CN111925691A - Powder particle ink for mechanoluminescence ceramic material and preparation method and application thereof - Google Patents

Abstract

The invention belongs to the technical field of mechanoluminescence ceramic materials, and particularly relates to powder particle ink for mechanoluminescence ceramic materials, and a preparation method and application thereof. The blue mechanoluminescence ceramic material powder particle ink is characterized in that the ink is prepared from a blue mechanoluminescence ceramic material powder particle suspension solvent, and the chemical composition general formula of the ceramic material is Ca_1‑x‑yAl₃O₄N:xEu²⁺,yRe³⁺Wherein Re is one or two combinations of Nd and Sm, and the value ranges of x and y are respectively as follows: x is more than or equal to 0.01 and less than or equal to 0.1, and y is more than or equal to 0.01 and less than or equal to 0.2. And then coating the substrate with the pressure sensor to prepare the blue mechanoluminescence sensor, wherein the pressure sensor prepared by the method is applied to a wind tunnel experiment.

Description

Powder particle ink for mechanoluminescence ceramic material and preparation method and application thereof

The invention is a divisional application, and the original application number is: 201711061636.7, the filing date is: 2017-11-02, the patent name is: a blue mechanoluminescence ceramic material and a preparation method thereof.

Technical Field

The invention belongs to the technical field of mechanoluminescence materials, and particularly relates to powder particle ink for mechanoluminescence ceramic materials, and a preparation method and application thereof.

Background

The physical phenomenon that a material emits visible light under the action of stress, friction, fracture or ultrasonic oscillation is called forceA phenomenon of luminescence. Like the long persistence luminescence phenomenon, mechanoluminescence is a physical phenomenon that has long been recognized by humans. There are many materials capable of generating the mechanoluminescence phenomenon, including organic and inorganic materials such as sugar crystals, quartz crystals and the long afterglow phosphor SrAl, which has rapidly developed in recent years₂O₄Eu, etc. The mechanoluminescence phenomenon of the materials has not been put into practical use all the time because of the low mechanoluminescence intensity and short duration of the common materials and the low level of the prior art of weak light detection. At the end of the last 90 s, researchers found strong mechanoluminescence in long-afterglow materials, which arouses great interest of researchers in the field of sensors, reports about mechanoluminescence are rapidly increasing, and published papers in related fields are increasing year by year.

In recent years, scientists have successively discovered various materials with high-efficiency photoluminescence performance, which have the advantages of low cost, stable luminescence performance, light-emitting intensity in direct proportion to the stress, and the like, and are applied to a plurality of important occasions. For example, sensors made using the mechanoluminescence properties of mechanoluminescence materials can be used to detect the formation and propagation of fine cracks when bridges and buildings are impacted. In engineering construction, in order to ensure the reliability of an engineering structure, stress distribution measurement is generally required, the stress distribution measurement can use an X-ray diffraction method, a thermal imaging method, an optical fiber network and the like, and another simple, reliable and low-cost method is provided for structure damage detection and stress distribution by utilizing the mechanoluminescence characteristic of a mechanoluminescence material. With the development of the low-light-level detection technology and the improvement of the luminous intensity of the mechanoluminescence material, the mechanoluminescence material has a very strong application prospect in the aspects of mechanical sensors, material stress distribution analysis, building safety, life science, earthquake and volcanic eruption prediction and the like.

Disclosure of Invention

In order to overcome a series of problems of weak luminous intensity, difficult low-light-level detection and the like of the mechanoluminescence material in the prior art, the invention provides a blue mechanoluminescence ceramic material and a preparation method thereof.

In order to solve the defects of the prior art, the technical scheme adopted by the invention is as follows:

a blue mechanoluminescence ceramic material having a chemical composition of the general formula Ca_1-x-yAl₃O₄N: xEu²⁺, yRe³⁺Wherein Re is one or two combinations of Nd and Sm, and the value ranges of x and y are respectively as follows: x is more than or equal to 0.01 and less than or equal to 0.1, and y is more than or equal to 0.01 and less than or equal to 0.2. In particular, the luminescent center of the ceramic is Eu²⁺Ions by introduction of Nd³⁺And Sm³⁺The rare earth impurity ions can effectively enhance the mechanoluminescence effect.

A preparation method of a blue mechanoluminescence ceramic material is characterized by comprising the following steps:

(1) preparing materials: as high purity CaCO₃、Al₂O₃AlN and Eu₂O₃And Nd₂O₃And Sm₂O₃One or two of the raw materials are combined to be used as raw materials according to a chemical composition general formula Ca_1-x-yAl₃O₄N: xEu²⁺, yRe³⁺The raw materials are accurately weighed according to the proportion of the elements in the raw materials; the value ranges of x and y are respectively as follows: x is more than or equal to 0.01 and less than or equal to 0.1, and y is more than or equal to 0.01 and less than or equal to 0.2;

(2) mixing materials: the method comprises the steps of taking agate balls as grinding balls, taking absolute ethyl alcohol as a ball milling medium, simultaneously putting the agate balls, the absolute ethyl alcohol and raw materials into a ball milling tank, and carrying out ball milling and mixing on a planetary ball mill for 5-20 hours to form a slurry-shaped mixture, wherein the mass ratio of the absolute ethyl alcohol to the raw materials is 2: 3;

(3) drying: placing the obtained slurry-like mixture in an oven, carrying out heat preservation and drying for 4-6 hours at the temperature of 80 ℃, and then sieving the dried raw material with a 200-mesh sieve to obtain a uniformly mixed raw material;

(4) molding: weighing a certain amount of uniformly mixed raw materials, and putting the raw materials into a stainless steel mold for dry pressing and forming under the pressure of 10-15 MPa to obtain a cylindrical ceramic blank;

(5) and (3) sintering: will be describedThe ceramic blank is sintered at high temperature under the condition of reducing atmosphere, and the sintering atmosphere is 5 percent of H₂/95%N₂The heating rate of the hydrogen-nitrogen mixed gas is 5 ℃/min, the sintering temperature is 1100-1400 ℃, the sintering time is 6-10 hours, and the blue mechanoluminescence ceramic material is obtained after cooling and taking out.

Compared with the prior art, the invention has the beneficial effects that:

(1) the invention provides a blue mechanoluminescence ceramic material, the matrix composition of which is CaAl₃O₄N, by rare earth ion Eu²⁺Doping to obtain blue photoluminescence, wherein the luminescence peak is about 470 nm;

(2) by introducing Nd³⁺And Sm³⁺When rare earth impurity ions are subjected to plasma treatment, a trap energy level is generated, and the mechanoluminescence effect can be effectively enhanced;

(3) the mechanoluminescence ceramic provided by the invention has high compressive strength, can work under a larger pressure condition, and has the characteristic of repeated use after the pressure is eliminated.

The invention also discloses a stress luminescent element, which is a substrate made of the blue force luminescent ceramic material.

The invention also discloses a stress luminescent element, which comprises a substrate and a pressure luminescent film attached to the substrate, wherein the pressure luminescent film is the blue mechanoluminescence ceramic material powder or the blue mechanoluminescence ceramic material sheet.

The invention also discloses a stress light-emitting element which comprises a substrate and a pressure light-emitting film attached to the substrate, wherein the pressure light-emitting film is blue mechanoluminescence ceramic material powder or a blue mechanoluminescence ceramic material sheet.

Preferably, the thickness of the pressure luminescence film is 1-10 mm.

The substrate of the present invention may be a rigid substrate or a flexible substrate. Preferably, the rigid substrate may be selected from glass, silicon, steel, ceramic, cement, wood, and stone, and the flexible substrate may be selected from PDMS (polydimethylsiloxane) film, PET (polyethylene terephthalate) film, PS (polystyrene) film, PU (polyurethane) film, PI (polyimide) film, and PVA (polyvinyl alcohol) film.

The preparation method of the stress light-emitting element comprises the following steps: a suspension of blue mechanoluminescent ceramic material powder particles as described above is coated on a substrate as described above.

Although the sensor meeting the requirement of the present invention can be prepared by preparing the suspension from the suspension solvent of the blue mechanoluminescence ceramic material powder particles, and then coating the suspension on the substrate, when the suspension also contains a high molecular substance, the sensitivity and accuracy of the finally prepared sensor can be further improved.

The content of the blue photoluminescent ceramic material powder particles may also vary within wide limits, preferably in the range of 0.5 to 10 parts by weight, preferably 1 to 5 parts by weight, based on 100 parts by weight of the suspension.

Preferably, the high molecular substance is selected from one or more of PVA, EVA (ethylene vinyl acetate), PDMS, PU, PMMA (polymethyl methacrylate), PAM (polyacrylamide), PVP (polyvinylpyrrolidone), starch, cellulose, vegetable gum, animal gum, carboxymethyl starch, starch acetate, hydroxymethyl cellulose, and carboxymethyl cellulose.

According to the invention, the content of the polymer substance can also vary within wide limits, preferably from 1 to 10 parts by weight, preferably from 3 to 8 parts by weight, based on 100 parts by weight of the suspension.

According to the present invention, the solvent may be various solvents conventionally used in the art, preferably selected from one or more of water, methanol, ethanol, acetone, ethylene glycol, isopropyl alcohol, diethylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol butyl ether, ethylene glycol phenyl ether, ethylene glycol benzyl ether, kosmol, diethylene glycol methyl ether, diethylene glycol ethyl ether, diethylene glycol butyl ether, triethylene glycol methyl ether, diacetone alcohol, tridecanol, tetradecanol, dioctyl phthalate, ethyl acetate, butyl acetate, cyclohexanone, xylene, dicyclohexyl, cyclohexane, n-butanol, methyl ethyl ketone, dimethyl phthalate, and sorbitol.

According to the present invention, the method for applying the suspension of blue mechanoluminescence ceramic material powder particles on the surface of the substrate may be selected conventionally in the art, for example, a coating method such as spray coating, spin coating, etc. may be used, and a printing technique may also be used. The invention preferably prints the suspension of blue mechanoluminescence ceramic material powder particles on the surface of the substrate by the printing technology, thereby further improving the sensitivity and accuracy of the prepared sensor. Wherein the printing technique may be selected from one of dispensing, ink jet printing, water transfer printing, screen printing, and roll-to-roll printing. When the suspension of the blue mechanoluminescence ceramic material powder particles is printed on the surface of the substrate by using a printing technique, the suspension is preferably prepared into ink by blending and stirring or blending and ultrasonically dispersing the suspension.

The blue mechanoluminescence ceramic material powder particles, the pressure sensing component and the application of the pressure sensor prepared by the method in wind tunnel experiments are provided.

The invention also discloses a stress luminescent element, which comprises a high polymer material and the blue mechanoluminescence ceramic material powder, wherein the blue mechanoluminescence ceramic material powder is uniformly distributed in the high polymer material, and the addition amount of the blue mechanoluminescence ceramic material powder is 1-90%; preferably 10 to 80%. The polymeric material may be selected from PDMS (polydimethylsiloxane), PET (polyethylene terephthalate), PS (polystyrene), PU (polyurethane), PI (polyimide), and PVA (polyvinyl alcohol) films. In order to improve the processing performance, a coupling agent, a lubricant, a plasticizer and the like can be added into the film material.

The invention also discloses ink which comprises conventional ink components and the blue mechanoluminescence ceramic material powder, wherein the blue mechanoluminescence ceramic material powder is uniformly distributed in the conventional ink components, and the addition amount of the blue mechanoluminescence ceramic material powder is 1-30%; preferably 5 to 10%. The ink resin system may be polyamide, chlorinated polypropylene, polyurethane or acrylic. The ink may be either an oil-based ink or a water-based ink.

The invention also discloses a coating, which comprises conventional coating components and the blue mechanoluminescence ceramic material powder, wherein the blue mechanoluminescence ceramic material powder is uniformly distributed in the conventional coating components, and the addition amount of the blue mechanoluminescence ceramic material powder is 1-30%; preferably 5 to 10%. The coating resin system may be polyamide, chlorinated polypropylene, polyurethane or acrylic. The paint may be either an oil paint or a water paint.

Further, by forming a blue photoluminescent ceramic material on the outer surface of a general paper, synthetic paper, or a polymer material such as epoxy resin, polyethylene terephthalate, polyester, polypropylene, or polyvinyl chloride, natural rubber or synthetic rubber, glass, ceramic, metal, wood, artificial fiber or natural fiber, concrete, or a combination thereof, or a processed product thereof, or by incorporating a blue photoluminescent ceramic material inside, it is possible to detect an abnormality, or diagnose the deterioration of various structures or members by applying a shock wave (stress-strain detection, stress distribution measurement). For example, the following are: large structures such as buildings, viaducts, bridges, roads, rails, pillars, towers, pipelines, tunnels, floor materials, tiles, wall materials, prefabricated plate materials, paving materials, building materials such as wood, steel, and concrete, transmission members such as gears and cams, exterior parts or interior parts (engine parts, tires, belts, and the like) used in bicycles, automobiles, electric trains, ships, and airplanes, bearing parts, bearing retainers, and connecting parts such as bearings with optical sensors, screws, nuts, and washers, and the like. Further, as applications thereof, it is expected that: the leakage of the secondary battery of the non-aqueous electrolyte solution in which the electrolyte solution or the polymer electrolyte is injected is detected. Further, the internal stress distribution in the adhesive layer of the adhesive containing the blue mechanoluminescence ceramic material can be visualized, and the cracks in the adhesive can be grasped.

When the blue mechanoluminescence ceramic material is used as a stress light-emitting element, it can be used for electronic machines and apparatuses such as pressure-sensitive devices, touch panels, touch sensors, photodiodes or phototransistors, piezoelectric actuators or electrostatic actuators, light-emitting polymer actuators, liquid amount detecting devices, impact force detecting devices, optical waveguides, optical waveguide devices, mechano-optical devices, detecting devices, information processing devices, switches, operation buttons, input devices, keyboard input devices, etc., and can perform non-contact control, automation processes, and remote control operations of the apparatuses and systems. Examples thereof include: height measuring device for connection terminal of semiconductor component, cavitation generation amount measuring device, sound pressure intensity distribution and energy density distribution measuring device using ultrasonic wave for medical examination, stress/strain distribution measuring device acting on member such as living bone or bone-simulated implant, transmission cable, transmission device, laser processing device, device for detecting bending amount of steering shaft, radiation imaging device for specifying position of imaging part, parallelism inspecting device for flow velocity detector die press, solid-state imaging device capable of generating stress corresponding to thermal energy of infrared light and imaging, light emitting head for converting mechanical external force such as friction, shearing force, impact force, pressure into optical signal and transmitting, remote switch system using remote control mechanical device, light emitting head, and method for measuring sound pressure intensity distribution, A detection system for detecting a couple by the light emitting head, a detachable body detachably attached to a main body of various electric, electronic, and mechanical devices, for example, an ink cartridge of an ink jet printer, a detection device for detecting the attached state and the unattached state of a sheet cassette, and a detachable body; an imprint apparatus capable of inspecting the ultraviolet curable resin remaining in the uneven portion in a short time, an operation apparatus requiring no wiring, a small wireless light source (stress light emitting particle) capable of being introduced into a living body or in a dark place, an inspection apparatus provided with the same, an inspection method, a stress history recording system, and the like. In addition, it can also be used for: a gasket, a method for measuring the sealability of a seal, a ground contact surface shape of a tire, a ground contact pressure distribution, a dental occlusion force, a ground contact portion measuring tool of a tire, a method for measuring the amount of cavitation generated, and the like.

Can also be applied as a tactile sensor element. Examples thereof include: a human-coordinated robot, an artificial hand, an artificial finger, an artificial limb, a diagnostic palpator, a hardness/softness tester for various industries, and the like. Further, by measuring the emission energy generated by the action with the radiation, it is also possible to expect measurement of the amount of radiation exposure of the radiation and measurement of the distribution of the exposure intensity.

In addition to the above-described measuring device, the present invention can also be used as illumination and safety display. For example, the following are: lighting devices such as a vibration lamp and a wind power lamp; emergency, abnormal notification, emergency equipment, hazard display, emergency light, emergency sign, sign for life saving tool, signboard, display device; safety fences, tension ropes hung around factory buildings, animal guard rails; a step tread, a handrail, and a destination line body provided in a state of being half-buried in a road or the like; health equipment, walking aids (walking sticks for walking aids, light-emitting notification antennas, etc.); earrings, necklaces, and other jewelry; a pole for supporting a flag, a road-cutting rod of a road-cutting machine for a railway or the like, an exterior or interior member of a bicycle, an automobile, an electric car, a ship, an airplane or the like, a fishing tool (e.g., a lure, a fishing rod, a fishing net, etc.; a luminescent fiber structure, a luminescent fishing tool, a fishing line, a fishing net, etc.), a float (e.g., a float, a buoy); position display of pets such as humans, dogs, cats, and livestock such as cattle, pigs, sheep, and chickens; fans (blades of wind power generation, fan fans, etc.), clothing (shoes, sportswear, artificial lighting cloth, artificial lighting filaments, artificial lighting fibers, etc.); packages (boxes, holders, devices, envelopes, cardboard, outer skin packages, external coatings), medical articles (breathing aids, devices for experimental research), robots (artificial luminous hair structures, artificial luminous skin, artificial luminous body), and the like. Examples of applications in which the blue-colored photoluminescent ceramic material is contained in the coating composition, the ink composition, the adhesive, and the surface covering agent include: postal articles such as pressure-bonded postcard sheets containing a blue-color photoluminescent ceramic material as an adhesive used in financial institutions, public institutions, credit card companies, distribution industries, and the like; furniture such as chairs and beds; building materials such as flooring, tiles, wall materials, prefabricated plate materials, paving materials, wood, steel, concrete, and the like; an automatic navigation system device mounted on a vehicle; an operation device for operating an audio device, an air conditioner, and the like; input devices such as home electric appliances, portable devices, and electronic computers; digital cameras, CCD cameras, film, photo, image storage means, and the like.

Since a blue photoluminescent ceramic material can emit light to give a new appearance, the development of the material into amusement goods such as toys and event goods and living goods is also considered. Examples thereof include: dynamic toys, kites, carp-shaped banners and other wind banner, swings, fast scooters, hobbyhorses, arches and the like; a non-power type light emitting device (wind bell, etc.) that generates sound and light simultaneously by wind force. Luminescent balls (golf balls, baseball balls, table tennis balls, billiards balls, etc.), windmill with luminescent mechanism; a balloon; the sheet structure is paper, coiled flute, folded paper, paper balloon, folding fan, congratulation plate and picture book; sports goods (pole for pole jump, fencing, arrow and other long-sized objects); pressure sensitive sealing element for confirming golf club score, circuit tester for tennis court, dynamic decorative body, dynamic carving and dynamic memorial; a dynamic display device; an impact luminescent decorative device; acoustic devices such as speakers, musical instruments (stringed instruments such as violins and guitars, percussion instruments such as xylophones and drums, wind instruments such as trumpets and flute, diaphragms such as glass), tuning forks, and the like; entertainment goods such as event goods; aquatic plants and containers such as ornamental tanks for aquariums; a light emitting watch, a light emitting sand timer or a sand timer type light emitting device; a light-emitting type simulated candle device; an artificial plant capable of emitting light; an artificial eye; cosmetic compositions containing an adhesive polymer, printed matter and securities which can be visually recognized as counterfeit, printing inks containing stress-emitting particles, bills, checks, stocks, bonds, various securities, commodity tickets, graphics and coupons, tickets for transportation organizations, tickets for toll facilities, admission tickets for projects, lottery tickets, winning tickets for public sports competitions, banknotes, identification cards, tickets, passes and the like, printed matter of passports and written organic ciphertext books, sealing seals and the like.

The stress emitter-photocatalyst composite obtained by activating the photocatalyst attached to the surface of the blue mechanoluminescence-ceramic material by luminescence accompanied by stress can be used for: antibacterial, bactericidal, treatment of non-human animals, decontamination of dirt from antibacterial articles such as handrails and grips of vehicles, and decontamination by flow energy of fluid on the inner wall surface of piping or the like located in a dark place. The stress luminescent material can also promote crosslinking by activating a photocrosslinker in the polymer resin by luminescence.

The resin composition of the present invention can be formed by blending the blue mechanoluminescence ceramic material of the present invention into a resin.

In addition, the stress light-emitting body of the present invention can also be formed by adding another inorganic material or organic material to the resin composition of the present invention to form a composite material.

For example, when the resin is an epoxy resin, an acrylic resin, or the like, 1 to 200 parts by mass of the blue photoluminescent ceramic material is blended with 100 parts by mass of the resin, and when the resin is a polyethylene resin, a soft vinyl chloride resin, or the like, 30 to 300 parts by mass of the blue photoluminescent ceramic material is blended with 100 parts by mass of the resin. The compound can be used to prepare a resin composition by using a mixer such as a cone mixer, a V-type mixer, a ribbon mixer, a henschel mixer, a banbury mixer, or a three-roll mill.

When a stress light-emitting body is formed from the resin composition, for example, when a sheet-shaped stress light-emitting body is obtained, for example, 50 to 200 parts by mass of the blue-electroluminescence ceramic material, 3 to 5 parts by mass of a calcium-zinc stabilizer, and 30 to 100 parts by mass of dioctyl phthalate as a plasticizer are blended with 100 parts by mass of a polyvinyl chloride resin, and kneaded at 150 to 200 ℃ by a two-roll mill, whereby a flexible sheet-shaped stress light-emitting body can be obtained.

When a thin-film stress light-emitting body is obtained, for example, a thin-film stress light-emitting body can be obtained by blending 20 to 50 parts by mass of the blue-color mechanoluminescence ceramic material with 100 parts by mass of a polyethylene terephthalate resin, kneading the mixture at 250 to 300 ℃ by a twin-screw extruder or a blow-up machine, and molding the kneaded mixture.

When a stress light-emitting body having another shape is obtained, for example, a stress light-emitting body in a band shape, a plate shape, a rod shape, or a pellet shape can be obtained by mixing 5 to 100 parts by mass of a blue-based mechanoluminescence ceramic material with 100 parts by mass of a polypropylene resin, kneading the mixture at 170 to 200 ℃ by a twin-screw extruder, and molding the mixture. In addition, the granular stress luminophor is processed and molded at 170-200 ℃ by using an injection molding machine, so that the stress luminophor with a three-dimensional shape can be obtained.

When a mechanical external force is applied to the stressed light-emitting body, light is emitted due to mechanical deformation.

Examples of the resin or other organic material include: resins such as thermoplastic resins and thermosetting resins. Examples of the thermoplastic resin include: polyethylene such as low-density polyethylene, medium-density polyethylene, high-density polyethylene, and linear low-density polyethylene, styrene polymers or copolymers such as polypropylene, polystyrene, polyvinyl chloride, polyvinyl fluoride, polyvinylidene chloride, and acrylonitrile-butadiene-styrene copolymer (ABS resin), polyamides such as 6-nylon, 66-nylon, and 12-nylon, acrylic resins such as polyamideimide, polyimide, polyetherimide, polyurethane, and polymethyl methacrylate, acrylic resins such as polyvinyl acetate, ethylene-vinyl acetate copolymer, polyvinylidene fluoride, and polytetrafluoroethylene, fluorine resins such as alkenyl aromatic resins, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, and polyesters such as polylactic acid, polycarbonates such as bisphenol A-based polycarbonates, and the like, Polyacrylic acids such AS polyacetal, polyphenylene sulfide, polymethylpentene, cellulose, polyvinyl alcohol, polyvinyl acetate, polyacrylonitrile, styrene-acrylonitrile copolymers (AS resins), polyphenylene ether (PPE), modified PPE, polyarylate, polyphenylene sulfide, polysulfone, polyethersulfone, polyether nitrile, polyether ketone, polyketone, liquid crystal polymers, copolymers of ethylene and propylene, copolymers of ethylene or propylene with other α -olefins (1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, etc.), copolymers of ethylene with other ethylenically unsaturated monomers (vinyl acetate, acrylic acid ester, methacrylic acid ester, vinyl alcohol, etc.), and the like.

The thermoplastic resin may be used alone or in combination of 2 or more. When the thermoplastic resin is a copolymer, the thermoplastic resin may be a copolymer in any form such as a random copolymer or a block copolymer. Examples of the thermosetting resin include: phenol resins, urea resins, melamine resins, unsaturated polyester resins, diallyl phthalate resins, epoxy resins, silicone resins, alkyd resins, polyimides, polyaminobismaleimides, casein resins, furan resins, polyurethane resins, and the like. Further, there may be mentioned: resins cured by ultraviolet rays or radiation rays.

Further, there may be mentioned: rubber-based materials such as natural rubber, polyisoprene rubber, styrene-butadiene rubber, polybutadiene rubber, ethylene-propylene-diene rubber, butyl rubber, chloroprene rubber, acrylonitrile butadiene rubber, and silicone rubber.

In addition, a pigment, a dye, a lubricant, an antioxidant, an ultraviolet absorber, a light stabilizer, an antistatic agent, a flame retardant, a bactericide, an antibacterial agent, a curing catalyst, a photopolymerization initiator, and the like may be mixed with the blue mechanoluminescence ceramic material of the present invention and molded into an arbitrary shape such as a rod, a plate, a film, a fiber, a film, a needle, a sphere, a foil, a granule, a sand, a flake, a sheet, a liquid, a gel, a sol, a suspension, an aggregate, a capsule, and the like.

Examples of the pigment include inorganic pigments and organic pigments.

Examples of the inorganic pigment include: titanium oxide, barium sulfate, calcium carbonate, zinc oxide, lead sulfate, yellow lead, zinc yellow, carmine (red iron (III) oxide), cadmium red, ultramarine, chromium oxide green, cobalt green, ochre color, titanium black, synthetic iron black, carbon black, mica, alumina covered with titanium oxide, iron oxide, mica covered with titanium oxide, iron oxide, glass flake, holographic pigment, and the like. In addition, examples of the metal powder pigment include: aluminum powder, copper powder, stainless steel powder, metal colloid, transparent pearl mica having an interference action, colored mica, interference alumina, interference silica (interference glass), and the like.

Examples of the organic pigment include: azo pigments (monoazo yellow, condensed azo yellow, azomethine yellow, etc.), yellow pigments such as yellow iron oxide, titanium yellow, bismuth vanadate, benzimidazolone, isoindolinone, isoindoline, quinophthalone, benzidine yellow, permanent yellow, etc.; orange pigments such as permanent orange; red pigments such AS red iron oxide, naphthol AS-based azo reds, anthanthrone, anthraquinone reds, pyrene reddish brown, quinacridone reds, diketopyrrolopyrrole reds, permanent reds, and the like; violet pigments such as cobalt violet, quinacridone violet, and dioxazine violet; blue pigments such as cobalt blue, phthalocyanine-based pigments (such as phthalocyanine blue), and anthracene blue; green pigments such as phthalocyanine green, and organic dyes such as azo-based disperse dyes and anthraquinone-based disperse dyes.

Examples of the dye include: azo dyes, anthraquinone dyes, indigo dyes, sulfur dyes, triphenylmethane dyes, pyrazolone dyes, stilbene dyes, diphenylmethane dyes, xanthene dyes, alizarin dyes, acridine dyes, quinonimine dyes (oxazine dyes, thiazine dyes), thiazole dyes, alkyne dyes, nitro dyes, nitroso dyes, and the like.

Examples of the antioxidant include: hindered phenol compounds, phosphite compounds, phosphonite compounds, thioether compounds, and the like.

Examples of the hindered phenol compound include: alpha-tocopherol, butylhydroxytoluene, sinapyl alcohol, vitamin E, N-octadecyl-beta- (4 '-hydroxy-3', 5 '-di-tert-butylphenyl) propionate, 2-tert-butyl-6- (3' -tert-butyl-5 '-methyl-2' -hydroxybenzyl) -4-methylphenyl acrylate, 2, 6-di-tert-butyl-4- (N, N-dimethylaminomethyl) phenol, diethyl 3, 5-di-tert-butyl-4-hydroxybenzylphosphonate, 2 '-methylenebis (4-methyl-6-tert-butylphenol), 2' -methylenebis (4-ethyl-6-tert-butylphenol), 4,4 '-methylenebis (2, 6-di-tert-butylphenol), 2' -methylenebis (4-methyl-6-cyclohexylphenol), 2 '-dimethylene-bis (6-. alpha. -methyl-benzyl-p-cresol) 2, 2' -ethylidene-bis (4, 6-di-tert-butylphenol), 2 '-butylidene-bis (4-methyl-6-tert-butylphenol), 4' -butylidene-bis (3-methyl-6-tert-butylphenol), triethylene glycol-N-bis-3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate, 1, 6-hexanediol bis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], bis [ 2-tert-butyl-4-methyl-6- (3-tert-butyl-5-methyl-2-hydroxybenzyl) phenyl ] terephthalate, 3, 9-bis {2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy ] -1, 1-dimethylethyl } -2,4,8, 10-tetraoxaspiro [5,5] undecane, 4 ' -thiobis (6-tert-butyl-m-cresol), 4 ' -thiobis (3-methyl-6-tert-butylphenol), 2 ' -thiobis (4-methyl-6-tert-butylphenol) Bis (3, 5-di-tert-butyl-4-hydroxybenzyl) sulfide, 4 ' -dithiobis (2, 6-di-tert-butylphenol), 4 ' -trithiobis (2, 6-di-tert-butylphenol), 2-thiodiethylene bis- [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], 2, 4-bis (N-octylthio) -6- (4-hydroxy-3 ', 5 ' -di-tert-butylanilino) -1,3, 5-triazine, N ' -hexamethylenebis- (3, 5-di-tert-butyl-4-hydroxyhydrocinnamide), N ' -bis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl ] hydrazine, N ' -bis (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl ] hydrazine, 1,1, 3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3, 5-trimethyl-2, 4, 6-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) benzene, tris (3, 5-di-tert-butyl-4-hydroxyphenyl) isocyanurate, tris (3, 5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3, 5-tris (4-tert-butyl-3-hydroxy-2, 6-dimethylbenzyl) isocyanurate, 1,3, 5-tris 2[3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyloxy ] ethyl isocyanurate and tetrakis [ methylene-3- (3', 5' -di-t-butyl-4-hydroxyphenyl) propionate ] methane, and the like.

Examples of the phosphite-based compound include triphenyl phosphite, tris (nonylphenyl) phosphite, tridecyl phosphite, trioctyl phosphite, trioctadecyl phosphite, didecylmonophenyl phosphite, dioctylmonophenyl phosphite, diisopropyl monophenyl phosphite, monobutyldiphenyl phosphite, monodecyl diphenyl phosphite, monooctyldiphenyl phosphite, tris (diethylphenyl) phosphite, tris (diisopropylphenyl) phosphite, tris (di-n-butylphenyl) phosphite, tris (2, 4-di-t-butylphenyl) phosphite, tris (2, 6-di-t-butylphenyl) phosphite, distearylpentaerythritol diphosphite, bis (2, 4-di-t-butylphenyl) pentaerythritol diphosphite, bis (2, 6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite, Bis (2, 6-di-t-butyl-4-ethylphenyl) pentaerythritol diphosphite, bis {2, 4-bis (1-methyl-1-phenylethyl) phenyl } pentaerythritol diphosphite, phenyl bisphenol a pentaerythritol diphosphite, bis (nonylphenyl) pentaerythritol diphosphite, dicyclohexylpentaerythritol diphosphite and the like. Examples of the phosphite ester compound include phosphite ester compounds having a cyclic structure obtained by reacting a diphenol with the phosphite ester compound.

Examples of the phosphonite-based compound include: tetrakis (2, 4-di-tert-butylphenyl) -4,4 '-biphenylene diphosphonite, tetrakis (2, 4-di-tert-butylphenyl) -4, 3' -biphenylene diphosphonite, tetrakis (2, 4-di-tert-butylphenyl) -3,3 '-biphenylene diphosphonite, tetrakis (2, 6-di-tert-butylphenyl) -4, 4' -biphenylene diphosphonite, tetrakis (2, 6-di-tert-butylphenyl) -4,3 '-biphenylene diphosphonite, tetrakis (2, 6-di-tert-butylphenyl) -3, 3' -biphenylene diphosphonite, bis (2, 4-di-tert-butylphenyl) -4-phenyl phosphonite, bis (2, 4-di-tert-butylphenyl) -3-phenyl phosphonite, bis (2, 4-di-tert-butylphenyl) -3, Bis (2, 6-di-n-butylphenyl) -3-phenyl-phenylphosphonite, bis (2, 6-di-tert-butylphenyl) -4-phenyl-phenylphosphonite, bis (2, 6-di-tert-butylphenyl) -3-phenyl-phenylphosphonite and the like.

Examples of the thioether-based compound include: dilauryl thiodipropionate, ditridecyl thiodipropionate, dimyristyl thiodipropionate, distearyl thiodipropionate, pentaerythritol-tetrakis (3-laurylthiopropionate), pentaerythritol-tetrakis (3-octadecylthiopropionate), pentaerythritol-tetrakis (3-myristylthiopropionate), pentaerythritol-tetrakis (3-stearylthiopropionate), and the like. Examples of the light stabilizer containing an ultraviolet absorber include: benzophenone-based compounds, benzotriazole-based compounds, aromatic benzoate-based compounds, oxalanilide-based compounds, cyanoacrylate-based compounds, hindered amine-based compounds, and the like.

Examples of the benzophenone-based compound include: benzophenone, 2, 4-dihydroxybenzophenone, 2 ', 4,4 ' -tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2 ' -dihydroxy-4, 4 ' -dimethoxybenzophenone, 2 ' -dihydroxy-4, 4 ' -dimethoxy-5-sulfonylbenzophenone, 2-hydroxy-4-octyloxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, 2-hydroxy-4-octyloxybenzophenone, 2-hydroxy-4-methoxy-5-sulfonylbenzophenone, 5-chloro-2-hydroxybenzophenone, 2,4 ' -dihydroxybenzophenone, 2 ' -dihydroxy-4-octyloxybenzophenone, 5-chloro-2-hydroxybenzophenone, 2 ' -hydroxy-4-methoxy-5-sulfonylbenzophenone, a, 2-hydroxy-4-octyloxybenzophenone, 2-hydroxy-4-methoxy-2' -carboxybenzophenone, and 2-hydroxy-4- (2-hydroxy-3-methyl-acryloyloxy-isopropoxy) benzophenone, and the like.

Examples of the benzotriazole-based compound include: 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- (3, 5-di-tert-butyl-2-hydroxyphenyl) benzotriazole, 2- (3, 5-di-tert-amyl-2-hydroxyphenyl) benzotriazole, 2- (3 ', 5 ' -di-tert-butyl-4 ' -methyl-2 ' -hydroxyphenyl) benzotriazole, 2- (3, 5-di-tert-amyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (5-tert-butyl-2-hydroxyphenyl) benzotriazole, 2- [2 ' -hydroxy-3 ', 5 ' -bis (alpha, alpha-dimethylbenzyl) phenyl ] benzotriazole, 2- [2 ' -hydroxy-3 ', 5 ' -bis (. alpha.,. alpha. -dimethylbenzyl) phenyl ] -2H-benzotriazole, 2- (4 ' -octyloxy-2 ' -hydroxyphenyl) benzotriazole and the like.

Examples of the aromatic benzoate-based compound include: and alkylphenyl salicylates such as p-tert-butylphenyl salicylate and p-octylphenyl salicylate.

Examples of the oxalanilide compound include: 2-ethoxy-2 ' -ethyloxanilide, 2-ethoxy-5-tert-butyl-2 ' -ethyloxanilide, 2-ethoxy-3 ' -dodecyloxanilide, and the like.

Examples of the cyanoacrylate-based compound include: ethyl-2-cyano-3, 3 '-diphenylacrylate, 2-ethylhexyl-cyano-3, 3' -diphenylacrylate, and the like.

Examples of the hindered amine compound include: 4-acetoxy-2, 2,6, 6-tetramethylpiperidine, 4-stearoyloxy-2, 2,6, 6-tetramethylpiperidine, 4-acryloyloxy-2, 2,6, 6-tetramethylpiperidine, 4- (phenylacetoxy) -2,2,6, 6-tetramethylpiperidine, 4-benzoyloxy-2, 2,6, 6-tetramethylpiperidine, 4-methoxy-2, 2,6, 6-tetramethylpiperidine, 4-octadecyloxy-2, 2,6, 6-tetramethylpiperidine, 4-cyclohexyloxy-2, 2,6, 6-tetramethylpiperidine, 4-benzyloxy-2, 2,6, 6-tetramethylpiperidine, 4-phenoxy-2, 2,6, 6-tetramethylpiperidine, 4- (ethylcarbamoyloxy) -2,2,6, 6-tetramethylpiperidine, 4- (cyclohexylcarbamoyloxy) -2,2,6, 6-tetramethylpiperidine, 4- (phenylcarbamoyloxy) -2,2,6, 6-tetramethylpiperidine, bis (2,2,6, 6-tetramethyl-4-piperidyl) carbonate, bis (2,2,6, 6-tetramethyl-4-piperidyl) oxalate, bis (2,2,6, 6-tetramethyl-4-piperidyl) malonate, bis (2,2,6, 6-tetramethyl-4-piperidyl) sebacate, bis (2,2,6, 6-tetramethyl-4-piperidyl) adipate, Bis (2,2,6, 6-tetramethyl-4-piperidyl) terephthalate, 1, 2-bis (2,2,6, 6-tetramethyl-4-piperidyloxy) -ethane, α' -bis (2,2,6, 6-tetramethyl-4-piperidyloxy) -p-xylene, bis (2,2,6, 6-tetramethyl-4-piperidyl) -toluylene-2, 4-dicarbamate, bis (2,2,6, 6-tetramethyl-4-piperidyl) -hexamethylene-1, 6-dicarbamate, tris (2,2,6, 6-tetramethyl-4-piperidyl) -benzene-1, 3, 5-tricarboxylate, di (tert-butyl-ethyl-2, 6, 6-tetramethyl-4-piperid, Tris (2,2,6, 6-tetramethyl-4-piperidyl) -benzene-1, 3, 4-tricarboxylate, 1,2- {3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyloxy } -2,2,6, 6-tetramethylpiperidine, and a condensate of 1,2,3, 4-butanetetracarboxylic acid and 1,2,2,6, 6-pentamethyl-4-hydroxypiperidine and β, β, β ', β' -tetramethyl-3, 9- [2,4,8, 10-tetraoxaspiro (5,5) undecane ] dimethanol, and the like.

Examples of the antistatic agent include: carbon powder such as carbon black and graphite, tin-antimony composite oxide, antimony-indium-tin composite oxide, conductive indium oxide doped with Sn, F, Cl, etc., metal oxide such as tin oxide, zinc oxide, etc., inorganic antistatic agents such as various metal particles (powder) or metal fibers of copper, nickel, silver, gold, aluminum, etc., and organic antistatic agents such as quaternary ammonium salts, sulfonate compounds, alkyl phosphate compounds, etc. (β -lauroyl propionyl) trimethylammonium sulfate, sodium dodecylbenzenesulfonate, etc.

Examples of the flame retardant include: bromine flame retardants, phosphorus flame retardants, chlorine flame retardants, triazine flame retardants, and salts of phosphoric acid and piperazine.

Examples of the bromine-based flame retardant include: brominated polystyrene, brominated polyacrylate, brominated polyphenylene oxide, brominated bisphenol a epoxy resin, a modified product in which a part or all of glycidyl groups at molecular chain terminals of brominated bisphenol a epoxy resin are capped, a polycarbonate oligomer synthesized from brominated bisphenol a as a raw material, a brominated diphenylene compound such as brominated bis-phthalimide compound, brominated diphenyl ether, and 1, 2-bis (pentabromophenyl) ethane, and the like. Among them, there are: brominated polystyrene such as polytribromostyrene, poly (dibromophenylene ether), decabromodiphenyl ether, bis (tribromophenoxy) ethane, 1, 2-bis (pentabromophenyl) ethane, ethylene-bis- (tetrabromophthalimide), tetrabromobisphenol A, brominated polycarbonate oligomer, brominated polystyrene such as polytribromostyrene, and 1, 2-bis (pentabromophenyl) ethane.

Examples of the phosphorus-based flame retardant include: trimethyl phosphate, triethyl phosphate, tributyl phosphate, tris (2-ethylhexyl) phosphate, tributoxyethyl phosphate, triphenyl phosphate, tricresyl phosphate, trixylyl phosphate, tri (isopropylphenyl) phosphate, tris (phenylphenyl) phosphate, trinaphthyl phosphate, tolyldiphenyl phosphate, ditolyl diphenyl phosphate, diphenyl (2-ethylhexyl) phosphate, di (isopropylphenyl) phenyl phosphate, monoisodecyl phosphate, 2-acryloyloxyethyl acid phosphate, 2-methacryloyloxyethyl acid phosphate, diphenyl-2-acryloyloxyethyl phosphate, diphenyl-2-methacryloyloxyethyl phosphate, melamine phosphate, di (melamine) phosphate, melamine pyrophosphate, methyl ethyl phosphate, methyl propyl phosphate, And condensed phosphates such as triphenylphosphine oxide, tricresylphosphine oxide, diphenyl methanephosphonate, diethyl phenylphosphonate and the like, resorcinol polyphenyl phosphate, 1, 3-phenylene bis (2, 6-dimethylphenyl phosphate), resorcinol poly (di-2, 6-xylyl) phosphate, bisphenol a polytoluene phosphate, bisphenol a polyphenyl phosphate, hydroquinone poly (2, 6-xylyl) phosphate, and aromatic condensed phosphates such as condensates thereof.

Examples of the chlorine-based flame retardant include: pentachloropentadecane, hexachlorobenzene, pentachlorotoluene, tetrachlorobisphenol A, polychlorostyrene, and the like. Examples of triazine flame retardants include: melamine, methylguanamine, benzoguanamine, acrylylylylguanamine, 2, 4-diamino-6-nonyl-1, 3, 5-triazine, 2, 4-diamino-6-hydroxy-1, 3, 5-triazine, 2-amino-4, 6-dihydroxy-1, 3, 5-triazine, 2, 4-diamino-6-methoxy-1, 3, 5-triazine, 2, 4-diamino-6-ethoxy-1, 3, 5-triazine, 2, 4-diamino-6-propoxy-1, 3, 5-triazine, 2, 4-diamino-6-isopropoxy-1, 3, 5-triazine, 2, 4-diamino-6-mercapto-1, 3, 5-triazine and 2-amino-4, 6-dimercapto-1, 3, 5-triazine.

Examples of the salt of phosphoric acid and piperazine include: piperazine orthophosphate, piperazine pyrophosphate, piperazine polyphosphate, and the like.

Examples of the inorganic flame retardant include: antimony compounds such as antimony trioxide and antimony pentachloride, zinc borate, sodium borate, aluminum hydroxide, magnesium hydroxide, red phosphorus, and the like.

Examples of the bactericide include: copper fungicides such as oxine-copper, organic chlorine fungicides such as Zineb (Zineb) and Maneb (Maneb), organic chlorine fungicides such as captan and chlorothalonil, benzimidazole fungicides such as thiophanate-methyl, beneste, carbendazim and thiabendazole, dicarboximide fungicides such as iprodione, vinclozolin and procymidone, amide fungicides such as furametpyr, phenylpyrrole fungicides such as fludioxonil, morpholine fungicides such as dimethomorph, strobilurin fungicides such as oribiright, anilinopyrimidine fungicides such as mepanid and pyrimethanil, ergosterol biosynthesis inhibitors such as triadimefon and triflumizole, soil fungicides such as trichloronitromethane and PCNB, fluazinam, o-phenylphenol (OPP), diphenyl, chlorodiphenyl, cresol, 1, 2-bis (bromoacetoxy) ethane, captan, chlorothalonil, and mepiquat, Cinnamaldehyde, phenyl acetate, allyl isothiocyanate, α -methylacetophenone, thymol, perchlorocyclopentadiene, bromoacetic acid, 2-dibromo-3-nitrilopropionamide, ethyl chloroacetate, butyl chloroacetate, methyl chloroacetate, 5-chloro-2-methylisothiazolin-3-one, glutaraldehyde, hinokitiol, and the like.

Examples of the antibacterial agent include: an inorganic powder obtained by supporting an inorganic compound with one or more than 2 antibacterial metals of silver, zinc and copper. Examples of the carrier include: zeolites, apatites, zirconium phosphates, titanium oxides, silica gels, aluminum sulfate hydroxides, calcium phosphates, calcium silicates, and the like. Further, there can be mentioned: an antibacterial glass powder obtained by adding one or more than 2 antibacterial metals of silver, zinc and copper to glass which is composed of one or more than 2 kinds of phosphoric, boric and silicic acid glasses.

Examples of the lubricant include: fatty acids, fatty acid metal salts, oxofatty acids, paraffins, low molecular weight polyolefins, fatty amides, alkylenebis fatty amides, fatty ketones, partially saponified esters of fatty acids, fatty acid lower alcohol esters, fatty acid polyol esters, fatty acid polyethylene esters, modified silicones, and the like.

Examples of the fatty acid include: and fatty acids having 6 to 40 carbon atoms such as oleic acid, stearic acid, lauric acid, hydroxystearic acid, behenic acid, arachidonic acid, linoleic acid, linolenic acid, ricinoleic acid, palmitic acid, montanic acid, and mixtures thereof. Examples of the fatty acid metal salt include: alkali (earth) metal salts of fatty acids having 6 to 40 carbon atoms such as sodium laurate, potassium laurate, magnesium laurate, calcium laurate, zinc laurate, sodium stearate, potassium stearate, magnesium stearate, calcium stearate, zinc stearate, barium stearate, sodium behenate, potassium behenate, magnesium behenate, calcium behenate, zinc behenate, barium behenate, sodium montanate, and calcium montanate.

Examples of the oxofatty acid include: 1, 2-oxostearic acid, and the like.

Examples of the paraffin wax include: liquid paraffin, natural paraffin, microcrystalline wax and vaseline with carbon number of more than 18.

Examples of the low-molecular-weight polyolefin include: polyolefin having a molecular weight of 5000 or less, such as polyethylene wax, maleic acid-modified polyethylene wax, oxidized polyethylene wax, chlorinated polyethylene wax, and polypropylene wax. Specific examples of the fatty amide include: fatty amides having 6 or more carbon atoms such as oleamide, erucamide, and behenamide.

Examples of the alkylene bis-fatty amide include: alkylene bis fatty amides having 6 or more carbon atoms such as methylene bis stearamide, ethylene bis stearamide and N, N-bis (2-hydroxyethyl) stearamide.

Examples of the aliphatic ketone include: aliphatic ketones having 6 or more carbon atoms such as higher aliphatic ketones. Examples of the partially saponified fatty acid ester include: partially saponified montanic acid ester, and the like.

Examples of the fatty acid lower alcohol ester include: stearate, oleate, linoleate, linolenate, adipate, behenate, arachidonate, montanate, isostearate and the like.

As the fatty acid polyol ester, there may be mentioned: glycerol tristearate, glycerol distearate, glycerol monostearate, pentaerythritol tetrastearate, pentaerythritol tristearate, pentaerythritol dimyristate, pentaerythritol monostearate, pentaerythritol adipate stearate, sorbitan monobehenate, and the like.

Examples of the fatty acid polyglycol ester include: polyethylene glycol fatty acid esters, polytrimethylene glycol fatty acid esters, polypropylene glycol fatty acid esters, and the like.

Examples of the modified silicone include: polyether-modified silicone, higher fatty acid alkoxy-modified silicone, silicone containing higher fatty acid, higher fatty acid ester-modified silicone, methacrylic acid-modified silicone, fluorine-modified silicone, and the like.

Examples of the curing catalyst include: organic peroxides such as t-butyl peroxybenzoate, benzoyl peroxide, methyl ethyl ketone peroxide, and azo compounds such as azobisisobutyronitrile and azobisisovaleronitrile, tin octylate, dibutyltin bis (2-ethylhexanoate), dioctyltin diacetate, dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin oxide, dioctyltin oxide, dibutyltin fatty acid salts, lead 2-ethylhexanoate, zinc octylate, zinc naphthenate, zinc fatty acid salts, cobalt naphthenate, calcium octylate, copper naphthenate, lead 2-ethylhexanoate, lead octylate, and tetra-n-butyltitanate, and organic metal derivatives such as salts of metals with organic and inorganic acids, such as hydrochloric acid, nitric acid, sulfuric acid, and other inorganic acids, p-toluenesulfonic acid, dodecylbenzenesulfonic acid, dinonylnaphthalenesulfonic acid, and other acids, and salts of organic and inorganic acids such as p-toluenesulfonic acid, dodecylbenzenesulfonic acid, dinonylnaphthalenesulfonic acid, and other salts, Sulfonic acid compounds such as dinonylnaphthalene disulfonic acid, amine-neutralized products of sulfonic acid compounds, organic amines such as triethylamine, phosphoric acid, pyrophosphoric acid, phosphoric monoesters or phosphoric diesters, and the like. Examples of the phosphoric monoester include: mono octyl phosphate, mono propyl phosphate, mono lauryl phosphate, and the like. Examples of the phosphoric acid diester include: dioctyl phosphate, dipropyl phosphate, dilauryl phosphate, and the like. Further, there may be mentioned: phosphoric acid compounds such as mono (2- (meth) acryloyloxyethyl) acid phosphate, diazabicycloundecene-based catalysts, lewis acids, acid anhydrides, and the like.

Examples of the photopolymerization initiator include: hydroxybenzoyl compounds (2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, benzoin alkyl ether, etc.), benzoyl formate compounds (methyl benzoyl formate, etc.), thioxanthone compounds (isopropyl thioxanthone, etc.), benzophenone compounds (benzophenone, etc.), phosphate ester compounds (1,3, 5-trimethylbenzoyldiphenylphosphine oxide, etc.), benzil dimethyl ketal, and the like.

Further, the stress-luminescent coating composition of the present invention can be produced by blending the blue-photoluminescent ceramic material of the present invention with a coating material.

The stress luminescence coating composition of the present invention can be applied to the surface of other materials, and when a mechanical external force is applied to the material coated with the luminescent material, the luminescent material layer on the surface of the material emits light due to deformation.

Further, the luminescent coating composition of the present invention containing the blue photoluminescent ceramic material of the present invention has high luminescent brightness, and therefore can be coated with high visibility.

As the coating composition, a coating composition containing a film-forming resin can be used. The coating composition may contain, as necessary: a solvent, a dispersant, a filler, a thickener, a leveling agent, a curing agent, a crosslinking agent, a pigment, an antifoaming agent, an antioxidant, a light stabilizer including an ultraviolet absorber, a flame retardant, a curing catalyst, a bactericide, an antibacterial agent, and other additives for coating materials.

As the material used in the coating composition, various resins such as a thermosetting resin, a room temperature curable resin, an ultraviolet curable resin, and a radiation curable resin can be used, and examples thereof include: acrylic resins, alkyd resins, polyurethane resins, polyester resins, amino resins and the like, organosilicates, organotitanates and the like.

Examples of the ink film forming material include: polyurethane resins, acrylic resins, polyamide resins, vinyl chloride-vinyl acetate resins, chlorinated acrylic resins, and the like.

Examples of the solvent include: aliphatic hydrocarbons, aromatic hydrocarbons (C7-10, such as toluene, xylene, and ethylbenzene), esters or ether esters (C4-10, such as methoxybutylacetate), ethers (C4-10, such as tetrahydrofuran, monoethyl ether of EG, monobutyl ether of EG, monomethyl ether of PG, and monoethyl ether of DEG), ketones (C3-10, such as methyl isobutyl ketone, di-N-butyl ketone), alcohols (C1-10, such as methanol, ethanol, N-propanol, and isopropanol, N-butanol, isobutanol, sec-butanol, and tert-butanol, and 2-ethylhexyl alcohol), amides (C3-6, such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone), sulfoxides (C2-4, such as dimethyl sulfoxide), and mixed solvents of 2 or more thereof, water, or the mixed solvents thereof. The dispersant may be a polymer dispersant, and examples thereof include: formalin condensates of naphthalenesulfonates [ alkali metal (Na, K, etc.) salts, ammonium salts, etc. ], polystyrene sulfonates (the same as those described above), polyacrylates (the same as those described above), salts of poly (2-4) carboxylic acids (maleic acid/glycerin/monoallyl ether copolymers, etc.) (the same as those described above), carboxymethylcellulose (Mn 2000-10000), polyvinyl alcohol (Mn 2000-100000), and the like.

Examples of the low-molecular-weight dispersant include the following.

(1) Polyoxyalkylene type

1 to 30 mol adduct of aliphatic alcohol (C4 to 30), alkyl (C1 to 30) phenol, aliphatic (C4 to 30) amine and aliphatic (C4 to 30) amide AO (C2 to 4).

As the aliphatic alcohol, there are n-butanol, isobutanol, sec-butanol, tert-butanol, octanol, dodecanol, etc.; as the (alkyl) phenol, there are phenol, methylphenol, nonylphenol and the like; as the aliphatic amine, lauryl amine, methyl stearyl amine, and the like; and as the aliphatic amide, stearamide and the like are mentioned.

(2) Polyhydric alcohol type

Monoester compounds of C4-30 fatty acids (such as lauric acid and stearic acid) and polyhydric (2-6 or more) alcohols (such as GR, PE, sorbitol and sorbitan).

(3) Carboxylate salt form

An alkali metal salt (same as above) of a fatty acid (same as above) having C4-30.

(4) Sulfuric acid ester type

And alkali metal sulfates (same as above) of 1 to 30 mol adducts of aliphatic alcohols (same as above) and aliphatic alcohols AO (C2 to 4) of C4 to 30.

(5) Sulfonate type

[ alkyl (C1-30) ] phenol (the same as above) sulfonic acid alkali metal (the same as above) salt.

(6) Phosphoric ester type

Salts of monophosphoric acid esters or diphosphoric acid esters of 1 to 30 mol adducts of aliphatic alcohols (same as described above) having 4 to 30 mol adducts with AO (C2 to 4) of aliphatic alcohols [ alkali metal salts (same as described above), quaternary ammonium salts, etc. ].

(7) Primary to tertiary amine salt forms

Salts of aliphatic amines [ primary amines (e.g., laurylamine), secondary amines (e.g., dibutylamine), and tertiary amines (e.g., dimethylstearylamine) ] hydrochloride of C4 to 30 and inorganic acids (e.g., hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid) of monoesters of triethanolamine and fatty acids (the same as described above) of C4 to 30.

(8) Quaternary ammonium salt type

And inorganic acid (same as above) salts of C4-30 quaternary ammonium (such as butyltrimethylammonium, diethyllaurylmethylammonium, and dimethyldistearylammonium).

Examples of the inorganic dispersant include: alkali metal (same as above) salts of polyphosphoric acid, phosphoric acid-based dispersants (phosphoric acid, monoalkyl phosphate esters, dialkyl phosphate esters, and the like), and the like.

Examples of the filler include: fine powders of inorganic oxides such as silica, alumina, zirconia and mica, fine powders of inorganic non-oxides such as silicon carbide and silicon nitride, and organic compounds such as acrylic resins and fluororesins. Further, metal powder such as aluminum, zinc, and copper may be added according to the application. Further, specific examples of the filler include: sols such as silica sol, zirconia sol, alumina sol, and titania sol; silica-based materials such as silica sand, quartz, dense quartz salt, diatomaceous earth, and the like; synthesizing amorphous silicon dioxide; silicates such as kaolinite, mica, talc, wollastonite, asbestos, calcium silicate, and aluminum silicate; glass bodies such as glass powder, glass spheres, hollow glass spheres, glass flakes, foam glass spheres and the like; non-oxide inorganic substances such as boron nitride, boron carbide, aluminum nitride, aluminum carbide, silicon nitride, silicon carbide, titanium boride, titanium nitride, and titanium carbide; calcium carbonate; metal oxides such as zinc oxide, aluminum oxide, magnesium oxide, titanium oxide, and beryllium oxide: inorganic substances such as barium sulfate, molybdenum disulfide, tungsten disulfide, carbon fluoride and the like; metal powders of aluminum, bronze, lead, stainless steel, zinc, etc.; and carbon bodies such as carbon black, coke, graphite, pyrolytic carbon, hollow carbon spheres, and the like.

Examples of the thickener include: montmorillonite clay mineral, bentonite containing these minerals, inorganic filler thickeners such as colloidal alumina, cellulose thickeners such as methylcellulose, carboxymethylcellulose, hexylmethylcellulose, hydroxyethylcellulose and hydroxypropylcellulose, polyethylene thickeners such as polyurethane resin thickeners, polyvinyl alcohol, polyvinylpyrrolidone and polyvinyl benzyl ether copolymers, polyether resin thickeners such as polyether dialkyl esters, polyether dialkyl ethers and polyether epoxy modified products, associative thickeners such as urethane modified polyethers, special polymer nonionic thickeners such as polyether polyol polyurethane resin, surfactant thickeners such as nonionic surfactants, protein thickeners such as casein, sodium caseinate and ammonium caseinate, and acrylic thickeners such as sodium alginate.

Examples of the leveling agent include: PEG-type nonionic surfactants (nonylphenol EO 1-40 mol adduct, stearic acid EO 1-40 mol adduct, etc.), polyol-type nonionic surfactants (sorbitan palmitate monoester, sorbitan stearate triester, etc.), fluorine-containing surfactants (perfluoroalkyl EO 1-50 mol adduct, perfluoroalkyl carboxylate, perfluoroalkyl betaine, etc.), and modified silicone oils [ polyether-modified silicone oil, (meth) acrylate-modified silicone oil, etc. ].

Examples of the curing agent include polyol-based curing agents: isocyanates curable at ordinary temperature, such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, isophorone diisocyanate, hydrogenated diphenylmethane diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, tolylene diisocyanate, hydrogenated tolylene diisocyanate, lysine diisocyanate, nurate products of polyisocyanate compounds, buret products, adducts of polyisocyanate compounds with a polyol such as ethylene glycol, propylene glycol or trimethylolpropane, blocked polyisocyanate curing agents, or other monomers or mixtures of 2 or more types thereof, polyol adducts thereof, copolymers thereof, and block polymers thereof. Examples of the curing agent for epoxy resins include: acid anhydrides, phenol resins, polyamide resins, amine adducts, urea resins, melamine resins, isocyanates, and the like.

Examples of the crosslinking agent include: melamine resin, urea resin, polyisocyanate compound, blocked polyisocyanate compound, epoxy compound or resin, carboxyl group-containing compound or resin, acid anhydride, alkoxysilyl group-containing compound or resin, and a compound having a hydroxymethyl group, a methoxymethyl group, an ethoxymethyl group or the like, such as hexamethoxymethylated melamine, N' -tetrahydroxymethylsuccinamide, tetramethoxymethylated urea, 2,4, 6-tetrahydroxymethylated phenol.

Examples of the pigment include, in addition to the above pigments: vanadium compounds such as vanadium pentoxide, calcium vanadate, magnesium vanadate, and ammonium metavanadate; phosphate-based anticorrosive pigments such as magnesium phosphate, magnesium ammonium phosphate eutectoid, magnesium monohydrogen phosphate, magnesium dihydrogen phosphate, magnesium calcium phosphate eutectoid, magnesium cobalt phosphate eutectoid, magnesium nickel phosphate eutectoid, magnesium phosphite, magnesium calcium phosphite eutectoid, aluminum dihydrogen tripolyphosphate, magnesium oxide-treated products of aluminum dihydrogen tripolyphosphate, magnesium oxide-treated products of zinc dihydrogen tripolyphosphate, and magnesium phosphate-containing compounds such as magnesium phosphate-modified compounds of magnesium phosphate such as silica-modified magnesium phosphate; zinc-free rust preventive pigments such as zinc phosphate-containing rust preventive pigments, magnesium-treated aluminum dihydrogen tripolyphosphate, and calcium-treated calcium phosphate; calcium silicate such as calcium silicate complex containing calcium metasilicate component or calcium metasilicate component; metal ion-exchanged silica such as calcium ion-exchanged silica and magnesium ion-exchanged silica; and rust preventive pigments containing hexavalent chromium, lead, and the like.

Examples of the defoaming agent include: silicone defoaming agents such as silicone oil, dimethylpolysiloxane, organomodified polysiloxane, and fluorine-modified polysiloxane, mineral oil defoaming agents, non-silicone/polymer defoaming agents, defoaming agents containing at least 1 selected from the group consisting of organically modified fluorine compounds and polyoxyalkylene compounds, and defoaming agents containing aliphatic alcohols having 18 or more carbon atoms.

The antioxidant, light stabilizer including ultraviolet absorber, flame retardant, curing catalyst, bactericide, antibacterial agent and the like can be exemplified by those mentioned above.

Drawings

FIG. 1 is a chart of the mechanoluminescence spectra of the samples of examples 1-2 and comparative example 1 provided by the present invention.

FIG. 2 is a graph showing the relationship between the relative luminance and the pressure for the samples of examples 3-4 provided by the present invention.

FIG. 3 is a mechanoluminescence spectrum of the samples of examples 5 to 6 provided by the present invention, and the test pressure is 20 MPa.

FIG. 4 is a graph showing the relationship between the relative luminance and the magnitude of the pressure for the samples of examples 1 to 6 according to the present invention.

Detailed Description

The invention will be described in further detail below with reference to the accompanying figures 1-4 and specific examples.

Example 1

A blue-color mechanoluminescence ceramic material having a chemical composition of Ca_0.98Al₃O₄N: 0.01Eu²⁺, 0.01Nd³⁺。

As high purity CaCO₃、Al₂O₃、AlN、Eu₂O₃And Nd₂O₃As a raw material, Ca in accordance with the chemical composition_0.98Al₃O₄N: 0.01Eu²⁺, 0.01Nd³⁺The raw materials are accurately weighed according to the proportion of the elements in the raw materials; the method comprises the following steps of taking agate balls as grinding balls, taking absolute ethyl alcohol as a ball milling medium, simultaneously putting the agate balls, the absolute ethyl alcohol and raw materials into a ball milling tank, and carrying out ball milling and mixing on a planetary ball mill for 5 hours to form a slurry-shaped mixture, wherein the mass ratio of the absolute ethyl alcohol to the raw materials is 2: 3; placing the obtained slurry-like mixture in an oven, keeping the temperature and drying for 5 hours at the temperature of 80 ℃, and sieving the dried raw material with a 200-mesh sieve to obtain the uniformly mixed raw material; weighing a certain amount of uniformly mixed raw materials, and putting the raw materials into a stainless steel mold for dry pressing and forming under the pressure of 15MPa to obtain a cylindrical ceramic blank; sintering the ceramic blank at high temperature under the condition of reducing atmosphere, wherein the sintering atmosphere is 5% H₂/95%N₂The heating rate of the mixed gas of hydrogen and nitrogen is 5 ℃/min, the sintering temperature is 1400 ℃, the sintering time is 6 hours, and the blue mechanoluminescence ceramic material is obtained after cooling and taking out.

Example 2

A blue-color mechanoluminescence ceramic material having a chemical composition of Ca_0.98Al₃O₄N: 0.01Eu²⁺, 0.01Sm³⁺。

As high purity CaCO₃、Al₂O₃、AlN、Eu₂O₃And Sm₂O₃As a raw material, Ca in accordance with the chemical composition_0.98Al₃O₄N: 0.01Eu²⁺, 0.01Sm³⁺The raw materials are accurately weighed according to the proportion of the elements in the raw materials; the method comprises the following steps of taking agate balls as grinding balls, taking absolute ethyl alcohol as a ball milling medium, simultaneously putting the agate balls, the absolute ethyl alcohol and raw materials into a ball milling tank, and carrying out ball milling and mixing on a planetary ball mill for 10 hours to form a slurry-shaped mixture, wherein the mass ratio of the absolute ethyl alcohol to the raw materials is 2: 3; placing the obtained slurry-like mixture in an oven, keeping the temperature and drying for 4 hours at the temperature of 80 ℃, and sieving the dried raw material with a 200-mesh sieve to obtain the uniformly mixed raw material; weighing a certain amount of uniformly mixed raw materials, and putting the raw materials into a stainless steel mold for dry pressing and forming under the pressure of 15MPa to obtain a cylindrical ceramic blank; sintering the ceramic blank at high temperature under the condition of reducing atmosphere, wherein the sintering atmosphere is 5% H₂/95%N₂The heating rate of the hydrogen-nitrogen mixed gas is 5 ℃/min, the sintering temperature is 1300 ℃, the sintering time is 8 hours, and the blue mechanoluminescence ceramic material is obtained after cooling and taking out.

Example 3

A blue-color mechanoluminescence ceramic material having a chemical composition of Ca_0.92Al₃O₄N: 0.04Eu²⁺, 0.02Nd³⁺, 0.02Sm^{3 +}。

As high purity CaCO₃、Al₂O₃、AlN、Eu₂O₃、Nd₂O₃And Sm₂O₃As a raw material, Ca in accordance with the chemical composition_0.92Al₃O₄N: 0.04Eu²⁺, 0.02Nd³⁺, 0.02Sm³⁺The raw materials are accurately weighed according to the proportion of the elements in the raw materials; the method comprises the steps of taking agate balls as grinding balls, taking absolute ethyl alcohol as a ball milling medium, simultaneously putting the agate balls, the absolute ethyl alcohol and raw materials into a ball milling tank, and carrying out ball milling on the mixture for 20 hours on a planetary ball mill to form a slurry-shaped mixture, wherein the mass ratio of the absolute ethyl alcohol to the raw materials is 2: 3; mixing the obtained slurryPlacing the mixture in an oven, keeping the temperature and drying for 6 hours at 80 ℃, and sieving the dried raw material with a 200-mesh sieve to obtain a uniformly mixed raw material; weighing a certain amount of uniformly mixed raw materials, putting the raw materials into a stainless steel mold, and performing dry pressing molding under the pressure of 10MPa to obtain a cylindrical ceramic blank; sintering the ceramic blank at high temperature under the condition of reducing atmosphere, wherein the sintering atmosphere is 5% H₂/95%N₂The heating rate of the mixed gas of hydrogen and nitrogen is 5 ℃/min, the sintering temperature is 1100 ℃, the sintering time is 10 hours, and the blue mechanoluminescence ceramic material is obtained after cooling and taking out.

Example 4

A blue-color mechanoluminescence ceramic material having a chemical composition of Ca_0.9Al₃O₄N: 0.06Eu²⁺, 0.02Nd³⁺, 0.02Sm^{3 +}。

As high purity CaCO₃、Al₂O₃、AlN、Eu₂O₃、Nd₂O₃And Sm₂O₃As a raw material, Ca in accordance with the chemical composition_0.9Al₃O₄N: 0.06Eu²⁺, 0.02Nd³⁺, 0.02Sm³⁺The raw materials are accurately weighed according to the proportion of the elements in the raw materials; the method comprises the steps of taking agate balls as grinding balls, taking absolute ethyl alcohol as a ball milling medium, simultaneously putting the agate balls, the absolute ethyl alcohol and raw materials into a ball milling tank, and carrying out ball milling and mixing on a planetary ball mill for 15 hours to form a slurry-shaped mixture, wherein the mass ratio of the absolute ethyl alcohol to the raw materials is 2: 3; placing the obtained slurry-like mixture in an oven, keeping the temperature and drying for 6 hours at the temperature of 80 ℃, and sieving the dried raw material with a 200-mesh sieve to obtain the uniformly mixed raw material; weighing a certain amount of uniformly mixed raw materials, putting the raw materials into a stainless steel mold, and performing dry pressing molding under the pressure of 12MPa to obtain a cylindrical greenware; sintering the ceramic blank at high temperature under the condition of reducing atmosphere, wherein the sintering atmosphere is 5% H₂/95%N₂The heating rate of the hydrogen-nitrogen mixed gas is 5 ℃/min, the sintering temperature is 1200 ℃, the sintering time is 8 hours, and the blue mechanoluminescence ceramic material is obtained after cooling and taking out.

Example 5

A blue-color mechanoluminescence ceramic material having a chemical composition of Ca_0.84Al₃O₄N: 0.08Eu²⁺, 0.04Nd³⁺, 0.04Sm^{3 +}。

As high purity CaCO₃、Al₂O₃、AlN、Eu₂O₃、Nd₂O₃And Sm₂O₃As a raw material, Ca in accordance with the chemical composition_0.84Al₃O₄N: 0.08Eu²⁺, 0.04Nd³⁺, 0.04Sm³⁺The raw materials are accurately weighed according to the proportion of the elements in the raw materials; the method comprises the steps of taking agate balls as grinding balls, taking absolute ethyl alcohol as a ball milling medium, simultaneously putting the agate balls, the absolute ethyl alcohol and raw materials into a ball milling tank, and carrying out ball milling and mixing on a planetary ball mill for 16 hours to form a slurry-shaped mixture, wherein the mass ratio of the absolute ethyl alcohol to the raw materials is 2: 3; placing the obtained slurry-like mixture in an oven, keeping the temperature and drying for 4 hours at the temperature of 80 ℃, and sieving the dried raw material with a 200-mesh sieve to obtain the uniformly mixed raw material; weighing a certain amount of uniformly mixed raw materials, and putting the raw materials into a stainless steel mold for dry pressing and forming under the pressure of 15MPa to obtain a cylindrical ceramic blank; sintering the ceramic blank at high temperature under the condition of reducing atmosphere, wherein the sintering atmosphere is 5% H₂/95%N₂The heating rate of the hydrogen-nitrogen mixed gas is 5 ℃/min, the sintering temperature is 1300 ℃, the sintering time is 6 hours, and the blue mechanoluminescence ceramic material is obtained after cooling and taking out.

Example 6

A blue-color mechanoluminescence ceramic material having a chemical composition of Ca_0.8Al₃O₄N: 0.1Eu²⁺, 0.06Nd³⁺, 0.04Sm³⁺。

As high purity CaCO₃、Al₂O₃、AlN、Eu₂O₃、Nd₂O₃And Sm₂O₃As a raw material, Ca in accordance with the chemical composition_0.8Al₃O₄N: 0.1Eu²⁺, 0.06Nd³⁺, 0.04Sm³⁺The raw materials are accurately weighed according to the proportion of the elements in the raw materials; agate balls are used as grinding balls, absolute ethyl alcohol is used as a ball milling medium, and maca is addedPlacing the agate balls, the absolute ethyl alcohol and the raw materials into a ball milling tank at the same time, and carrying out ball milling and mixing on a planetary ball mill for 15 hours to form a slurry-shaped mixture, wherein the mass ratio of the absolute ethyl alcohol to the raw materials is 2: 3; placing the obtained slurry-like mixture in an oven, keeping the temperature and drying for 5 hours at the temperature of 80 ℃, and sieving the dried raw material with a 200-mesh sieve to obtain the uniformly mixed raw material; weighing a certain amount of uniformly mixed raw materials, putting the raw materials into a stainless steel mold, and performing dry pressing molding under the pressure of 16MPa to obtain a cylindrical ceramic blank; sintering the ceramic blank at high temperature under the condition of reducing atmosphere, wherein the sintering atmosphere is 5% H₂/95%N₂The heating rate of the mixed gas of hydrogen and nitrogen is 5 ℃/min, the sintering temperature is 1400 ℃, the sintering time is 10 hours, and the blue mechanoluminescence ceramic material is obtained after cooling and taking out.

Comparative example 1

A blue-color mechanoluminescence ceramic material having a chemical composition of Ca_0.99Al₃O₄N: 0.01Eu²⁺。

As high purity CaCO₃、Al₂O₃AlN and Eu₂O₃As a raw material, Ca in accordance with the chemical composition_0.99Al₃O₄N: 0.01Eu²⁺The raw materials are accurately weighed according to the proportion of the elements in the raw materials; the method comprises the following steps of taking agate balls as grinding balls, taking absolute ethyl alcohol as a ball milling medium, simultaneously putting the agate balls, the absolute ethyl alcohol and raw materials into a ball milling tank, and carrying out ball milling and mixing on a planetary ball mill for 5 hours to form a slurry-shaped mixture, wherein the mass ratio of the absolute ethyl alcohol to the raw materials is 2: 3; placing the obtained slurry-like mixture in an oven, keeping the temperature and drying for 5 hours at the temperature of 80 ℃, and sieving the dried raw material with a 200-mesh sieve to obtain the uniformly mixed raw material; weighing a certain amount of uniformly mixed raw materials, and putting the raw materials into a stainless steel mold for dry pressing and forming under the pressure of 15MPa to obtain a cylindrical ceramic blank; sintering the ceramic blank at high temperature under the condition of reducing atmosphere, wherein the sintering atmosphere is 5% H₂/95%N₂The heating rate of the mixed gas of hydrogen and nitrogen is 5 ℃/min, the sintering temperature is 1400 ℃, the sintering time is 6 hours, and the blue mechanoluminescence ceramic material is obtained after cooling and taking out.

FIG. 1 is a mechanoluminescence spectrum of samples of examples 1-2 and comparative example 1 provided by the present invention, and the test pressure is 20 MPa. Wherein comparative example 1 and example 1 were prepared under the same conditions, except that no Nd was introduced into comparative example 1³⁺Or Sm³⁺And the like, and impurities such as rare earth ions. As can be seen from the figure, under a certain pressure condition, the examples 1-2 have obvious mechanoluminescence effect, the emission peak wavelength is positioned in a blue light region of 470nm, while the comparative example 1 has weaker mechanoluminescence effect, which indicates that Nd is introduced³⁺Or Sm³⁺The rare earth ions with the same impurities can effectively enhance the mechanoluminescence effect.

FIG. 2 is a mechanoluminescence spectrum of the samples of examples 3 to 4 provided by the present invention, and the test pressure is 20 MPa. Wherein examples 3 and 4 differ in the activation of the ion Eu²⁺The doping concentrations of the materials are different, and it can be seen from the figure that under certain pressure conditions, the examples 3-4 have obvious mechanoluminescence effects, and the emission peak wavelength is in the blue light region of 470nm, wherein the example 3 is the preferable result.

FIG. 3 is a mechanoluminescence spectrum of the samples of examples 5 to 6 provided by the present invention, and the test pressure is 20 MPa. As can be seen from the figure, under certain pressure conditions, the examples 5 to 6 have obvious mechanoluminescence effects, and the emission peak wavelength is in the blue region of 470 nm.

FIG. 4 is a graph showing the relationship between the relative luminance and the intensity of pressure of the samples of examples 1-6 provided by the present invention, and it can be seen from the graph that when the intensity of pressure is less than 25MPa, the intensity of light emission of the samples is in direct proportion to the intensity of pressure, which indicates that the intensity of pressure can be represented by the intensity of light emission, and Eu doped with different concentrations is added²⁺、Nd³⁺And Sm³⁺Under the same pressure conditions, the photoluminescence intensity is different, with example 3 being the preferred result.

The performance of the mechanoluminescence material depends mainly on three basic components of the crystal structure of the matrix, the active ion and the auxiliary active ion. (1) Influence of the matrix: in the crystal, hole defects VM²⁺VO, electron defect^2-And Eu²⁺Are attracted to each other by electrostatic fieldRecently, and a system of interrelated defects is formed. Under excitation of the excitation source, the probability that an electron is excited to a conduction band with higher energy is not high, and the electron can only transit in a mutually related defect system. Therefore, different substrate bonding conditions, different lattice parameters and different ionic radii are used for Eu²⁺The luminescence property of (A) has a great influence. (2) Influence of activating ions: the commonly used activating ion is Yb²⁺、Eu²⁺、Ce³⁺、Pr³⁺、Tm³⁺And Tb³⁺And the like, because of differences in various aspects such as atomic number, ionization energy, electronegativity, energy level structure and the like of various rare earth ions, the light emitting characteristics are generally different even in the same lattice environment, the emitted light intensity and the emitted wavelength are not predictable, and the light emitting characteristics cannot be obtained by simple derivation in the prior art. The invention uses Eu²⁺Ion as activating ion with chemical composition formula of Ca_1-x-yAl₃O₄N: xEu²⁺, yRe³⁺The material can emit bright blue light by pressure induction. (3) Influence of auxiliary activating ions: a common auxiliary activating ion is Dy³⁺、Pr³⁺、Y³⁺、Ce³⁺、La³⁺、Ho³⁺、Sm³⁺、Tb³⁺、Sm³⁺、Nd³⁺、Er³⁺、Yb³⁺、Tm³⁺And Sm³⁺Etc. the change in the size and shape of the crystal lattice due to the doping of the co-activator results in impurity levels resulting from holes generated when the co-activator ions substitute for the host cations, the impurity levels being at Eu²⁺Between the ground state energy level and the excited state energy level. Under the irradiation of an excitation source, Eu²⁺Electrons in the ground state are excited to transit to the excited state, some electrons release energy in the form of light by transitioning back to a low energy level during excitation, other electrons enter an impurity level of a hole, and after excitation is stopped, the electrons stored in the impurity level absorb energy due to strong thermal disturbance generated by external pressure on the substrate, and enter Eu²⁺And in the process of transition back to the ground state energy level with lightRelease energy in the form of heat. The mechanoluminescence intensity mainly depends on the number and density of electrons in the impurity level and the return of these electrons from the impurity level to Eu²⁺And therefore, the selection of a suitable co-activating ion is critical. The present invention provides two suitable auxiliary activating ions, namely Nd³⁺And Sm³⁺The ionic can obviously improve the mechanoluminescence performance of the material.

Claims (8)

1. The blue mechanoluminescence ceramic material powder particle ink is characterized in that the ink is prepared from a blue mechanoluminescence ceramic material powder particle suspension solvent, and the chemical composition general formula of the ceramic material is Ca_1-x-yAl₃O₄N: xEu^{2 +}, yRe³⁺Wherein Re is one or two combinations of Nd and Sm, and the value ranges of x and y are respectively as follows: x is more than or equal to 0.01 and less than or equal to 0.1, and y is more than or equal to 0.01 and less than or equal to 0.2.

2. The ink of claim 1, wherein the blue photoluminescent ceramic material powder particles are present in an amount of 0.5 to 10 parts by weight, based on 100 parts by weight of the suspension; preferably, the content of the blue mechanoluminescence ceramic material powder particles is 1 to 5 parts by weight.

3. The blue photoluminescent ceramic material powder particle ink according to claim 1, wherein the suspension further comprises a polymeric material.

4. A blue mechanoluminescence ceramic material powder particle ink according to claim 4, wherein said high molecular substance is selected from one or more of PVA, EVA, PDMS, PU, PMMA, PAM, PVP, starch, cellulose, vegetable gum, animal gum, carboxymethyl starch, starch acetate, hydroxymethyl cellulose and carboxymethyl cellulose.

5. A blue photoluminescent ceramic material powder particle ink according to claim 4, wherein the polymer is present in an amount of 1 to 10 parts by weight, based on 100 parts by weight of the suspension; preferably, the content of the polymer is 3 to 8 parts by weight.

6. A blue electroluminescent ceramic powder particle ink according to claim 1, wherein said solvent is selected from one or more of water, methanol, ethanol, acetone, ethylene glycol, isopropanol, diethylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol butyl ether, ethylene glycol phenyl ether, ethylene glycol benzyl ether, Kanglun alcohol, diethylene glycol methyl ether, diethylene glycol ethyl ether, diethylene glycol butyl ether, triethylene glycol methyl ether, diacetone alcohol, tridecanol, tetradecanol, dioctyl phthalate, ethyl acetate, butyl acetate, cyclohexanone, xylene, dicyclohexyl, cyclohexane, n-butanol, methyl ethyl ketone, dimethyl phthalate and sorbitol.

7. The blue mechanoluminescence-ceramic powder particle ink as claimed in claim 1, wherein said suspension of blue mechanoluminescence-ceramic powder particles is applied to the surface of said substrate by a coating method such as spray coating, spin coating or printing.

8. The blue mechanoluminescent ceramic material powder particle ink according to claim 1, wherein a suspension of blue mechanoluminescent ceramic material powder particles is printed on the surface of the substrate using a printing technique; the printing technique is selected from one of dispensing, ink jet printing, water transfer printing, screen printing, and roll-to-roll printing.

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