A phase separation-induced self-calibrating stress luminescent material and preparation and application thereof

Abstract

The application provides a self-calibration stress luminescence material caused by phase separation and preparation and application thereof. 2‑ x B2O5 as a matrix, Mn x as an activator, 0.16 < x < 0.22, to prepare the stress luminescence material Ca 2‑x B2O5:Mn x The stress luminescence material prepared by the application is combined by a high-temperature solid-phase method in air, is low in cost, is environment-friendly, does not generate harmful substances in the preparation process, does not need pre-irradiation, has strong stress luminescence under mechanical action, can be directly observed by naked eyes in a dark environment, reduces the interference of the environment through a proportional self-calibration scheme, replaces stress visualization of absolute intensity, and improves reliability.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of stress luminescent materials, and particularly relates to a self-calibration stress luminescent material caused by phase separation and a preparation method and application thereof. BACKGROUND

[0002] Stress luminescence refers to a phenomenon that a solid material releases photons under the action of mechanical force, and the mechanical force includes collision, extrusion, friction, stretching, ultrasonic and the like. In recent years, with the research of people, stress luminescent materials show great application potential in stress sensing, stress visualization, structure damage monitoring, information storage and security anti-counterfeiting and the like.

[0003] Some optical sensors based on fluorescence intensity need pre-excitation, such as ultraviolet lamp irradiation or incandescent lamp irradiation, so that they are inconvenient to carry, and are easily affected by errors caused by signal acquisition efficiency changes, and environmental uncertainty inevitably amplifies this influence, resulting in serious errors of optical sensors. In fact, this negative influence can be reduced by a proportional self-calibration scheme, instead of an absolute intensity-based scheme, to obtain better reliability. The previous stress visualization can be qualitatively analyzed, while the stress visualization of the ratio type self-calibration can realize quantitative analysis. At the same time, the proportional self-calibration scheme usually causes the change of luminescent color, which is beneficial to the visualization sensing. Therefore, it is particularly important to develop a ratio type self-calibration stress visualization material in the field. SUMMARY

[0004] The present application provides a ratio type self-calibration stress visualization material caused by phase separation and a preparation and application thereof, so as to provide a stress luminescent material Ca 2-x B2O5 as a matrix, Mn x (0.16 < x < 0.22) as an activator. 2-x B2O5:Mn x , sintered in air, low cost, environmentally friendly, and no harmful substances generated in the preparation process.

[0005] The technical scheme of the present application is as follows: a self-calibration stress luminescent material caused by phase separation, the stress luminescent material is Ca 2-x B2O5:Mn x , 0.16 < x < 0.22.

[0006] Further, 0.17 ≤ x ≤ 0.21.

[0007] The self-calibration stress luminescent material caused by phase separation is prepared from the following molar fraction of raw materials: 50% of H3BO3, 49.6%-49.7% of CaO and 0.3%-0.4% of MnCO3.

[0008] The phase separation induced self-calibration stress luminescent material is prepared from raw materials with the following molar fractions: 50% of H3BO3, 49.6%-49.7% of CaO and 0.325%-0.375% of MnCO3.

[0009] The preparation method of the stress luminescent material comprises the following steps:

[0010] Grinding and uniformly mixing H3BO3, CaO and MnCO3 to obtain a mixture;

[0011] Sintering the mixture in air at 750-850℃ for 6h, and grinding to obtain the phase separation induced ratio type self-calibration stress luminescent material Ca 2-x B2O5:Mn x , 0.16

[0012] Further, the sintering method of the mixture is as follows: heating to 300℃ at 20℃ / min, then heating to 750-850℃ at 10℃ / min for sintering for 6h, then heating to 200℃ at 20℃ / min, and finally naturally cooling to room temperature.

[0013] The phase separation induced ratio type self-calibration stress luminescent film is prepared from the stress luminescent material and PDMS colloid.

[0014] Further, the preparation method of the stress luminescent film is as follows: uniformly mixing the stress luminescent material and PDMS colloid to obtain a mixed liquid, uniformly coating the mixed liquid in a mold, sealing and covering after heating and curing the colloid to obtain the phase separation induced ratio type self-calibration stress luminescent film.

[0015] Further, in the mixed liquid, the mass percentage of the stress luminescent material is 30%-40%.

[0016] Further, the heating and curing temperature is 80℃, and the curing time is 0.5h-2h.

[0017] Ca 2-x B2O5:Mn x As the application of the phase separation induced ratio type self-calibration stress luminescent material, 0.16

[0018] Ca 2-x B2O5:Mn x As the application of the phase separation induced ratio type self-calibration stress luminescent material in stress visualization, 0.16

[0019] The beneficial effects of the present application are as follows:

[0020] The present application takes Ca 2-x B2O5 as the matrix, and takes Mnx (0.16 < x < 0.22) is an activator, and the stress luminescent material Ca 2- x B2O5:Mn x The preparation method of the stress luminescent material in the application adopts a high-temperature solid-phase method, the preparation process is simple, the sintering temperature is low, sintering in air can be carried out, and the condition is easy to control; no toxic gas is generated in the preparation process, and the environment is not polluted; the interference of the environment is reduced through a proportional self-calibration scheme, the stress visualization of absolute intensity is taken, and the reliability is improved.

[0021] The Ca 2-x B2O5:Mn x As a stress luminescent material of proportional self-calibration caused by phase separation, no pre-UV irradiation is needed. The Ca 2-x B2O5:Mn x After mixing and curing with PDMS glue, the prepared stress luminescent film has proportional self-calibration stress luminescence within the elastic limit of the material, has strong stress luminescence under mechanical action (such as stretching, friction, etc.), can be directly observed by naked eyes in a dark environment, and has different stress luminescence colors under different stresses, and has very wide application value in the field of visual sensing. BRIEF DESCRIPTION OF DRAWINGS

[0022] In order to more clearly illustrate the technical solutions of the embodiments of the application or the prior art, the following will briefly introduce the drawings needed to be used in the embodiment or prior art description. Obviously, the drawings in the following description only some embodiments of the application, and for those skilled in the art, other drawings can also be obtained without creative labor on the basis of these drawings.

[0023] Figure 1 The XRD pattern of the stress luminescent material Ca 2-x B2O5:Mn x ;

[0024] Figure 2 The photoluminescence pattern of the Ca2B2O5:0.35% Mn prepared in Example 1 is shown in the figure;

[0025] Figure 3 The stress luminescence pattern of the stress luminescent material Ca2B2O5:0.35% Mn prepared in Example 1 is shown in the figure;

[0026] Figure 4 The stress luminescence pattern of the stress luminescent material Ca2B2O5:0.35% Mn prepared in Example 1 is shown in the figure;

[0027] Figure 5CIE diagram of the stress luminescent material Ca2B2O5: 0.35% Mn prepared in Example 1;

[0028] Figure 6 CIE diagram of Ca2B2O5: 0.325% Mn prepared in Example 4; <000015s>

[0029] Figure 7 CIE diagram of Ca2B2O5: 0.375% Mn prepared in Example 5;

[0030] Figure 8 CIE diagram of the stress luminescent material Ca2B2O5: 0.3% Mn prepared in Example 3;

[0031] Figure 9 CIE diagram of the stress luminescent material Ca2B2O5: 0.4% Mn prepared in Example 2. Detailed implementation manners

[0032] Next, the technical solutions in the embodiments of the present invention will be clearly and completely described in conjunction with the accompanying drawings in the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention.

[0033] Select H3BO3, CaO, and MnCO3 as raw materials, and weigh the corresponding elements of H3BO3, CaO, and MnCO3 according to the composition and ratio; grind and mix the H3BO3, CaO, and MnCO3 raw materials by ball milling to obtain a mixture; sinter the mixture in air at 750 - 850 °C for 6 h, and then grind to obtain the ratio-type self-calibrated stress luminescent material Ca 2-x B2O5:Mn x (0.16 < x < 0.22); mix the ratio-type self-calibrated stress luminescent material evenly with PDMS colloid to obtain a mixed liquid, coat the mixed liquid evenly in a polytetrafluoroethylene mold, wrap it with plastic wrap, and heat to cure the colloid to obtain a ratio-type self-calibrated stress luminescent film caused by phase separation.

[0034] The following is a detailed description in conjunction with specific embodiments.

[0035] Example 1

[0036] Take Ca 1.8077 B2O5:Mn 0.1923 as an example, a preparation method of a self-calibrated stress luminescent material caused by phase separation includes the following steps:

[0037] (1) grinding and mixing high purity H3BO3, CaO and MnCO3 to obtain mixed powder; taking the mole fraction of the mixed powder as 100%, H3BO3 accounts for 50%, CaO accounts for 49.65% and MnCO3 accounts for 0.35% in the mixed powder;

[0038] (2) placing the mixed powder of step (1) in air at a temperature of 800°C and sintering for 6h, and grinding to obtain Ca 1.8077 B2O5:Mn 0.1923 .

[0039] Ca 1.8077 B2O5:Mn 0.1923 stress luminescence material of step (2) is mixed with PDMS glue to obtain mixed liquid, the mixed liquid is uniformly coated in a mold, and after being wrapped with preservative film, it is heated and solidified at 80°C for 30min to obtain Ca 1.8077 B2O5:Mn 0.1923 stress luminescence film (abbreviated as Ca2B2O5:0.35%Mn).

[0040] Example 2

[0041] Taking Ca 1.7802 B2O5:Mn 0.2198 as an example, a preparation method of a self-calibration stress luminescence material caused by phase separation includes the following steps:

[0042] (1) grinding and mixing high purity H3BO3, CaO and MnCO3 to obtain mixed powder; taking the mole fraction of the mixed powder as 100%, H3BO3 accounts for 50%, CaO accounts for 49.65% and MnCO3 accounts for 0.35% in the mixed powder;

[0043] (2) placing the mixed powder of step (1) in air at a temperature of 800°C and sintering for 6h, and grinding to obtain Ca 1.7802 B2O5:Mn 0.2198 a stress luminescence material caused by phase separation.

[0044] Ca 1.7802 B2O5:Mn 0.2198 stress luminescence material of step (2) is mixed with PDMS glue to obtain mixed liquid, the mixed liquid is uniformly coated in a mold, and after being wrapped with preservative film, it is heated and solidified at 80°C for 30min to obtain Ca 1.7802 B2O5:Mn 0.2198 stress luminescence film (abbreviated as Ca2B2O5:0.35%Mn).

[0045] Example 3

[0046] Ca 1.8352 B2O5:Mn 0.1648 For example, a preparation method of a phase separation induced self-calibration stress luminescent material, comprising the following steps:

[0047] (1) grinding and uniformly mixing high-purity H3BO3, CaO and MnCO3 to obtain a mixed powder; taking the mole fraction of the mixed powder as 100%, H3BO3 accounts for 50%, CaO accounts for 49.7%, and MnCO3 accounts for 0.3% in the mixed powder;

[0048] (2) placing the mixed powder of step (1) in an air atmosphere at a temperature of 800°C and high-temperature sintering for 6h, and grinding to obtain a phase separation induced ratio type self-calibration stress luminescent material Ca 1.8352 B2O5:Mn 0.1648 .

[0049] The Ca 1.8352 B2O5:Mn 0.1648 stress luminescent material of step (2) is uniformly mixed with a PDMS colloid to obtain a mixed liquid, the mixed liquid is uniformly coated in a mold, and after being wrapped with a preservative film, it is heated and solidified at 80°C for 30min to obtain a Ca 1.8352 B2O5:Mn 0.1648 stress luminescent film (abbreviated as Ca2B2O5:0.3%Mn).

[0050] Example 4

[0051] Ca 1.8215 B2O5:Mn 0.17858 For example, a preparation method of a phase separation induced self-calibration stress luminescent material, comprising the following steps:

[0052] (1) grinding and uniformly mixing high-purity H3BO3, CaO and MnCO3 to obtain a mixed powder; taking the mole fraction of the mixed powder as 100%, H3BO3 accounts for 50%, CaO accounts for 49.675%, and MnCO3 accounts for 0.325% in the mixed powder;

[0053] (2) placing the mixed powder of step (1) in an air atmosphere at a temperature of 800°C and high-temperature sintering for 6h, and grinding to obtain a phase separation induced ratio type self-calibration stress luminescent material Ca 1.8215 B2O5:Mn 0.17858 .

[0054] The Ca 1.8215 B2O5:Mn 0.17858 stress luminescent material of step (2) is uniformly mixed with a PDMS colloid to obtain a mixed liquid, the mixed liquid is uniformly coated in a mold, and after being wrapped with a preservative film, it is heated and solidified at 80°C for 30min to obtain a Ca 1.8215B2O5:Mn 0.17858 Ca2B2O5:0.325%Mn stress luminescence film.

[0055] Example 5

[0056] Ca 1.7940 B2O5:Mn 0.2060 For example, a preparation method of a phase separation induced self-calibration stress luminescence material includes the following steps:

[0057] (1) high-purity H3BO3, CaO and MnCO3 are ground and mixed to obtain a mixed powder; taking the molar fraction of the mixed powder as 100%, H3BO3 accounts for 50%, CaO accounts for 49.625%, and MnCO3 accounts for 0.375% in the mixed powder;

[0058] (2) the mixed powder in step (1) is placed in high-temperature sintering at 800°C in air for 6h, and grinding is performed to obtain a phase separation induced ratio type self-calibration stress luminescence material Ca 1.7940 B2O5:Mn 0.2060 .

[0059] The Ca 1.7940 B2O5:Mn 0.2060 stress luminescence material in step (2) is uniformly mixed with PDMS glue to obtain a mixed liquid, the mixed liquid is uniformly coated in a mold, and after being coated with a preservative film, it is heated and solidified at 80°C for 30min to obtain a Ca 1.7940 B2O5:Mn 0.2060 stress luminescence film (abbreviated as Ca2B2O5:0.375%Mn).

[0060] Comparative Example 1

[0061] Ca 1.9451 B2O5:Mn 0.0549 For example, a preparation method of a phase separation induced self-calibration stress luminescence material includes the following steps:

[0062] (1) high-purity H3BO3, CaO and MnCO3 are ground and mixed to obtain a mixed powder; taking the molar fraction of the mixed powder as 100%, H3BO3 accounts for 50%, CaO accounts for 49.9%, and MnCO3 accounts for 0.1% in the mixed powder;

[0063] (2) the mixed powder in step (1) is placed in high-temperature sintering at 800°C in air for 6h, and grinding is performed to obtain a phase separation induced ratio type self-calibration stress luminescence material Ca 1.9451 B2O5:Mn 0.0549 .

[0064] The Ca1.9451 B2O5:Mn 0.0549 The stress luminescence material is mixed with the PDMS glue to obtain a mixed liquid, the mixed liquid is uniformly coated in a mold, and after being wrapped with a preservative film, the mixed liquid is heated and solidified at 80°C for 30 min to obtain Ca 1.9451 B2O5:Mn 0.0549 The stress luminescence coating.

[0065] Comparative Example 2

[0066] The Ca 1.4506 B2O5:Mn 0.5494 For example, a preparation method of a self-calibration stress luminescence material caused by phase separation, comprising the following steps:

[0067] (1) high-purity H3BO3, CaO and MnCO3 are ground and uniformly mixed to obtain a mixed powder; taking the molar fraction of the mixed powder as 100%, H3BO3 accounts for 50%, CaO accounts for 49% and MnCO3 accounts for 1% in the mixed powder;

[0068] (2) the mixed material powder in step (1) is placed in high-temperature sintering at 800°C in air for 6h, and grinding is performed to obtain Ca 1.4506 B2O5:Mn 0.5494 A ratio type self-calibration stress luminescence material caused by phase separation.

[0069] The Ca 1.4506 B2O5:Mn 0.5494 The stress luminescence material is mixed with the PDMS glue to obtain a mixed liquid, the mixed liquid is uniformly coated in a mold, and after being wrapped with a preservative film, the mixed liquid is heated and solidified at 80°C for 30 min to obtain Ca 1.4506 B2O5:Mn 0.5494 The stress luminescence coating.

[0070] Comparative Example 3

[0071] This comparative example is basically the same as Example 1, except that Ca 1.8901 B2O5:Mn 0.10998 For example, H3BO3 accounts for 50%, CaO accounts for 49.8% and MnCO3 accounts for 0.2% in the mixed material.

[0072] Comparative Example 4

[0073] This comparative example is basically the same as Example 1, except that Ca 1.5605 B2O5:Mn 0.4395 For example, H3BO3 accounts for 50%, CaO accounts for 49.2% and MnCO3 accounts for 0.8% in the mixed material.

[0074] The stress luminescent material prepared in Example 1-5 and Comparative Example 1-4 and the PDMS glue were mixed in a mass ratio of about 1:2, the mass ratio of PDMS and curing agent in the PDMS glue was 10:1, the length and width of the mold coating layer were 3 cm and 0.5 cm respectively, and the thickness was 0.5 mm.

[0075] Figure 1 The XRD pattern of the stress luminescent material Ca2B2O5:0.35%Mn prepared in Example 1. 2-x B2O5:Mn x The XRD pattern of the stress luminescent material Ca2B2O5:0.35%Mn prepared in Example 1. Figure 1 The XRD pattern of the stress luminescent material Ca2B2O5:0.35%Mn prepared in Example 1 was well matched with the PDF standard card (JCDP#22-0139), but the XRD pattern changed with the change of the Mn doping concentration, the peaks in the standard card (JCDP#32-0155) appeared, and phase separation occurred in the range of 0.3% to 0.4% of the MnCO3 molar fraction, and phase separation occurred in a certain concentration range of Mn.

[0076] Figure 2 The photoluminescence pattern of the stress luminescent material Ca2B2O5:0.35%Mn prepared in Example 1 appeared two luminescence centers at different excitation wavelengths, and the double peaks changed with the change of the excitation wavelength, and excitation dependence occurred.

[0077] Figure 3 The stress luminescence pattern of the stress luminescent material Ca2B2O5:0.35%Mn prepared in Example 1 was stretched by a linear motor, and the stress luminescence intensity increased from Figure 4 It can be seen from the stress luminescence pattern of the stress luminescent material Ca2B2O5:0.35%Mn that the stress luminescence intensity increased with the increase of the strain from 40% to 100%, and the stress luminescence intensity also increased. The stress luminescence intensity of Ca2B2O5:0.35%Mn was about 500.

[0078] Figure 4 The stress luminescence pattern of the stress luminescent material Ca2B2O5:0.35%Mn prepared in Example 1 at different strains, the stress luminescence color changed from yellow-green to orange-yellow with the increase of the strain.

[0079] Figure 5 The CIE pattern of the stress luminescent material Ca2B2O5:0.35%Mn prepared in Example 1, from the CIE pattern, it can also be seen that the stress luminescence color changed from yellow-green to orange-yellow with the increase of the strain.

[0080] Figure 6 The CIE pattern of the stress luminescent material Ca2B2O5:0.35%Mn prepared in Example 1, from the CIE pattern, it can also be seen that the stress luminescence color changed from yellow-green to orange-yellow with the increase of the strain.

[0081] Figure 7 The image shows the CIE diagram of the stress-luminescent material Ca2B2O5:0.375%Mn prepared in Example 5. The change in its stress-luminescent color can also be seen from the CIE diagram.

[0082] Figure 8 The image shows the CIE diagram of the stress-luminescent material Ca2B2O5:0.3%Mn prepared in Example 3. The CIE diagram also shows that the stress-luminescent color changes slightly with strain.

[0083] Figure 9 The image shows the CIE diagram of the stress-luminescent material Ca2B2O5:0.4%Mn prepared in Example 2. The CIE diagram also shows that the stress-luminescent color changes slightly with strain.

[0084] Depend on Figures 5-7 It can be seen that the stress-luminescent materials Ca2B2O5:0.325%Mn and Ca2B2O5:0.375%Mn will change their stress-luminescent color with increasing strain, but the degree of change is not as obvious as that of the stress-luminescent material Ca2B2O5:0.35%Mn.

[0085] The above tests confirm that phase separation can cause stress emission colors to differ under different strains, thus achieving ratio-based self-calibrated stress visualization.

[0086] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. Ca 2-x B2O5: Mn x The use of self-calibrating stress luminescence materials as a result of phase separation in stress visualization is characterized in that The preparation method of the self-calibration stress luminescent material comprises the following steps: H3BO3 with a mole fraction of 50%, CaO with a mole fraction of 49.6%-49.7%, and MnCO3 with a mole fraction of 0.3%-0.4% are ground and mixed uniformly to obtain a mixture; The mixture is sintered in air at 750-850 °C for 6 h, and after grinding, the self-calibrating stress luminescence material Ca 2-x B2O5: Mn x .

2. Use according to claim 1, characterized in that, The mole fractions of the raw materials are as follows: H3BO3 with a mole fraction of 50%, CaO with a mole fraction of 49.625%-49.675%, and MnCO3 with a mole fraction of 0.325%-0.375%.

3. Use according to claim 1, characterized in that, The sintering method of the mixture is as follows: heating at a rate of 20 ℃ / min to 300 ℃, then heating at a rate of 10 ℃ / min to 750-850 ℃ and sintering for 6 h, then heating at a rate of 20 ℃ / min to 200 ℃, and finally naturally cooling to room temperature.

4. A self-calibrating stress luminescence film, characterized by, Preparation from the self-calibration stress luminescent material and the PDMS colloid in any one of claims 1-3.

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