Material for making passive detector for safe invasion identification, detector and method and use thereof

Abstract

The application discloses a kind of safe invasion mark passive detector manufacturing materials, detector and its manufacturing method and purposes, material chemical formula is (Bi 0.2 Na 0.2 K 0.2 Ba 0.2 Pb 0.2 )TiO3:xEr 3+ , 0 < x ≤ 0.04;The manufacturing method of the above-mentioned safe invasion mark passive detector is as follows: the material is ground into powder and introduced into the pressing mold to be pressed and sintered into a sheet body, and a light-proof adhesive tape is attached to one side surface of the sheet body;Another manufacturing method is as follows: the material is ground into powder and combined with an organic compound system to form a flexible sheet body, and a light-proof adhesive tape is attached to one side surface of the sheet body;The detector is used for safe invasion mark;The detector can directly display the light signal without an external power supply, and can be restored to the initial state by heating, and can quickly and effectively respond to the light signal again under light irradiation and has reversibility, which overcomes the drawbacks of the existing safe anti-theft security alarm system that requires power supply, and improves the safe anti-theft coefficient of the safe.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of information security protection devices, in particular to a safe invasion identification passive detector manufacturing material, a detector and a manufacturing method and use thereof. BACKGROUND

[0002] With the rapid development of network technology and communication technology, the amount of information generated in daily life is enough to be described by hundreds of millions, making the current network information security the focus of attention in the security field. In contrast, traditional information and property security issues receive less attention, however, for a long time, people are used to storing valuable property, confidential documents and other private valuable property in safes. The existing safes mainly rely on anti-theft security alarm systems to realize early warning of theft of the safes, but generally the power supply of the safe is cut off by the thief before the safe is stolen, causing the security alarm system to malfunction and fail to realize effective early warning, thus leading to events such as property theft and confidential document theft. Based on this, it is urgent to develop a passive invasion detector that can be placed inside the safe, so that the safe can timely understand whether there is illegal invasion during use, and effectively protect the safety of information and property. SUMMARY

[0003] The purpose of the present application is to provide a safe invasion identification passive detector manufacturing material to solve the above technical problems.

[0004] Another purpose of the present application is to provide a detector made of the above safe invasion identification passive detector manufacturing material.

[0005] Another purpose of the present application is to provide a manufacturing method of the above safe invasion identification passive detector.

[0006] Another purpose of the present application is to provide a use of the above safe invasion identification passive detector.

[0007] To this end, the technical solution of the present application is as follows:

[0008] A safe invasion identification passive detector manufacturing material, the chemical formula of the material is:

[0009] (Bi 0.2 Na 0.2 K 0.2 Ba 0.2 Pb 0.2 )TiO3:xEr 3+ , wherein 0 < x ≤ 0.04.

[0010] A manufacturing method of the above safe invasion identification passive detector, the steps are as follows:

[0011] S1, preparing a material for making a passive detector for safe identification of intrusion, and grinding into powder material;

[0012] S2, pouring the powder material prepared in step S1 into a pressing mold, demolding after pressing, and preparing a circular sheet-shaped body with uniform thickness and smooth surface;

[0013] S3, sintering the circular sheet-shaped body prepared in step S2;

[0014] S4, pasting at least one light-proof adhesive tape on one side surface of the sintered circular sheet-shaped body prepared in step S3.

[0015] Preferably, in step S2, the pressing pressure of the powder material in the pressing mold is 8-15 MPa; in step S3, the sintering temperature is 1000-1200°C, and the time length is 1-5 h.

[0016] Preferably, in the sintering process of step S3, the temperature is raised at a rate of 2-8°C / min to the specified sintering temperature, and after the sintering time reaches the specified length, the temperature is first lowered to 550°C at a rate of 3-7°C / min, and then naturally cooled to room temperature.

[0017] Preferably, after the sintering step of step S3 is completed, the surface of the circular sheet-shaped body is polished, ground and cleaned in sequence, and a circular sheet-shaped body with smooth surface is prepared.

[0018] A method for making a passive detector for safe identification of intrusion, characterized in that the steps are as follows:

[0019] S1, preparing a material for making a passive detector for safe identification of intrusion, and grinding into powder material;

[0020] S2, at room temperature, mixing and stirring the powder material prepared in step S1, polydimethylsiloxane (C2H6OSi) with vinyl active group, hydrogen-containing polydimethylsiloxane and methyl silicone oil according to the weight ratio of (20-30):(5-15):(0.5-3):(1-5) to obtain a mixed mucilage; n , hydrogen-containing polydimethylsiloxane and methyl silicone oil according to the weight ratio of (20-30):(5-15):(0.5-3):(1-5) to obtain a mixed mucilage;

[0021] S3, slowly pouring the mixed mucilage prepared in step S2 into a shaping mold, demolding after drying, and preparing a flexible film with uniform thickness and smooth surface;

[0022] S4, pasting at least one light-proof adhesive tape on one side surface of the sintered circular sheet-shaped body prepared in step S3, and preparing a passive detector for safe identification of intrusion.

[0023] Preferably, the particle size of the powder material in step S1 is 700-300 mesh.

[0024] Preferably, the drying temperature in step S3 is 50℃~130℃, and the drying time is 0.3h~3.5h.

[0025] Preferably, the thickness of the flexible film in step S3 is 0.05 mm to 0.25 mm.

[0026] One application of the passive detector for safe intrusion identification is to attach the passive detector for safe intrusion identification to a visible light position when the safe door is open, so as to determine whether there is an intrusion into the safe by detecting whether the detector surface changes color or emits self-emission.

[0027] Compared with existing technologies, this passive detector for safe intrusion identification can directly display light signals without an external power supply, and can be restored to its initial state by heating. Under light irradiation, it again shows a fast and effective response to light signals, demonstrating excellent reversibility. To a certain extent, it overcomes the drawback of existing safe anti-theft alarm systems that require power to drive, effectively improving the security and anti-theft coefficient of safes. Furthermore, by mixing it with various organic materials to prepare a flexible thin-film detector, its practical application scenarios are greatly enriched. Attached Figure Description

[0028] Figure 1(a) is a schematic diagram of the passive detector for safe intrusion identification prepared in Examples 2 to 4 of the present invention;

[0029] Figure 1(b) is a schematic diagram of the passive detector for safe intrusion identification prepared in Examples 5 to 8 of the present invention;

[0030] Figure 2(a) is a quantitative characterization diagram of the color-changing performance of the passive detector for safe intrusion identification prepared in Example 2 of the present invention;

[0031] Figure 2(b) is a quantitative characterization diagram of the color-changing performance of the passive detector for safe intrusion identification prepared in Example 3 of the present invention;

[0032] Figure 2(c) is a quantitative characterization diagram of the color-changing performance of the passive detector for safe intrusion identification prepared in Example 4 of the present invention;

[0033] Figure 3(a) shows the emission spectrum of the passive detector for safe intrusion identification prepared in Example 2 of the present invention in the range of 450 nm to 750 nm.

[0034] Figure 3(b) shows the emission spectrum of the passive detector for safe intrusion identification prepared in Example 3 of the present invention in the range of 450 nm to 750 nm.

[0035] Figure 3(c) is the emission spectrum of the passive probe for safe identification of intrusion prepared by Example 4 of the present application in the range of 450nm to 750nm;

[0036] Figure 4(a) is the reflectance change of the passive probe for safe identification of intrusion prepared by Example 2 of the present application in the multiple reversible color change performance test;

[0037] Figure 4(b) is the luminescence intensity change of the passive probe for safe identification of intrusion prepared by Example 2 of the present application in the multiple reversible color change performance test;

[0038] Figure 5(a) is the structural schematic diagram of the passive probe for safe identification of intrusion prepared by Example 2 of the present application in the initial state (without black light-proof tape);

[0039] Figure 5(b) is the photo of the passive probe for safe identification of intrusion prepared by Example 2 of the present application (the surface is covered with a black template with hollow number 8);

[0040] Figure 5(c) is the photo of the passive probe for safe identification of intrusion prepared by Example 2 of the present application (the black template with hollow number 8 is removed) after white light irradiation for 120s;

[0041] Figure 5(d) is the photo of the passive probe for safe identification of intrusion prepared by Example 2 of the present application (the black template with hollow number 8 is removed) after white light irradiation for 120s under the luminescence state of 980nm light irradiation;

[0042] Figure 6(a) is the photo of the passive probe for safe identification of intrusion prepared by Example 5 of the present application in the flat state;

[0043] Figure 6(b) is the photo of the passive probe for safe identification of intrusion prepared by Example 5 of the present application in the folded state;

[0044] Figure 6(c) is the photo of the passive probe for safe identification of intrusion prepared by Example 5 of the present application (the surface is covered with a heart-shaped pattern) after white light irradiation for 120s under the luminescence state of 980nm light irradiation. DETAILED DESCRIPTION

[0045] The present application will be further described in conjunction with the drawings and specific examples, but the following examples are by no means limiting to the present application.

[0046] Example 1

[0047] A kind of passive probe for safe identification of intrusion manufacturing material, it is prepared by the following method:

[0048] S1, Bi2O3, Na2CO3, K2CO3, BaCO3, PbO, TiO2 and Er2O3 powders are weighed according to the mass ratio shown in Table 1 below, and are added to a ball mill tank with absolute ethanol, and ball milled to obtain a mixture; the amount of absolute ethanol is preferably 4 / 5 of the volume of the ball mill tank, and the ball milling time is 24h;

[0049] Table 1:

[0050] Name Chemical Formula n(Bi):n(Na):n(K):n(Ba):n(Pb):n(Ti):n(Er) Material 1 (Bi 0.2 Na 0.2 K 0.2 Ba 0.2 Pb 0.2 )TiO3:0.005Er 3+ ]]> 0.199:0.199:0.199:0.199:0.199:1:0.005 Material 2 (Bi 0.2 Na 0.2 K 0.2 Ba 0.2 Pb 0.2 )TiO3:0.01Er 3+ ]]> 0.198:0.198:0.198:0.198:0.198:1:0.01 Material 3 (Bi 0.2 Na 0.2 K 0.2 Ba 0.2 Pb 0.2 )TiO3:0.02Er 3+ ]]> 0.196:0.196:0.196:0.196:0.196:1:0.02 Material 4 (Bi 0.2 Na 0.2 K 0.2 Ba 0.2 Pb 0.2 )TiO3:0.04Er 3+ ]]> 0.192:0.192:0.192:0.192:0.192:1:0.02

[0051] S2, the mixture obtained in step S1 is placed in an electrically heated constant temperature drying oven and dried at 90℃ for 12h to obtain a mixed powder;

[0052] S3, the mixed powder obtained in step S2 is placed in a box furnace, heated to 1000℃ at a rate of 4℃ / min and fired for 4h, and then cooled to room temperature at a rate of 5℃ / min to obtain a manufacturing material.

[0053] Example 2

[0054] A passive detector for safe identification of intrusion is prepared by the following method:

[0055] S1, the manufacturing material (Bi 0.2 Na 0.2 K 0.2 Ba 0.2 Pb 0.2 )TiO3:0.005Er 3+ is fired and ground to a powder without obvious particles;

[0056] S2, the powder material prepared in step S1 is weighed and poured into a circular pressing mold, and is pressed into a sheet under a pressure of 11Mpa, and the mold is removed to obtain a circular sheet-shaped body with uniform thickness and smooth surface;

[0057] S3, the circular sheet-shaped body prepared in step S2 is placed in a box furnace for sintering: the temperature is raised to 1100℃ at a rate of 4℃ / min and calcined for 2h, and then cooled to 550℃ at a rate of 5℃ / min, and then naturally cooled to room temperature; the surface of the sintered circular sheet-shaped body is polished, ground and cleaned to obtain a circular sheet-shaped body with smooth surface;

[0058] S4, a light-proof adhesive tape is pasted on one side surface of the circular sheet-shaped body prepared in step S3 to obtain a passive detector for safe identification of intrusion.

[0059] Example 3

[0060] A passive detector for safe identification of invasion, which is prepared by the following method:

[0061] S1, the material (Bi 0.2 Na 0.2 K 0.2 Ba 0.2 Pb 0.2 )TiO3:0.01Er 3+ , and ground to a powder without obvious particles;

[0062] S2, the powder material prepared by step S1 is weighed and poured into a circular pressing mold, and a pressure of 11Mpa is applied to press into a sheet, and the mold is removed to obtain a circular sheet with uniform thickness and smooth surface;

[0063] S3, the circular sheet prepared by step S2 is placed in a box furnace for sintering: the temperature is raised at a rate of 4℃ / min, and the temperature is optimized to 1100℃ and calcined for 2h, then the temperature is lowered at a rate of 5℃ / min to 550℃, and then naturally cooled to room temperature; the surface of the sintered circular sheet is polished and polished and cleaned to obtain a circular sheet with smooth surface;

[0064] S4, a light-proof tape is pasted on one side surface of the circular sheet prepared by step S3, and a passive detector for safe identification of invasion is obtained.

[0065] Example 4

[0066] A passive detector for safe identification of invasion, which is prepared by the following method:

[0067] S1, the material (Bi 0.2 Na 0.2 K 0.2 Ba 0.2 Pb 0.2 )TiO3:0.02Er 3+ , and ground to a powder without obvious particles;

[0068] S2, the powder material prepared by step S1 is weighed and poured into a circular pressing mold, and a pressure of 11Mpa is applied to press into a sheet, and the mold is removed to obtain a circular sheet with uniform thickness and smooth surface;

[0069] S3, the circular sheet prepared by step S2 is placed in a box furnace for sintering: the temperature is raised at a rate of 4℃ / min, and the temperature is optimized to 1100℃ and calcined for 2h, then the temperature is lowered at a rate of 5℃ / min to 550℃, and then naturally cooled to room temperature; the surface of the sintered circular sheet is polished and polished and cleaned to obtain a circular sheet with smooth surface;

[0070] S4, sticking a light-proof adhesive tape on one side surface of the circular sheet-shaped body prepared in step S3, to obtain the passive detector for identifying invasion of a safe.

[0071] The passive detector for identifying invasion of a safe prepared in Embodiments 2-4 has a structure as shown in FIG. 1(a), wherein the thickness of the circular sheet-shaped body obtained by sintering in step S3 is about 1.3 mm; the light-proof adhesive tape covers the position of the sheet-shaped body for detecting color change of the detector, i.e., in use, the color change of the detector surface and the position covered by the light-proof adhesive tape is compared to determine whether the safe is illegally invaded by whether the color of the detector changes.

[0072] Embodiment 5

[0073] A passive detector for identifying invasion of a safe is prepared by the following method:

[0074] S1, sintering a material (Bi 0.2 Na 0.2 K 0.2 Ba 0.2 Pb 0.2 )TiO3:0.005Er 3+ to a powder without obvious grain feeling, and sieving the powder by using a 300-700 mesh sieve;

[0075] S2, mixing and stirring the powder material prepared in step S1, polydimethylsiloxane with vinyl active groups, polydimethylsiloxane with hydrogen groups and methyl silicone oil in a weight ratio of 25:10:1:2 at room temperature to obtain a mixed mucilage;

[0076] S3, slowly pouring the mixed mucilage prepared in step S2 into a square forming mold, drying at 100°C for 2.5 h, and demolding after drying to obtain a flexible film with uniform thickness and smooth surface; wherein the thickness of the flexible film is 0.1 mm;

[0077] S4, sticking at least one light-proof adhesive tape on one side surface of the circular sheet-shaped body prepared in step S3, to obtain the passive detector for identifying invasion of a safe.

[0078] Embodiment 6

[0079] A passive detector for identifying invasion of a safe is prepared by the following method:

[0080] S1, sintering a material (Bi 0.2 Na 0.2 K 0.2 Ba 0.2 Pb 0.2 )TiO3:0.01Er 3+and ground to a powder without obvious particles, and the powder is sieved using a 300-700 mesh screen;

[0081] S2, at room temperature, the powder material prepared from step S1 is mixed with polydimethylsiloxane ((C2H6OSi) n ) containing a hydrogen group and methyl silicone oil in a weight ratio of 20:5:0.5:1 to obtain a mixed mucilage;

[0082] S3, the mixed mucilage prepared from step S2 is slowly poured into a square shaping mold, and dried at 100°C for 2.5h, and then demolded after drying to obtain a flexible film with uniform thickness and smooth surface; wherein the thickness of the flexible film is 0.1mm;

[0083] S4, at least one light-proof adhesive tape is pasted on one side surface of the circular sheet-shaped body prepared from step S3, to obtain a passive detector for safe identification of intrusion.

[0084] Example 7

[0085] A passive detector for safe identification of intrusion is prepared by the following method:

[0086] S1, a material (Bi 0.2 Na 0.2 K 0.2 Ba 0.2 Pb 0.2 )TiO3:0.02Er 3+ is calcined, and ground to a powder without obvious particles, and the powder is sieved using a 300-700 mesh screen;

[0087] S2, at room temperature, the powder material prepared from step S1 is mixed with polydimethylsiloxane ((C2H6OSi) n ) containing a hydrogen group and methyl silicone oil in a weight ratio of 20:5:0.5:1 to obtain a mixed mucilage;

[0088] S3, the mixed mucilage prepared from step S2 is slowly poured into a square shaping mold, and dried at 100°C for 2.5h, and then demolded after drying to obtain a flexible film with uniform thickness and smooth surface; wherein the thickness of the flexible film is 0.1mm;

[0089] S4, at least one light-proof adhesive tape is pasted on one side surface of the circular sheet-shaped body prepared from step S3, to obtain a passive detector for safe identification of intrusion.

[0090] The passive detector structure for safe box intrusion identification prepared from the above-mentioned embodiments 5-7 is shown in Fig. 1(b), and its use method and working principle are the same as those of the detectors prepared in embodiments 2-4. Compared with the detectors prepared in embodiments 2-4, the detector prepared in embodiments 5-7 is a flexible thin film, which is not easy to be damaged due to folding, and thus can be placed at the folding corner or bending part of the safe box during use, and compared with the sheet detector, the application scene is more abundant.

[0091] Performance characteristics and tests:

[0092] (I) Reversible color change performance characterization:

[0093] The color change performance of the passive detector for safe box intrusion identification prepared in embodiments 2-4 was characterized. The specific characterization method was that the diffuse reflectance spectra of the detector surface before and after color change were tested, and the quantitative characterization diagram of the color change performance of the passive detector for safe box intrusion identification prepared in embodiment 2 is shown in Fig. 2(a), the quantitative characterization diagram of the color change performance of the passive detector for safe box intrusion identification prepared in embodiment 3 is shown in Fig. 2(b), and the quantitative characterization diagram of the color change performance of the passive detector for safe box intrusion identification prepared in embodiment 4 is shown in Fig. 2(c).

[0094] In each characterization diagram, there are three curves, which are black dashed line, red solid line, and green dotted line, which correspond to the reflectivity of the detector surface at different wavelengths, unirradiated initial state, white light irradiation for 120 s, and heating at 250℃ for 60 s, respectively. According to the curve trend of each characterization diagram, it can be seen that the response degree of the detector to polychromatic light can be quantitatively described according to the change of the reflectivity value of the detector surface, that is, the detector successfully realizes the response detection of white light; specifically, after the detector is irradiated by white light for 120 seconds, the reflectivity of the detector surface in the wide visible light range of 400 nm-750 nm decreases obviously; and then, after the detector which has a significant response to white light is heated at 250℃ for 60 s, the reflectivity of the detector surface increases and is completely consistent with the measured reflectivity of the initial state, indicating that the detector has good reversibility and greatly prolongs the service life of the detector.

[0095] (II) Reversible luminescence performance characterization:

[0096] The luminescence performance of the passive detector for safe box intrusion identification prepared in Examples 2-4 was characterized. The specific characterization method was that the emission spectrum of the detector surface before and after color change was tested, and the emission spectrum of the passive detector for safe box intrusion identification of Example 2 in the range of 450 nm to 750 nm was obtained as shown in Figure 3(a), the emission spectrum of the passive detector for safe box intrusion identification of Example 3 in the range of 450 nm to 750 nm was obtained as shown in Figure 3(b), and the emission spectrum of the passive detector for safe box intrusion identification of Example 4 in the range of 450 nm to 750 nm was obtained as shown in Figure 3(c).

[0097] In each emission spectrum, there are three curves, which are black dashed line, red solid line and green dotted line, which correspond to the emission spectrum of the unirradiated initial state, the white light irradiation for 120 s and the sample after heating at 250℃ for 60 s at different wavelengths, respectively. According to the curve trend of each characterization graph, it can be seen that the luminescence intensity of the detector in the range of 450 nm to 750 nm is obviously reduced after the detector is irradiated by white light for 120 s. After heating the detector with significantly reduced luminescence intensity after white light irradiation for 120 s at 250℃ for 60 s, the luminescence intensity of the detector is restored and completely consistent with the initial state, indicating that the sample has good reversibility and greatly prolongs the service life of the detector. At the same time, the above characterization graphs can also prove that the use of 980 nm near-infrared non-visible light for irradiation can also read the response detection of the detector to white light.

[0098] According to the above performance characterization (I) and (II), the working principle of the detector of the present application is:

[0099] When the detector encounters an illegal invasion of the safe during use, the color of the detector surface will change obviously and be visible to the naked eye under light, while the color of the position where the light-proof tape is pasted will not change because it is not exposed to light. Based on this, when the user checks whether the safe has been invaded, two checking methods or one of them can be used for confirmation. One checking method is that the light-proof tape on the surface of the detector is torn off, and whether there is a color contrast between the position where the light-proof tape is pasted and other positions can be observed to understand whether the safe has been illegally invaded. The other checking method is that the surface of the detector is irradiated with 980 nm near-infrared non-visible light, and whether there is a green light intensity contrast on the surface of the detector is observed. If not, it indicates that the safe has not been illegally invaded, and the other method can also avoid the influence of visible light on the surface of the detector during the checking process. Then, when the checking is completed, the user can restore the detector to the initial state without color change by heating the detector to 250°C for 60 seconds. Since the detector shows stable reversibility, it has the characteristics of repeated use. When the user uses and repositions the detector in the safe, by trying to operate in a light-free or dark environment, the use and repositioning of the detector can be effectively avoided, and the problem of color change of the detector due to light can be avoided. For example, when the light is relatively dark, the detector is irradiated with 980 nm light to use the obvious green light emitted by the detector as a light source to complete the resetting of the detector in the safe.

[0100] As a comparative example of the present application, the applicant also prepared a series of materials (Bi 0.2 Na 0.2 K 0.2 Ba 0.2 Pb 0.2 )TiO3:xEr 3+ , x>0.04, by the same method as in Example 1 and entered the same performance test as above. After testing, the light emission intensity of the series of materials gradually decreased with the increase of the value of x under 980 nm light irradiation, which had poor effect in practical application and could not meet the requirements of passive invasion identification of the detector.

[0101] (III) Multiple cycle characterization:

[0102] The passive detectors for identifying invasion of safes prepared in Examples 2-7 were cyclically tested for reversible color change performance and reversible light emission performance as described above to verify the stability of the reversible performance of the detectors. The specific characterization method is that the detector surface before and after color change is tested by multiple diffuse reflectance spectroscopy and emission spectroscopy. After testing, the detectors prepared in each example can exhibit good reversible color change performance and reversible light emission performance.

[0103] Taking the safe invasion identifier passive probe prepared in Example 2 as an example, characterization was performed to obtain the reflectivity change graph of the safe invasion identifier passive probe prepared in Example 2 in the multiple reversible discoloration performance test as shown in Figure 4(a), and the luminescence intensity change graph of the safe invasion identifier passive probe prepared in Example 2 in the multiple reversible luminescence performance test as shown in Figure 4(b).

[0104] In the reflectivity change graph of Figure 4(a), the reflectivity difference before and after the discoloration of the probe after multiple detection discoloration and heating recovery changes little and is stable near 45%; in the luminescence intensity change graph of Figure 4(b), the luminescence intensity difference before and after the discoloration of the probe after multiple detection discoloration and heating recovery changes little and is stable near 75%; from the characterization results of the two graphs, it can be seen that the probe of the present application can exhibit stable reversible performance whether it is subjected to multiple reversible discoloration performance tests or reversible luminescence performance tests, proving that the probe has a long service life and greatly meets the needs of practical applications.

[0105] (IV) Application examples of the probe

[0106] In order to further confirm the effectiveness of the probe of the present application in practical application, the probe of the present application was put into practical application and the photos taken under different use conditions were compared.

[0107] I, the photo of the safe invasion identifier passive probe (without black light-proof tape) prepared by the method of Example 2 using the circular sheet-shaped probe as shown in Figure 5(a); in the initial state, the circular sheet-shaped probe is a light yellow circular substrate; in order to further more intuitively and obviously see the color contrast on the surface of the probe, a circular black template with a hollow number 8 is selected to cover the surface of the substrate instead of the black light-proof tape for testing, as shown in Figure 5(b), so as to facilitate observation of the change in the state of the substrate; Figure 5(c) shows the photo of the substrate after the black template is removed under irradiation after white light irradiation for 120s; Figure 5(d) shows the luminescence state photo of the substrate after the black template is removed under 980nm light irradiation after white light irradiation for 120s; from the above photos, it can be seen that the surface of the probe has extremely obvious color contrast visible to the naked eye after being irradiated by white light for 120s, and the luminescence intensity of the discolored area is obviously different from that of the non-discolored area under 980nm light irradiation, proving the feasibility of using 980nm light irradiation to read the response of the probe to white light.

[0108] II, the preparation method of example 6 is used to prepare the safe invasion identifier passive detector, the detector is a flexible thin film detector, as shown in figure 6 (a), the detector surface is flat, smooth and clean; The flexibility of the detector is tested, as shown in figure 6 (b), the detector is folded three times and kept in the folded state for 5 s, and then relaxed to return to the initial state naturally, the detector returns to the state shown in figure 6 (a), the surface is flat and smooth, no obvious fold appears, which shows that the flexible material prepared by the method has good flexibility.

[0109] In order to further prove that the flexible detector has excellent detection performance as the non-flexible detector, a heart-shaped pattern is placed on the surface of the flexible detector shown in figure 6 (a) and subjected to white light irradiation experiment; As shown in figure 6 (c), the heart-shaped pattern covered on the surface of the flexible detector after white light irradiation for 120 s under 980 nm light irradiation emits light; As can be seen from the light emission photo, the light emission intensity of the heart-shaped pattern at the center position of the flexible detector is obviously stronger than that at the surrounding position, because the heart-shaped pattern covered position is not irradiated by white light and the surrounding position is discolored after irradiated by white light, so when the heart-shaped pattern position emits light under 980 nm light irradiation, the light emission intensity is obviously stronger than that at the surrounding position, which shows that the flexible detector has excellent detection performance as the non-flexible detector, and is suitable for practical scene.

[0110] In summary, the safe invasion identifier passive detector can realize direct display of light signal without external power supply, and can recover to the initial state under heating state, and show rapid and effective response to light signal under light irradiation again, showing excellent reversible performance; To a certain extent, it overcomes the disadvantages of existing safe anti-theft alarm system which needs power supply, effectively improves the safety and anti-theft coefficient of the safe, and the flexible thin film detector greatly enriches the practical scene.

[0111] The above described examples are only preferred ways of the present application, and do not limit the scope of the present application, and various modifications and improvements of the technical solutions of the present application made by those skilled in the art without departing from the design spirit of the present application shall fall within the protection scope determined by the claims of the present application.

Claims

1. A material for a passive detector used for safe intrusion identification, characterized in that, The chemical formula of the material is (Bi) 0.2 Na 0.2 K 0.2 Ba 0.2 Pb 0.2 TiO3:xEr 3+ , where 0 < x ≤ 0.

04.

2. A method for manufacturing a passive detector for safe intrusion identification, characterized in that, It is prepared using the material described in claim 1, and the steps are as follows: S1. Prepare the material for the passive detector used for safe intrusion identification and grind it into powder. S2. Pour the powder material prepared in step S1 into a pressing mold, press it and then demold it to obtain a circular sheet with uniform thickness and a flat surface. S3. The circular sheet obtained in step S2 is subjected to sintering treatment. S4. At least one light-proof tape is attached to one side surface of the sintered circular sheet obtained in step S3.

3. The method for manufacturing a passive detector for safe intrusion identification according to claim 2, characterized in that, In step S2, the pressing pressure of the powder material in the pressing mold is 8 MPa to 15 MPa; in step S3, the sintering temperature is 1000℃ to 1200℃ and the sintering time is 1h to 5h.

4. A method for manufacturing a passive detector for safe intrusion identification, characterized in that, It is prepared using the material described in claim 1, and the steps are as follows: S1. Prepare the material for the passive detector used for safe intrusion identification and grind it into powder. S2. At room temperature, the powder material prepared in step S1 is mixed and stirred evenly with polydimethylsiloxane with vinyl active groups, hydrogen-containing polydimethylsiloxane and methyl silicone oil in a weight ratio of (20-30):(5-15):(0.5-3):(1-5) to obtain a mixed viscous liquid. S3. Slowly pour the mixed viscous liquid obtained in step S2 into the molding mold, and after drying, demold to obtain a flexible film with uniform thickness and smooth surface. S4. At least one strip of light-blocking tape is pasted onto one side surface of the circular sheet obtained in step S3 to obtain a passive detector for safe intrusion identification.

5. The method for manufacturing a passive detector for safe intrusion identification according to claim 4, characterized in that, The particle size of the powder material in step S1 is 700 mesh to 300 mesh.

6. The method for manufacturing a passive detector for safe intrusion identification according to claim 4, characterized in that, The drying temperature in step S3 is 50℃~130℃, and the drying time is 0.3h~3.5h.

7. The method for manufacturing a passive detector for safe intrusion identification according to claim 4, characterized in that, The thickness of the flexible film in step S3 is 0.05 mm to 0.25 mm.

8. The use of a passive detector for safe intrusion identification as described in any one of claims 2 to 7, characterized in that, A passive detector is attached to the visible light position of the safe when the door is open. The presence of an intrusion sign is determined by detecting whether the detector surface changes color or emits light.

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