometric ratio and mixed to obtain a mixed raw material; the obtained mixed raw material is then placed in an agate mortar, and sufficient anhydrous ethanol is added to completely immerse the mixed raw material; the mixed raw material is then ground and mixed until uniformly mixed to obtain a mixed powder; the mixed powder is then dried in an oven at 80°C to obtain a mixed powder;

[0072] Step 2: Place the mixed powder in an alumina crucible, heat it from room temperature (25°C) to 1000°C in a muffle furnace 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, calcine for 8 hours, and finally cool it naturally in the furnace;

[0073] 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.

[0074] Example 2

[0075] This embodiment provides a basalt-like structure intelligent stress luminescent material, the chemical formula of which is Mg2SiO4:0.4%Cr;

[0076] The preparation method of the above material is described using Mg2SiO4:0.4%Cr at 1350℃ as an example. The specific steps are as follows:

[0077] Step 1: The doping element Cr is prepared using its oxide Cr2O3 as a raw material, and the matrix is ​​prepared using MgO and SiO2 as raw materials; the raw materials of each element are weighed according to a stoichiometric ratio and mixed to obtain a mixed raw material; the obtained mixed raw material is then placed in an agate mortar, and sufficient anhydrous ethanol is added to completely immerse the mixed raw material; the mixed raw material is then ground and mixed until uniformly mixed to obtain a mixed powder; the mixed powder is then dried in an oven at 80°C to obtain a mixed powder;

[0078] Step 2: Place the mixed powder in an alumina crucible, heat it from room temperature (25°C) to 1000°C in a muffle furnace 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, calcine for 8 hours, and finally cool it naturally in the furnace;

[0079] 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.

[0080] Example 3

[0081] This embodiment provides a basalt-like structure intelligent stress luminescent material, the chemical formula of which is Mg2SiO4:0.4%Cr;

[0082] The preparation method of the above material is described using Mg2SiO4:0.4%Cr at 1400℃ as an example. The specific steps are as follows:

[0083] Step 1: The doping element Cr is prepared using its oxide Cr2O3 as a raw material, and the matrix is ​​prepared using MgO and SiO2 as raw materials; the raw materials of each element are weighed according to a stoichiometric ratio and mixed to obtain a mixed raw material; the obtained mixed raw material is then placed in an agate mortar, and sufficient anhydrous ethanol is added to completely immerse the mixed raw material; the mixed raw material is then ground and mixed until uniformly mixed to obtain a mixed powder; the mixed powder is then dried in an oven at 80°C to obtain a mixed powder;

[0084] Step 2: Place the mixed powder in an alumina crucible, heat it from room temperature (25°C) to 1000°C in a muffle furnace 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, calcine for 8 hours, and finally cool it naturally in the furnace;

[0085] 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.

[0086] Example 4

[0087] This embodiment provides a basalt-like structure intelligent stress luminescent material, the chemical formula of which is Mg2SiO4:0.4%Cr;

[0088] The preparation method of the above material is described using Mg2SiO4:0.4%Cr at 1450℃ as an example. The specific steps are as follows:

[0089] Step 1: The doping element Cr is prepared using its oxide Cr2O3 as a raw material, and the matrix is ​​prepared using MgO and SiO2 as raw materials; the raw materials of each element are weighed according to a stoichiometric ratio and mixed to obtain a mixed raw material; the obtained mixed raw material is then placed in an agate mortar, and sufficient anhydrous ethanol is added to completely immerse the mixed raw material; the mixed raw material is then ground and mixed until uniformly mixed to obtain a mixed powder; the mixed powder is then dried in an oven at 80°C to obtain a mixed powder;

[0090] Step 2: Place the mixed powder in an alumina crucible, heat it from room temperature (25°C) to 1000°C in a muffle furnace 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, calcine for 8 hours, and finally cool it naturally in the furnace;

[0091] 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.

[0092] Example 5

[0093] This embodiment provides a basalt-like structured intelligent stress luminescent material, the general chemical formula of which is Mg2SiO4:0%Cr;

[0094] The preparation method of the above material is described using Mg2SiO4:0%Cr at 1450℃ as an example. The specific steps are as follows:

[0095] Step 1: MgO and SiO2 are used as raw materials for the matrix; raw materials of each element are weighed according to the stoichiometric ratio and mixed to obtain a mixed raw material; the obtained mixed raw material is then placed in an agate mortar, and sufficient anhydrous ethanol is added to completely immerse the mixed raw material; the mixed raw material is then ground and mixed until it is uniformly mixed to obtain a mixed powder; the mixed powder is then dried in an oven at 80°C to finally obtain a mixed powder;

[0096] Step 2: Place the mixed powder in an alumina crucible, heat it from room temperature (25°C) to 1000°C in a muffle furnace 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, calcine for 4 hours, and finally cool it naturally in the furnace;

[0097] 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.

[0098] Example 6

[0099] This embodiment provides a basalt-like structure intelligent stress luminescent material, whose general chemical formula is Mg2SiO4:0.1%Cr;

[0100] The preparation method of the above material is described using Mg2SiO4:0.1%Cr at 1450℃ as an example. The specific steps are as follows:

[0101] Step 1: The doping element Cr is prepared using its oxide Cr2O3 as a raw material, and the matrix is ​​prepared using MgO and SiO2 as raw materials; the raw materials of each element are weighed according to a stoichiometric ratio and mixed to obtain a mixed raw material; the obtained mixed raw material is then placed in an agate mortar, and sufficient anhydrous ethanol is added to completely immerse the mixed raw material; the mixed raw material is then ground and mixed until uniformly mixed to obtain a mixed powder; the mixed powder is then dried in an oven at 80°C to obtain a mixed powder;

[0102] Step 2: Place the mixed powder in an alumina crucible, heat it from room temperature (25°C) to 1000°C in a muffle furnace 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, calcine for 4 hours, and finally cool it naturally in the furnace;

[0103] 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.

[0104] Example 7

[0105] This embodiment provides a basalt-like structure intelligent stress luminescent material, the chemical formula of which is Mg2SiO4:0.2%Cr;

[0106] The preparation method of the above material is described using Mg2SiO4:0.2%Cr at 1450℃ as an example. The specific steps are as follows:

[0107] Step 1: The doping element Cr is prepared using its oxide Cr2O3 as a raw material, and the matrix is ​​prepared using MgO and SiO2 as raw materials; the raw materials of each element are weighed according to a stoichiometric ratio and mixed to obtain a mixed raw material; the obtained mixed raw material is then placed in an agate mortar, and sufficient anhydrous ethanol is added to completely immerse the mixed raw material; the mixed raw material is then ground and mixed until uniformly mixed to obtain a mixed powder; the mixed powder is then dried in an oven at 80°C to obtain a mixed powder;

[0108] Step 2: Place the mixed powder in an alumina crucible, heat it from room temperature (25°C) to 1000°C in a muffle furnace 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, calcine for 4 hours, and finally cool it naturally in the furnace;

[0109] 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.

[0110] Example 8

[0111] This embodiment provides a basalt-like structured intelligent stress luminescent material, the general chemical formula of which is Mg2SiO4:1%Cr;

[0112] The preparation method of the above material is described using Mg2SiO4:1%Cr at 1450℃ as an example. The specific steps are as follows:

[0113] Step 1: The doping element Cr is prepared using its oxide Cr2O3 as a raw material, and the matrix is ​​prepared using MgO and SiO2 as raw materials; the raw materials of each element are weighed according to a stoichiometric ratio and mixed to obtain a mixed raw material; the obtained mixed raw material is then placed in an agate mortar, and sufficient anhydrous ethanol is added to completely immerse the mixed raw material; the mixed raw material is then ground and mixed until uniformly mixed to obtain a mixed powder; the mixed powder is then dried in an oven at 80°C to obtain a mixed powder;

[0114] Step 2: Place the mixed powder in an alumina crucible, heat it from room temperature (25°C) to 1000°C in a muffle furnace 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, calcine for 4 hours, and finally cool it naturally in the furnace;

[0115] 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.

[0116] Example 9

[0117] This embodiment provides a basalt-like structured intelligent stress luminescent material, the general chemical formula of which is Mg2SiO4:2%Cr;

[0118] The preparation method of the above material is described using Mg2SiO4:2%Cr at 1450℃ as an example. The specific steps are as follows:

[0119] Step 1: The doping element Cr is prepared using its oxide Cr2O3 as a raw material, and the matrix is ​​prepared using MgO and SiO2 as raw materials; the raw materials of each element are weighed according to a stoichiometric ratio and mixed to obtain a mixed raw material; the obtained mixed raw material is then placed in an agate mortar, and sufficient anhydrous ethanol is added to completely immerse the mixed raw material; the mixed raw material is then ground and mixed until uniformly mixed to obtain a mixed powder; the mixed powder is then dried in an oven at 80°C to obtain a mixed powder;

[0120] Step 2: Place the mixed powder in an alumina crucible, heat it from room temperature (25°C) to 1000°C in a muffle furnace 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, calcine for 4 hours, and finally cool it naturally in the furnace;

[0121] 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.

[0122] Example 10

[0123] This embodiment provides a basalt-like structure intelligent stress luminescent material, whose general chemical formula is Mg2SiO4:0.4%Cr,1%Yb;

[0124] The preparation method of the above material is described using Mg2SiO4:0.4%Cr,1%Yb at 1450℃ as an example. The specific steps are as follows:

[0125] Step 1: The doping element Cr uses its oxide Cr2O3 as a raw material, the doping element Yb uses its oxide Yb2O3 as a raw material, and the matrix uses MgO and SiO2 as raw materials; the raw materials of each element are weighed according to the stoichiometric ratio, and the raw materials are mixed to obtain a mixed raw material; the obtained mixed raw material is then placed in an agate mortar, and sufficient anhydrous ethanol is added to completely immerse the mixed raw material; the mixed raw material is then ground and mixed until it is uniformly mixed to obtain a mixed powder; and the mixed powder is then dried in an oven at 80°C to finally obtain a mixed powder;

[0126] Step 2: Place the mixed powder in an alumina crucible, heat it from room temperature (25°C) to 1000°C in a muffle furnace 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, calcine for 4 hours, and finally cool it naturally in the furnace;

[0127] 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.

[0128] Example 11

[0129] This embodiment provides a basalt-like structure intelligent stress luminescent material, whose general chemical formula is Mg2SiO4:0.4%Cr,2%Yb;

[0130] The preparation method of the above material is described using Mg2SiO4:0.4%Cr,2%Yb at 1450℃ as an example. The specific steps are as follows:

[0131] Step 1: The doping element Cr uses its oxide Cr2O3 as a raw material, the doping element Yb uses its oxide Yb2O3 as a raw material, and the matrix uses MgO and SiO2 as raw materials; the raw materials of each element are weighed according to the stoichiometric ratio, and the raw materials are mixed to obtain a mixed raw material; the obtained mixed raw material is then placed in an agate mortar, and sufficient anhydrous ethanol is added to completely immerse the mixed raw material; the mixed raw material is then ground and mixed until it is uniformly mixed to obtain a mixed powder; and the mixed powder is then dried in an oven at 80°C to finally obtain a mixed powder;

[0132] Step 2: Place the mixed powder in an alumina crucible, heat it from room temperature (25°C) to 1000°C in a muffle furnace 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, calcine for 4 hours, and finally cool it naturally in the furnace;

[0133] 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.

[0134] Example 12

[0135] This embodiment provides a basalt-like structure intelligent stress luminescent material, whose general chemical formula is Mg2SiO4:0.4%Cr,4%Yb;

[0136] The preparation method of the above material is described using Mg2SiO4:0.4%Cr,4%Yb at 1450℃ as an example. The specific steps are as follows:

[0137] Step 1: The doping element Cr uses its oxide Cr2O3 as a raw material, the doping element Yb uses its oxide Yb2O3 as a raw material, and the matrix uses MgO and SiO2 as raw materials; the raw materials of each element are weighed according to the stoichiometric ratio, and the raw materials are mixed to obtain a mixed raw material; the obtained mixed raw material is then placed in an agate mortar, and sufficient anhydrous ethanol is added to completely immerse the mixed raw material; the mixed raw material is then ground and mixed until it is uniformly mixed to obtain a mixed powder; and the mixed powder is then dried in an oven at 80°C to finally obtain a mixed powder;

[0138] Step 2: Place the mixed powder in an alumina crucible, heat it from room temperature (25°C) to 1000°C in a muffle furnace 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, calcine for 4 hours, and finally cool it naturally in the furnace;

[0139] 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.

[0140] Performance Characterization

[0141] Figure 2 The XRD patterns of the Mg2SiO4:0.4%Cr powders prepared in Examples 2 to 4 of the present invention are as follows: Figure 2 The curves correspond to the XRD spectra of Mg2SiO4:0.4%Cr powder materials generated at calcination temperatures of 1350°C (Example 2), 1400°C (Example 3), and 1450°C (Example 4), as well as the XRD standard card corresponding to Mg2SiO4.

[0142] from Figure 2 It can be seen that the XRD spectra of the Mg2SiO4:0.4%Cr powder material generated by the preparation method provided by the present invention at calcination temperatures of 1350°C (Example 2), 1400°C (Example 3), and 1450°C (Example 4) can correspond one-to-one to the diffraction peaks of the XRD standard card of the Mg2SiO4 material, indicating that the preparation method provided by the present invention can effectively generate the target product.

[0143] Figure 3 This is a stress luminescence spectrum of the Mg2SiO4:0.4%Cr powder material prepared in Examples 2 to 4 of the present invention under a force of 30N. Figure 3 The curves correspond to the stress luminescence spectra of Mg2SiO4:0.4%Cr powder materials calcined at 1300°C (Example 1), 1350°C (Example 2), 1400°C (Example 3), and 1450°C (Example 4), respectively. The inset shows the corresponding stress luminescence integrated intensity.

[0144] from Figure 3 It can be seen from the figure that the stress luminescence performance of the powder material will be affected by the sintering temperature, and its luminescence performance will be enhanced with the increase of the sintering temperature.

[0145] Figure 4 These are the XRD spectra of the Mg2SiO4:m%Cr powder material prepared under calcination conditions at 1450°C in Examples 4, 6 to 8 of the present invention and the corresponding XRD standard card of Mg2SiO4. Figure 4Mg2SiO4:1%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.

[0146] from Figure 4 It can be seen that the XRD spectrum of the Mg2SiO4:m%Cr powder material prepared by the preparation method provided by the present invention under calcination conditions at 1450°C can correspond one-to-one to the diffraction peaks of the XRD standard card of the Mg2SiO4 material, indicating that the preparation method provided by the present invention can effectively produce the target product.

[0147] Figure 5 The stress luminescence spectra of the Mg2SiO4:m%Cr powder materials prepared by calcining at 1450°C in Examples 4 to 9 of the present invention under a force of 30 N are shown. The inset is the corresponding stress luminescence integrated intensity graph. Figure 5 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.

[0148] from Figure 5 It can be seen from the figure that the Mg2SiO4 material without Cr doping has no stress luminescence phenomenon. As the Cr doping concentration increases, the stress luminescence performance of the material is enhanced until it reaches the optimal Cr doping concentration of 0.4%. Further increase in the Cr doping concentration leads to the concentration quenching effect, which weakens the stress luminescence performance of the material.

[0149] Figure 6 Schematic diagram of the stress luminescence integrated intensity corresponding to the Mg2SiO4:0.4%Cr powder material prepared in Example 4 of the present invention under forces of 5N, 10N, 20N, 30N and 40N respectively.

[0150] from Figure 6 It can be seen from the graph that the stress luminescence performance of the Mg2SiO4:0.4%Cr powder material prepared by the present invention is enhanced with the increase of applied stress, and is roughly in a linear relationship.

[0151] Figure 7 This is a graph showing the average stress luminescence integral intensity of Mg2SiO4:0.4%Cr powder material prepared in Example 4 of the present invention, which was repeatedly tested in 10 groups under a force of 10N, with 5 times in each group.

[0152] from Figure 7It can be seen from the figure that the Mg2SiO4:0.4%Cr powder material prepared by the present invention can still maintain its stress luminescence performance under the repeated action of 10N stress, verifying its self-recovery property of stress luminescence.

[0153] Figure 8 This is a stress luminescence spectrum of the Mg2SiO4:0.4%Cr,n%Yb powder material prepared under calcination conditions of 1450°C in Examples 10 to 12 of the present invention under a force of 30N. Figure 8 Here, 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.

[0154] from Figure 8 As can be seen in the figure, the Mg2SiO4:0.4%Cr,n%Yb powder material prepared by the method provided herein and calcined at 1450°C 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 material's stress luminescence performance improves until it reaches the optimal Yb doping concentration of 2%. Further increases in the Yb doping concentration lead to concentration quenching, which weakens the material's stress luminescence performance.

[0155] It can be understood that the various technical features of the above-described embodiments can be combined arbitrarily. In order to make the description concise, not all possible combinations of the various technical features in the above-described 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.

[0156] The above are merely preferred embodiments of the present application and only specifically describe the technical principles of the present application. These descriptions are intended only to explain the principles of the present application and should not be construed in any way as limiting the scope of protection of the present application. Based on the explanations herein, any modifications, equivalent substitutions, and improvements made within the spirit and principles of the present application, as well as other specific implementations of the present application that can be conceived by those skilled in the art without inventive effort, shall be included within the scope of protection of the present 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, 0.000001≤m≤10.9, 0≤n≤10.9; Wherein, m% represents the molar percentage of Cr element relative to Mg2SiO4, and n% represents the molar percentage of X relative to Mg2SiO4; The X element includes at least one of Yb, Eu, Er, Nd, Sm, Dy, Ni, Al, and Ga.

2. A method for preparing the basalt-like structured intelligent stress luminescent material according to claim 1, characterized in that: The following steps are involved: S1. Weighing raw materials according to the stoichiometric ratio of each element in the chemical formula of the stress luminescent material, mixing the raw materials to obtain a mixed raw material; adding anhydrous ethanol to the mixed raw material, grinding and mixing uniformly, and drying to obtain a mixed powder; S2, calcining the mixed powder in S1 in air or oxygen atmosphere, and cooling the furnace naturally; S3. Grind the powder cooled in S2 to obtain a basalt-like structured intelligent stress luminescent material.

3. The method for preparing the basalt-like structured intelligent stress luminescent material according to claim 2, wherein: In air or oxygen atmosphere, the temperature is raised to 1300-1450° C. at a heating rate of 1-100° C. / min, and calcined for 0.5-24 h.

4. The method for preparing the basalt-like structured intelligent stress luminescent material according to claim 2, wherein: Anhydrous ethanol is added to the mixed raw materials, the mixture is ground and mixed evenly, and then dried at 80-300° C. to obtain a mixed powder.

5. The method for preparing the basalt-like structured intelligent stress luminescent material according to claim 2, wherein: The raw materials corresponding to the Mg element include Mg oxides, hydroxides or carbonates, and natural ores; The natural ore includes at least one of magnesite, olivine, serpentine and stevensite; The raw materials corresponding to the Si element include Si oxides; The raw materials corresponding to the Cr element include Cr oxides, chlorides and soluble nitrates; The raw materials corresponding to the X element include X oxides, chlorides and soluble nitrates.

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