CN114316954B - Metal oxysulfide free of activated ion force luminescence, preparation method and application thereof - Google Patents
Metal oxysulfide free of activated ion force luminescence, preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a metal oxysulfide free of activated ion force luminescence, and a preparation method and application thereof. Respectively mixing a calcium oxide compound, a zinc sulfide compound and a barium oxide compound according to the molar ratio of Ca, ba, zn and S, adding a grinding aid ethanol, grinding and uniformly mixing, drying, sintering, cooling and grinding to obtain the metal oxysulfide free from the mechanoluminescence by activated ions. The metal oxysulfide can be effectively excited by ultraviolet light, has a wide excitation band, has strong absorption in the range of 220-300nm, and has a certain phosphorescence phenomenon; in addition to photoluminescence and phosphorescence, the metal oxysulfide of the present invention exhibits a bright mechanoluminescence phenomenon without activation by a transition metal or rare earth ion.
Description
Technical Field
The invention relates to a metal oxysulfide free of activated ionic force luminescence and a preparation method thereof, belonging to the technical field of luminescent material preparation.
Background
Mechanoluminescence (ML) is a phenomenon of luminescence radiation generated by a material subjected to a certain stress stimulus, and is a form of direct conversion of mechanical energy into light energy. The mechanoluminescence material has potential application prospects in a plurality of fields such as artificial intelligence skin, structural health diagnosis, mechanical drive luminescence, stress sensors and the like, and has attracted wide attention of researchers at home and abroad. The elastic stress luminescence has outstanding advantages in practical application due to the radiation intensity proportional to the pressure, and becomes a hot spot for research and development. Researchers have developed various elastic force luminescent materials, wherein, the metal oxysulfide material has low cost, stable luminescent performance and simple manufacture, and can emit light signals only under the action of certain force.
Researchers have developed various metal oxysulfide-based electroluminescent materials, such as ZnS: mn 2+ ，CaZnOS:Eu 3+ ，SrZnOS:Pr 3+ And the like. Such materials are typically doped in a metal oxysulfide hostThe mechanoluminescence radiation is obtained by means of activating ions, such as transition metals or rare earth ions. CN113214823A discloses a ternary metal oxysulfide with both long afterglow and mechanoluminescence and a preparation method thereof; CN111909689A discloses a mechanoluminescence composite material and a preparation method and application thereof; CN107298977A discloses a visible-near infrared ultra-wide dual-mode response force luminescent material and a preparation method thereof.
At present, under the condition of not introducing active particles, the macroscopic mechanoluminescence phenomenon is difficult to implement by only depending on the main structure of the oxysulfide, and few reports of metal oxysulfide elasto-mechanoluminescence materials free of active ions exist.
Disclosure of Invention
Aiming at the defects of the prior art, in particular to the shortage of the active ion-free luminescent material with a high-efficiency main structure, the invention provides the active ion-free metal oxysulfide and the preparation method thereof. The metal oxysulfide of the invention can be effectively excited by ultraviolet light, has a wider excitation band and strong absorption in the range of 220-300nm, and can show certain macroscopic phosphorescence and photoluminescence phenomena without activating ions in addition to photoluminescence.
The technical scheme of the invention is as follows:
a metal oxysulfide free from activating ionic force luminescence, with a general formula of Ca 1-x Ba x ZnOS，0<x<1。
Preferably, the metal oxysulfide is composed of a CaZnOS crystal belonging to a P63mc space point group or a hexagonal system and a BaZnOS crystal belonging to a Cmcm space point group or an orthorhombic system.
According to the invention, preferably, the metal oxysulfide free from activated ion photoluminescence has a general formula of 0.04 ≦ x ≦ 0.8. According to the present invention, preferably, the metal oxysulfide free from activated ionic electroluminescence has the following chemical formula:
Ca 0.96 Ba 0.04 ZnOS、Ca 0.92 Ba 0.08 ZnOS、Ca 0.88 Ba 0.12 ZnOS、Ca 0.84 Ba 0.16 ZnOS、Ca 0.8 Ba 0.2 ZnOS、Ca 0.75 Ba 0.25 ZnOS、Ca 0.5 Ba 0.5 ZnOS、Ca 0.2 Ba 0.8 ZnOS。
according to the invention, the preparation method of the metal oxysulfide free from activated ion force luminescence comprises the following steps:
respectively weighing calcium oxide compound, zinc sulfide compound and barium oxide compound according to the molar ratio of Ca, ba, zn and S, mixing, adding grinding aid ethanol, grinding, uniformly mixing, drying, sintering, cooling and grinding to obtain the metal oxysulfide free from activated ionic force luminescence.
According to the present invention, preferably, the calcium oxide compound is calcium carbonate or calcium oxide;
preferably, the sulfur zinc compound is zinc sulfide;
preferably, the barium oxide compound is barium carbonate or barium oxide.
According to the invention, a calcium oxide compound, a barium oxide compound and a sulfur zinc compound are respectively weighed according to Ca, ba, zn, S =1-x, 1:1.
According to the invention, the volume ratio of the total mass of the raw materials to the ethanol is preferably 1. The total mass of the raw materials is the total mass of calcium carbonate, zinc sulfide and barium carbonate.
According to the present invention, it is preferable that before sintering, the powder is ground to a particle size of 0.15mm or less.
According to the invention, the drying temperature is preferably 60-80 ℃ and the drying time is preferably 1-3h.
According to the invention, preferably, the sintering temperature is 1200-1400K, and the sintering time is 3-5h; preferably, the sintering temperature is 1275K, and the sintering time is 4h; the sintering temperature is too low, the crystallization is incomplete, the requirement on the tube furnace is high due to too high temperature, and the experimental risk is high;
preferably, the sintering atmosphere is an oxygen-free atmosphere, and further preferably Ar gas.
According to the present invention, it is preferable that the sintered product is cooled and then ground to a particle size of 0.155mm or less.
The invention also provides a preparation method of the metal oxysulfide bulk solid free from activating ionic force luminescence, which comprises the following steps:
uniformly mixing polydimethylsiloxane, metal oxysulfide and a curing agent, removing bubbles, and curing to obtain the metal oxysulfide blocky solid free of activating ionic force luminescence.
According to the present invention, it is preferable that the curing agent is a silane coupling agent. The silane coupling agent can be vinyl triethoxysilane, vinyl trimethoxysilane, vinyl tri (beta-methoxyethoxy) silane, and the like.
According to the invention, the mass ratio of the polydimethylsiloxane to the metal oxysulfide is preferably 4-6:1, preferably 5:1; the mass ratio of the polydimethylsiloxane to the curing agent is 8-12, and preferably 10.
According to the invention, the bubbles are removed by means of evacuation.
According to the invention, the curing temperature is preferably 70 to 90 ℃, preferably 80 ℃. The curing time is 1-3h, preferably 2h.
The invention also provides the application of the metal oxysulfide free from activated ion mechanoluminescence in the field of mechanoluminescence.
The invention has the technical characteristics and beneficial effects that:
1. the metal oxysulfide free of the mechanoluminescence by the activated ions can be effectively excited by ultraviolet light without the activated ions, has a wider excitation band and has strong absorption in the range of 220-300 nm.
2. The metal oxysulfide free from activated ionic force luminescence not only has photoluminescence and phosphorescence, but also has a high-sensitivity non-destructive force luminescence phenomenon without ultraviolet light activation, can emit light only in the presence of pressure, and does not need pre-irradiation and other treatments. The metal oxysulfide can detect the phenomenon of strong photoluminescence under low pressure, and is beneficial to the application of the metal oxysulfide in the field of high-sensitivity photoluminescence.
3. The metal oxysulfide free from activating ionic force luminescence can observe certain phosphorescence luminescence when a 365nm excitation source is turned off, and a luminescence spectrum can be detected within 160 s.
4. The metal oxysulfide free of the activated ion force luminescence has stable structure, simple synthesis method and convenient large-scale production.
5. The preparation process is simple, and the massive material with high crystallinity can be obtained without using a fluxing agent.
Drawings
Fig. 1 is a comparison graph of X-ray powder diffraction patterns and standard diffraction card patterns of metal oxysulfide samples prepared by the mixture ratios (1) to (8) of example 1 and free from activated ion photoluminescence.
FIG. 2 is a scanning electron micrograph and an EDS energy spectrum of a sample of the activated-ion-force-free metal oxysulfide prepared in the formulation (4) of example 1.
Fig. 3 is a diffuse reflection analysis chart of the metal sulfur oxide sample of the non-activated ionic photoluminescence prepared in the mixture ratio (1) to (8) of example 1.
FIG. 4 is the fluorescence emission spectra of the samples of metal oxysulfide produced by the formulations (1) to (8) of example 1, with an excitation wavelength of 365nm.
FIG. 5 is a fluorescence lifetime spectrum of a sample of metal oxysulfide produced by the formulation (4) of example 1, with an excitation wavelength of 365nm.
FIG. 6 is a phosphorescence spectrum of a sample of the metal oxysulfide produced by the mixture ratios (1) to (8) of example 1. The excitation wavelength was 365nm.
FIG. 7 is a graph showing the decay times of 20-160s of phosphorescence after the sample of the metal oxysulfide free from the electrogenic photoluminescence prepared in the mixture ratios (1) to (8) of example 1 is irradiated for 10s with a 365nm excitation light source.
FIG. 8 is the mechanoluminescence spectrum under the same pressure of the bulk solid sample of the metal oxysulfide free from mechanoluminescence prepared in the compounding ratios (1) to (8) of example 2.
FIG. 9 is a fluorescence emission spectrum of the metal oxysulfide sample prepared in comparative examples 1-2, with an excitation wavelength of 365nm.
FIG. 10 is a fluorescence emission spectrum of the metal oxysulfide samples prepared in comparative examples 3 to 4, with an excitation wavelength of 365nm.
FIG. 11 is a fluorescence emission spectrum of the metal oxysulfide sample prepared in comparative example 5, with an excitation wavelength of 365nm.
Detailed Description
The present invention will be further described with reference to the following examples, but is not limited thereto.
Meanwhile, the experimental methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials are commercially available, unless otherwise specified.
Example 1
A preparation method of metal oxysulfide free of activating ionic force luminescence comprises the following steps:
selecting calcium carbonate, zinc sulfide and barium carbonate as starting compound raw materials, and respectively weighing 10 groups of four compound raw materials according to the stoichiometric ratio of the following elements, wherein the mixture ratio is as follows:
(1) Ca: ba: zn: S =1, corresponding to x =0; the obtained metal oxysulfide is abbreviated as CaZnOS;
(2) Ca: ba: zn: S =1, corresponding to x =0.04; the obtained metal oxysulfide is abbreviated as Ca 0.96 Ba 0.04 ZnOS；
(3) Ca: ba: zn: S =1, corresponding to x =0.08; the resulting metal oxysulfide is abbreviated as Ca 0.92 Ba 0.08 ZnOS；
(4) Ca: ba: zn: S =1, corresponding to x =0.12; the resulting metal oxysulfide is abbreviated as Ca 0.88 Ba 0.12 ZnOS；
(5) Ca: ba: zn: S =1, corresponding to x =0.16; the obtained metal oxysulfide is abbreviated as Ca 0.84 Ba 0.16 ZnOS；
(6) Ca: ba: zn: S =1, corresponding to x =0.2; the resulting metal oxysulfide is abbreviated as Ca 0.8 Ba 0.2 ZnOS；
(7) Ca: ba: zn: S =1, corresponding to x =0.25; the resulting metal oxysulfide is abbreviated as Ca 0.75 Ba 0.25 ZnOS；
(8) Ca: ba: zn: S =1, corresponding to x =0.5; the resulting metal oxysulfide is abbreviated as Ca 0.5 Ba 0.5 ZnOS；
(9) Ca: ba: zn: S =1, corresponding to x =0.8; the obtained metal oxysulfide is abbreviated as Ca 0.2 Ba 0.8 ZnOS；
(10) Ca: ba: zn: S =0; the obtained metal oxysulfide is abbreviated as BaZnOS;
mixing the raw materials, adding ethanol as a grinding aid (the volume ratio of the total mass of the raw materials to the ethanol is 1:1, the total mass of the raw materials is the total mass of calcium carbonate, zinc sulfide and barium carbonate), grinding and uniformly mixing until the particle size of the raw materials is less than or equal to 0.15mm, putting the raw materials into a quartz crucible, and drying in an oven at 70 ℃ for 2 hours; the quartz crucible is placed in a corundum boat and put into a horizontal high-temperature tube furnace. Strictly controlling the heating rate (the heating rate is 10 ℃/min), calcining for 4h at 1275K in Ar gas atmosphere, cooling to room temperature, and grinding until the particle size is less than or equal to 0.355mm to obtain the metal oxysulfide crystal free from activating ionic force luminescence.
FIG. 1 is a graph comparing the X-ray powder diffraction pattern and the standard diffraction card pattern of the metal oxysulfide sample free from activated ion photoluminescence prepared in the ratios (1) to (8) in example 1 and the sample prepared in comparative example 1-2. A German Bruker AXS D8 Advance diffractometer is adopted, a radiation source is a Cu target, the test voltage is 40kV, the test current is 40mA, the scanning step size is 0.02 degree/step, and the scanning speed is 0.12s/step. The XRD pattern analysis shows that the sample diffraction peak obtained under 1275K can coincide with CaZnOS and BaZnOS standard diffraction card patterns, namely the prepared metal oxysulfide consists of CaZnOS crystals and BaZnOS crystals, the CaZnOS crystals belong to P63mc space point group, and the hexagonal system and the BaZnOS crystal structure belong to Cmcm space point group and the hexagonal system.
FIG. 2 is a scanning electron micrograph and an EDS energy spectrum of the metal oxysulfide sample prepared by the mixture ratio (4) of example 1, and measured by using a German Carl Zeiss G300 FE-SEM System and a Debrueck Nano GmbH Berlin. The appearance and the particle size of the ternary metal oxysulfide sample can be seen from fig. 2, and the appearance is a massive solid. EDS (enhanced data Spectroscopy) shows that the barium element is successfully doped into the metal oxysulfide sample, the molar contents of Ca, ba, zn and S in the sample are similar to the feeding ratio through element analysis, and the molar ratio of each element in the sample also approximately accords with the general formula (because of errors in element analysis and test).
Fig. 3 is a diffuse reflection analysis chart of the metal oxysulfide sample prepared by the mixture ratios (1) to (8) of example 1, wherein the material shows an ultraviolet excitation band of 220 to 300nm and a wide excitation band width.
FIG. 4 is a fluorescence emission spectrum of the metal oxysulfide sample prepared by the mixture ratios (1) to (8) in example 1, wherein the excitation wavelength is 365nm, the testing apparatus is a F320 type steady-state instant fluorescence spectrometer of Tianjin Hongkong scientific and technological development GmbH, and the xenon lamp is used as the excitation light source, and the excitation wavelength is 365nm. As shown in FIG. 4, under 365nm excitation, the metal oxysulfide sample prepared by the mixture ratios (1) to (8) and free from activated ion photoluminescence has two fluorescence peaks respectively positioned at about 490nm and 612 nm.
FIG. 5 is a fluorescence lifetime spectrum of the sample of the metal oxysulfide produced by the preparation (4) of example 1, wherein the excitation wavelength is 365nm, the emission wavelength is 612nm, and the fluorescence lifetime is 0.7355ms.
FIG. 6 is a phosphorescence spectrum of a sample of the metal oxysulfide produced by the mixture ratios (1) to (8) of example 1. The excitation wavelength is 365nm, the phosphorescence spectrum is strong only around 600nm, the position of the spectrum peak is red-shifted with the increase of the value of x, and the phosphorescence is strongest when x = 0.12.
Fig. 7 is a graph of the phosphorescence decay time of 20-160s after the metal oxysulfide sample of the non-activated ionic photoluminescence prepared by the mixture ratios (1) to (8) of the example 1 is irradiated for 10s by the 365nm excitation light source, the decay time of the sample is different along with the change of x value, the maximum decay time reaches 160s when x =0.08, and the minimum decay time is only 20s when x = 0.25. The obvious difference of the phosphorescence decay time indicates that the phosphorescence material is expected to be applied to the anti-counterfeiting field.
Example 2
A method for preparing a bulk solid of metal oxysulfide free from activating ionic force luminescence comprises the following steps:
the preparation method comprises the following steps of (1) selecting 8 groups of ternary metal oxysulfide crystals prepared according to the proportion in the example 1 as raw materials, respectively mixing the raw materials with a Dow Corning 184 silicon rubber A component (the main component is polydimethylsiloxane) (the mass ratio of the A component to the ternary metal oxysulfide crystals is 5:1), adding a Dow Corning 184 silicon rubber B component (curing agent), mixing the B component and the polydimethylsiloxane in a weight ratio of 1 to 10 uniformly, vacuumizing to remove bubbles, and curing for 2 hours at 80 ℃ to prepare a solid with a preset shape.
Fig. 8 is the mechanoluminescence spectra under the same pressure for the bulk solid samples of the free-activated ionic mechanoluminescence metal oxysulfide obtained in the formulations (1) to (8) of example 2. When the force-luminescence experiment was performed in a dark room, a red force-luminescence was observed. A mechanoluminescence spectrometer self-made in a laboratory is adopted, red mechanoluminescence is obtained in 8 proportions under the stimulation of 10N pressure in a dark room, the wavelength of a luminescence peak is 600-630 nm, the fluorescence peak is red-shifted along with the increase of x, and the mechanoluminescence is strongest when x = 0.16.
Comparative example 1
The preparation method of CaZnOS comprises the following steps:
calcium carbonate and zinc sulfide are selected as starting compound raw materials, the raw materials are respectively weighed according to the following stoichiometric ratio of each element, and the proportion of the comparative examples is as follows:
Ca:Zn:S＝1:1:1。
mixing the raw materials, adding ethanol as a grinding aid (the volume ratio of the total mass of the raw materials to the ethanol is 1:1, the total mass of the raw materials is the total mass of calcium carbonate and zinc sulfide), grinding and uniformly mixing until the particle size of the raw materials is less than or equal to 0.15mm, putting the raw materials into a quartz crucible, and drying in an oven at 70 ℃ for 2 hours; the quartz crucible is placed in a corundum boat and placed in a horizontal high-temperature tube furnace. Strictly controlling the heating rate (the heating rate is 10 ℃/min), calcining at 1275K for 4h, cooling to room temperature, and grinding until the particle size is less than or equal to 0.355mm to obtain the metal oxysulfide crystal.
The preparation method of the blocky solid comprises the following steps:
the prepared metal oxysulfide crystal is used as a raw material, and is respectively mixed with a Dow Corning 184 silicon rubber component A (the main component is polydimethylsiloxane) (the mass ratio of the component A to the ternary metal oxysulfide crystal is 5:1), a Dow Corning 184 silicon rubber component B (curing agent) is added, the weight ratio of the component B to the polydimethylsiloxane is 1.
Comparative example 2
The preparation method of BaZnOS comprises the following steps:
selecting zinc sulfide and barium carbonate, and respectively weighing the compound raw materials according to the following stoichiometric ratio of each element, wherein the ratio is as follows:
Ba:Zn:S＝1:1:1；
mixing the raw materials, adding ethanol as a grinding aid (the volume ratio of the total mass of the raw materials to the ethanol is 1:1, the total mass of the raw materials is the total mass of zinc sulfide and barium carbonate), grinding and uniformly mixing until the particle size of the raw materials is less than or equal to 0.15mm, putting the raw materials into a quartz crucible, and drying in an oven at 70 ℃ for 2 hours; the quartz crucible is placed in a corundum boat and put into a horizontal high-temperature tube furnace. Strictly controlling the heating rate (the heating rate is 10 ℃/min), calcining at 1275K for 4h, cooling to room temperature, and grinding until the particle size is less than or equal to 0.355mm to obtain the catalyst.
A bulk solid was prepared using BaZnOS prepared as described above as a raw material, and the preparation method was as in comparative example 1.
Fig. 9 is a fluorescence emission spectrum of the metal oxysulfide sample prepared in comparative examples 1-2, in which the excitation wavelength is 365nm, as shown in fig. 9, caZnOS shows a weak fluorescence phenomenon, while BaZnOS shows a single fluorescence peak at about 500nm, and no mechanoluminescence phenomenon was observed in both CaZnOS and BaZnOS when a mechanoluminescence experiment was performed in a dark room using a mechanoluminescence spectrometer manufactured by a laboratory.
Comparative example 3
O 2 The preparation method of CaZnOS under the atmosphere comprises the following steps:
selecting zinc sulfide and calcium carbonate as starting compound raw materials, and respectively weighing the compound raw materials according to the following stoichiometric ratio of each element, wherein the ratio is as follows:
Ca:Zn:S＝1:1:1；
mixing the raw materials, adding ethanol as a grinding aid (the volume ratio of the total mass of the raw materials to the ethanol is 1:1, the total mass of the raw materials is zinc sulfide and the total mass of calcium carbonate), grinding and uniformly mixing until the particle size of the raw materials is less than or equal to 0.15mm, putting the raw materials into a quartz crucible, and drying in an oven at 70 ℃ for 2 hours; the quartz crucible is placed in a corundum boat and put into a horizontal high-temperature tube furnace. Strictly controlling the heating rate (the heating rate is 10 ℃/min), calcining at 1275K for 4h, cooling to room temperature, and grinding until the particle size is less than or equal to 0.355mm to obtain the catalyst.
A bulk solid was prepared from CaZnOS prepared as described above as a raw material by the method of comparative example 1.
Comparative example 4
O 2 The preparation method of BaZnOS under the atmosphere comprises the following steps:
selecting zinc sulfide and calcium carbonate as starting compound raw materials, and respectively weighing the compound raw materials according to the following stoichiometric ratio of each element, wherein the ratio is as follows:
Ba:Zn:S＝1:1:1；
mixing the raw materials, adding ethanol as a grinding aid (the volume ratio of the total mass of the raw materials to the ethanol is 1:1, the total mass of the raw materials is zinc sulfide and the total mass of calcium carbonate), grinding and uniformly mixing until the particle size of the raw materials is less than or equal to 0.15mm, putting the raw materials into a quartz crucible, and drying in an oven at 70 ℃ for 2 hours; the quartz crucible is placed in a corundum boat and placed in a horizontal high-temperature tube furnace. Strictly controlling the heating rate (the heating rate is 10 ℃/min), calcining at 1275K for 4h, cooling to room temperature, and grinding until the particle size is less than or equal to 0.355mm to obtain the catalyst.
A bulk solid was prepared using BaZnOS prepared as described above as a raw material, and the preparation method was as in comparative example 1.
FIG. 10 is a fluorescence emission spectrum of the metal oxysulfide samples prepared in comparative examples 3 to 4, with an excitation wavelength of 365nm. CaZnOS and BaZnOS calcined under O2 atmosphere show weak fluorescence peaks only around 500 nm.
Comparative example 5
O 2 Ca under atmosphere 1-x Ba x ZnOS, wherein the value of x is 0.08 and 0.16, and the preparation method comprises the following steps:
selecting zinc sulfide and calcium carbonate as starting compound raw materials, and respectively weighing the compound raw materials according to the following stoichiometric ratio of each element, wherein the mixture ratio is as follows:
ca: ba: zn: S =0.92, 1;
ca: ba: zn: S = 0.84;
mixing the raw materials, adding ethanol as a grinding aid (the volume ratio of the total mass of the raw materials to the ethanol is 1:1, the total mass of the raw materials is zinc sulfide and the total mass of calcium carbonate), grinding and uniformly mixing until the particle size of the raw materials is less than or equal to 0.15mm, putting the raw materials into a quartz crucible, and drying in an oven at 70 ℃ for 2 hours; the quartz crucible is placed in a corundum boat and placed in a horizontal high-temperature tube furnace. Strictly controlling the heating rate (the heating rate is 10 ℃/min), calcining at 1275K for 4h, cooling to room temperature, and grinding until the particle size is less than or equal to 0.155mm.
O prepared as described above 2 Ca under atmosphere 1-x Ba x ZnOS was used as the starting material to prepare a bulk solid, prepared as in comparative example 1.
FIG. 11 is a fluorescence emission spectrum of the metal oxysulfide sample prepared in comparative example 5, with an excitation wavelength of 365nm. The sample shows weak fluorescence peak only around 500nm, and no mechanoluminescence phenomenon is observed in the sample when a mechanoluminescence spectrometer is used for carrying out a mechanoluminescence experiment in a dark room.
Claims (11)
1. The metal oxysulfide free from activating ionic force to cause luminescence is characterized in that the general formula of the metal oxysulfide is Ca 1-x Ba x ZnOS， 0<x<1。
2. The activated ion-free mechanoluminescence-containing metal sulfide according to claim 1, wherein 0.04. Ltoreq. X.ltoreq.0.8 in the general formula of the activated ion-free mechanoluminescence-containing metal sulfide.
3. The active-free ionic mechanoluminescence-containing metal sulfide according to claim 1, wherein said active-free ionic mechanoluminescence-containing metal sulfide has the following chemical formula:
Ca 0.96 Ba 0.04 ZnOS、Ca 0.92 Ba 0.08 ZnOS、Ca 0.88 Ba 0.12 ZnOS、Ca 0.84 Ba 0.16 ZnOS、Ca 0.8 Ba 0.2 ZnOS、
Ca 0.75 Ba 0.25 ZnOS、Ca 0.5 Ba 0.5 ZnOS、Ca 0.2 Ba 0.8 ZnOS。
4. a method for preparing the activated ion-free mechanoluminescence-promoting metal sulfide oxide as claimed in claim 1, comprising the steps of:
respectively weighing calcium oxide, sulfur zinc compound and barium oxide according to the molar ratio of Ca, ba, zn and S, mixing, adding grinding aid ethanol, grinding, uniformly mixing, drying, sintering, cooling and grinding to obtain the metal oxysulfide free from activating ionic force luminescence, wherein the sintering atmosphere is an oxygen-free atmosphere.
5. The method according to claim 4, wherein the calcium oxide compound is calcium carbonate or calcium oxide, the zinc sulfide compound is zinc sulfide, and the barium oxide compound is barium carbonate or barium oxide.
6. The method for preparing activated ion-free mechanoluminescence-promoting metal sulfide as claimed in claim 4, wherein the volume ratio of the total mass of the calcium oxide compound, the zinc sulfide compound and the barium oxide compound to ethanol is 1.
7. The method of claim 4, wherein the method comprises one or more of the following conditions:
i. grinding the mixture to a particle size of less than or equal to 0.15mm before sintering;
ii. The drying temperature is 60-80 ℃, and the drying time is 1-3h;
and iii, sintering, cooling, and grinding until the particle size is less than or equal to 0.355mm.
8. The method for preparing activated ion-free mechanoluminescence-promoting metal sulfide as claimed in claim 4, wherein the sintering temperature is 1200 to 1400K.
9. A method for preparing a bulk solid from the activated ion-free mechanoluminescence-inducing metal sulfide oxide of claim 1, comprising the steps of:
uniformly mixing polydimethylsiloxane, ternary metal oxysulfide and a curing agent, removing bubbles, and curing to obtain a blocky solid with phosphorescence and photoluminescence;
the general formula of the ternary metal oxysulfide is Ca 1-x Ba x ZnOS， 0<x<1。
10. The method of claim 9, wherein the method comprises one or more of the following conditions:
i. the curing agent is a silane coupling agent;
ii. The mass ratio of the polydimethylsiloxane to the ternary metal oxysulfide is 4-6:1; the mass ratio of the polydimethylsiloxane to the curing agent is 8-12;
iii, the curing temperature is 70-90 ℃, and the curing time is 1-3h.
11. The activated ion-free mechanoluminescence-containing metal sulfide according to claim 1, for use in the field of mechanoluminescence.
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