CN107739211A - A kind of yellow green mechanoluminescence ceramic material and preparation method thereof - Google Patents

A kind of yellow green mechanoluminescence ceramic material and preparation method thereof Download PDF

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CN107739211A
CN107739211A CN201711061732.1A CN201711061732A CN107739211A CN 107739211 A CN107739211 A CN 107739211A CN 201711061732 A CN201711061732 A CN 201711061732A CN 107739211 A CN107739211 A CN 107739211A
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mechanoluminescence
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CN107739211B (en
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杨道救
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CANGZHOU ZHONGLAN RARE EARTH NEW MATERIAL TECHNOLOGY Co.,Ltd.
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Hangzhou Qingqing Science And Technology Co Ltd
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Abstract

The invention discloses a kind of yellow green mechanoluminescence ceramic material and preparation method thereof, it is desirable to provide a kind of pressure sensitive material with mechanoluminescence performance, belongs to ceramic technology field.The ceramic chemical composition formula is Sr2‑x‑ySi7O4N8:xEu2+,yRe3+, wherein Re is one or both of Gd and Lu combination, and x and y span are respectively：0.01≤x≤0.1,0.01≤y≤0.2.The ceramic centre of luminescence is Eu2+Ion, by introducing Gd3+And Lu3+It can effectively strengthen its mechanoluminescence effect Deng rare earth impurities ion.Ceramics provided by the invention have the features such as compression strength is high, mechanoluminescence positive effect, available for the pressure sensitive part in pressure sensor.

Description

A kind of yellow green mechanoluminescence ceramic material and preparation method thereof
Technical field
The invention belongs to ceramic technology field, more particularly to a kind of yellow green mechanoluminescence ceramic material and its preparation side Method.
Background technology
Mechanoluminescence is a kind of special luminescence phenomenon, with luminescence generated by light, the cathode-ray luminescence of electron-beam excitation, electric shock The differences such as the thermoluminescence of electricity photoluminescence and thermal excitation, mechanoluminescence do not need special extraneous excitaton source, it is only necessary to by The effects such as stretching, impact, friction, compression can send optical signal.In the past few decades, on material mechanoluminescence phenomenon always Practical application is not obtained, reason is that the mechanoluminescence phenomenon of common material is very faint, and the duration is very short, it is difficult to quilt Detection instrument is caught.In recent years, scientist was found that a variety of materials with efficient electroluminescent properties successively, and it has cost The advantages such as cheap, stable luminescent property, luminous intensity be directly proportional to suffered stress intensity, are obtained in many important events Using.For example, it can be used as detecting bridge and building using the sensor made by the mechanoluminescence characteristic of mechanoluminescence material When being impacted, the formation and propagation of tiny slight crack.On engineering construction, in order to ensure the reliability of engineering structure, generally need Stress distribution is wanted to measure, stress distribution measurement can use X-ray diffraction method, thermal imaging method and fiber optic network etc., and utilize The mechanoluminescence characteristic of mechanoluminescence material provides that another is simple for structural damage detection and stress distribution, it is reliable and The method of low cost.With the development of weak light detection technique and the lifting of mechanoluminescence material emission intensity, mechanoluminescence material Material is in mechanics sensor, material stress distributional analysis, building safety, life science, earthquake and volcano eruption prediction etc. There is very strong application prospect.
Long after glow luminous material is one kind in external excitaton source（UV-visible, X ray, β rays etc.）After stopping Remain to reasonable time it is interior（Several seconds to more than ten hour）The material of macroscopic phosphorescence afterglow is maintained, in emergency lighting, police Indicating knowledge etc. starts to be widely used.However, the mechanoluminescence phenomenon of long-afterglow material is in recent years in state A research direction of association area researcher attention is obtained on border, in mechanics sensor, material stress analysis, building peace Entirely, earthquake and volcano eruption prediction etc. have important application prospect.Research for long after glow luminous material, 1866 Sidot by France et al. prepares the ZnS of green light first:Cu long-afterglow materials, then it is found that rare earth ion Ce3+ Tb3+Er3+The calcium sulfide long-afterglow material glow color of activation is also green since the 1960s, and people are gradual Research direction aluminate substrate series aspect is transferred to wherein, with Eu2+The material emission performance of doped strontium aluminate system compared with Good, the long-afterglow material of green light mainly has SrAl2O4: Eu2+(green-yellow light) SrAl2O4: Eu2+, Dy3+(green-yellow light) Sr4Al14O25: Eu2+,Dy3+(blue green light) SrAl4O7: Eu2+, Dy3+(blue green light) BaAl2O4: Eu2+, Dy3+It is (bluish-green Light) etc. comparatively, the light emitting region of silicate systems material is wider, and wherein green light mainly has (CaSr) MgSi2O7: Eu2+, Dy3+(blue green light) and Ba2MgSi2O7: Eu2+, Tm3+(green glow) in recent years, nitrogen oxides luminescent material is due to having concurrently Preparation technology is simple and the characteristics of good luminescence property, has been increasingly becoming the study hotspot of field of light emitting materials.Nitrogen oxides base 5d electronic energy of the matter due to electron cloud diffusion effect, can effectively reduce doping with rare-earth ions with big crystalline field splitting State, therefore, rare earth doped nitric oxide luminescent material have from ultraviolet to the broad band excitation band of visible region, by changing silicon substrate The chemical composition of nitric oxide fluorescent powder, it is possible to achieve blue, green, red, yellow all-wave length transmitting.Especially silicon substrate nitrogen oxides is sent out Luminescent material has the advantages such as specular removal, high color stability, adjustable color, high-color rendering, therefore, to nitrogen oxides luminescent material Research there is important scientific meaning and application value.But rare report nitrogen oxides luminescent material in existing literature Mechanoluminescence performance, the mechanoluminescence performance that reason is primarily due to existing nitrogen oxides luminescent material is weaker, micro light detecting compared with It is difficult.
The content of the invention
It is a series of in order to overcome that the luminous intensity of the above-mentioned material of mechanoluminescence in the prior art is weaker, micro light detecting is difficult etc. Problem, the invention provides a kind of yellow green mechanoluminescence ceramic material and preparation method thereof, the ceramics have compression strength height, The features such as mechanoluminescence positive effect, available for the pressure sensitive part in pressure sensor.
To solve above-mentioned the deficiencies in the prior art, the technical solution adopted in the present invention is as follows：
A kind of yellow green mechanoluminescence ceramic material, the chemical composition formula of the ceramic material is Sr2-x-ySi7O4N8: xEu2 +, yRe3+, wherein Re is one or both of Gd and Lu combination, and x and y span are respectively：0.01≤x≤0.1, 0.01≤y≤0.2.Especially, the ceramic centre of luminescence is Eu2+Ion, by introducing Gd3+And Lu3+Deng rare earth impurities from Son can effectively strengthen its mechanoluminescence effect.
A kind of preparation method of yellow green mechanoluminescence ceramic material, it is characterised in that comprise the following steps：
（1）Dispensing：With the SrCO of high-purity3、SiO2、Si3N4、Eu2O3、Gd2O3And Lu2O3As raw material, lead to according to chemical composition Formula Sr2-x-ySi7O4N8: xEu2+, yRe3+The proportioning of middle each element, accurately weighs raw material；
（2）Batch mixing：Using agate ball as mill ball, using absolute ethyl alcohol as ball-milling medium, by agate ball, absolute ethyl alcohol and raw material It is put into simultaneously in ball grinder, ball mill mixing 5 ~ 20 hours on planetary ball mill, forms pulp-like mixture, the anhydrous second The mass ratio of alcohol and raw material is 2:3；
（3）Drying：The pulp-like mixture of acquisition is placed in baking oven, insulation drying 4 ~ 6 hours under the conditions of 80 DEG C, then will be dry The raw material obtained after dry crosses 200 mesh sieve, obtains well mixed raw material；
（4）Shaping：A certain amount of well mixed raw material is weighed, is put into dry-pressing formed in stainless steel mould, pressure is 10 ~ 15MPa, Obtain cylindrical greenwave；
（5）Sintering：Described greenwave is subjected to high temperature sintering, sintering atmosphere 5%H under reducing atmosphere condition2/95%N2Hydrogen Nitrogen mixed gas, heating rate are 5 DEG C/min, and sintering temperature is 1400 ~ 1600 DEG C, and sintering time is 6 ~ 10 hours, is taken after cooling Go out to produce a kind of yellow green mechanoluminescence ceramic material.
Compared with prior art, the beneficial effects of the invention are as follows：
（1）The invention provides a kind of yellow green mechanoluminescence ceramic material, its matrix composition is Sr2Si7O4N8, pass through rare earth Ion Eu2+Doping obtains yellow mechanoluminescence phenomenon, and luminous peak position is in 550nm；
（2）By introducing Gd3+And Lu3+Deng rare earth impurities ion, impurity energy level is produced, can effectively strengthen its mechanoluminescence effect Fruit；
（3）Mechanoluminescence ceramic material compression strength provided by the invention is high, can be worked under larger pressure condition, pressure disappears There is the characteristics of reusable after removing.
The invention also discloses a kind of stress irradiance element, using substrate made of above-mentioned mechanoluminescence ceramic material.
The invention also discloses a kind of stress irradiance element, including substrate and the pressure light-emitting film that is attached in substrate, Described pressure light-emitting film is above-mentioned mechanoluminescence ceramic powder or mechanoluminescence ceramic material thin slice.
The invention also discloses a kind of stress irradiance element to include substrate and the pressure light-emitting film being attached in substrate, institute The pressure light-emitting film stated is mechanoluminescence ceramic powder or mechanoluminescence ceramic material thin slice.
Preferably, the thickness of pressure light-emitting film is 1-10mm.
The substrate of the present invention, can be rigid basement, or flexible substrates.Preferably, the rigid basement can So that PDMS (polydimethylsiloxanes can be selected from selected from glass, silicon, steel, ceramics, cement, timber and stone, the flexible substrates Alkane) film, PET (polyethylene terephthalate) film, PS (polystyrene) film, PU (polyurethane) film, PI (polyimides) film With PVA (polyvinyl alcohol) film.
Above-mentioned stress irradiance part making method, including：By mechanoluminescence ceramic powder particle as described above Suspension coated in substrate as described above.
Although suspension will be prepared into mechanoluminescence ceramic powder particle suspension liquid solvent as described above, then Coated on can prepare the sensor that meets application claims in the substrate, but when also containing macromolecule in the suspension During material, the sensitivity of final prepared sensor and precision can be lifted further.
The content of the mechanoluminescence ceramic powder particle can also change in wider scope, preferable case Under, the suspension based on 100 parts by weight, the content of the mechanoluminescence ceramic powder particle is 0.5-10 weight Part, preferably 1-5 parts by weight.
Preferably, the polymer substance is selected from PVA, EVA (ethene-vinyl acetate copolymer), PDMS, PU, PMMA (gather Methyl methacrylate), PAM (polyacrylamide), PVP (polyvinylpyrrolidone), starch, cellulose, natural plant gum, animal One or more in glue, CMS, acetic starch, hydroxymethyl cellulose and carboxymethyl cellulose.
According to the present invention, the content of the polymer substance can also change in wider scope, under preferable case, base In the suspension of 100 parts by weight, the high molecular content is 1-10 parts by weight, preferably 3-8 parts by weight.
According to the present invention, the solvent can be various solvents commonly used in the art, be preferably selected from water, methanol, second Alcohol, acetone, ethylene glycol, isopropanol, diethylene glycol (DEG), ethylene glycol monomethyl ether, ethylene glycol ethyl ether, butyl glycol ether, ethylene glycol phenyl ether, second two Alcohol benzyl oxide, health alcohol, diethylene glycol methyl ether, diethylene glycol ether, butyl carbitol, triethylene glycol methyl ether, diacetone alcohol, tridecanol, 14 Alcohol, dioctyl phthalate, ethyl acetate, butyl acetate, cyclohexanone, dimethylbenzene, bicyclohexyl, hexamethylene, n-butanol, One or more in butanone, repefral and D-sorbite.
According to the present invention, by the suspension of the mechanoluminescence ceramic powder particle coated on the substrate surface Method can be the conventional selection in this area, it is for instance possible to use the painting method such as spraying, spin coating, can also use and print Technology.The suspension of mechanoluminescence ceramic powder particle is imprinted on the surface of substrate by present invention printing technique preferred herein On, so that the sensitivity for the sensor being prepared and precision are further lifted.Wherein, the printing technique can With one kind in dispensing, inkjet printing, water transfer, silk-screen printing and volume to volume printing.When use printing technique is by described in When the suspension of mechanoluminescence ceramic powder particle is printed on the surface of the substrate, the suspension is preferably prepared into ink Water, the preparation method of the ink is by the way that the suspension blending and stirring or blending ultrasonic disperse are obtained.
Mechanoluminescence ceramic powder particle of the present invention, pressure sensitive part as described above and as described above Application of the pressure sensor in wind tunnel experiment for preparing of method.
The invention also discloses a kind of stress irradiance element, the stress irradiance element includes high polymer material and described power Photoluminescence ceramic powder, mechanoluminescence ceramic powder are evenly distributed in high polymer material, mechanoluminescence ceramics material The addition at feed powder end is 1 ~ 90%；Preferably 10 ~ 80%.High polymer material can be selected from PDMS (dimethyl silicone polymer), PET (polyethylene terephthalate), PS (polystyrene), PU (polyurethane), PI (polyimides) and PVA (polyvinyl alcohol) are thin. Appropriateness in order to improve the performance of processing, the thin-film material can also add coupling agent, lubricant, plasticizer etc..
The invention also discloses a kind of ink, the ink includes ink conventional ingredient and described mechanoluminescence ceramic material Powder, mechanoluminescence ceramic powder are evenly distributed in ink conventional ingredient, the addition of mechanoluminescence ceramic powder Measure as 1 ~ 30%；Preferably 5 ~ 10%.Ink resin system can be polyamide, chlorination polypropylene, polyurethane or acrylic acid.Both may be used To be that oil-based ink can also be water-based ink.
The invention also discloses a kind of coating, the coating includes coating conventional ingredient and described mechanoluminescence ceramic material Powder, mechanoluminescence ceramic powder are evenly distributed in coating conventional ingredient, the addition of mechanoluminescence ceramic powder Measure as 1 ~ 30%；Preferably 5 ~ 10%.Coating resin system can be polyamide, chlorination polypropylene, polyurethane or acrylic acid.Both may be used To be that oil paint can also be water paint.
In addition, it is formed at common paper, synthetic paper or epoxy resin, poly- second by the way that mechanoluminescence ceramic material will be included The macromolecule such as alkene, polyethylene terephthalate, polyester, polypropylene, polyvinyl chloride raw material, natural rubber or synthesis rubber Glue, glass, ceramics, metal, wood, artificial fiber or natural fiber, concrete or combinations thereof and their fabricated product Deng exterior trim surface, or by internally containing mechanoluminescence ceramic material, so as to detect exception, or pass through and apply impact Ripple and the deterioration (stress-strain detection, stress distribution measure) for diagnosing various works, component.For example,：Mansion building, The large structures such as overpass, bridge, road, rail, pillar, tower, pipeline and tunnel, flooring material, ceramic tile, wall material, The driving members such as the construction materials such as prefabricated board material, paveio(u)r, timber, steel, concrete, gear, cam, bicycle, vapour Exterior trim part or build-in components (engine components, tire, belt etc.), the bearing portion used in car, electric car, ship, aircraft etc. Link part such as part, bearing retainer and bearing with optical sensor, screw, screw rod, nut, packing ring etc..In addition, As its application, can expect：Detection battery, valve seat, feed pipe, sprinkler head, it is filled with electrolyte or polymer dielectric Nonaqueous electrolytic solution secondary battery leakage.Furthermore it is possible to make the bond layer of the bonding agent containing mechanoluminescence ceramic material Internal stress distribution visualization, the cracking of bonding agent can also be held.
During using mechanoluminescence ceramic material as stress irradiance element, it can be used for pressure-sensitive device, touch screen, touch-control sensing Device, photodiode or phototransistor, piezoelectric actuator or electrostatic actuators, photism polymer actuator, liquid inspection Device, impact force detector part, fiber waveguide, optical waveguide device, mechanical optics device, detection means, information processor, open The e-machines such as pass, operation button, input unit, finger-impu system and machine, the non-contact of device and system can be carried out Control, automation process, straighforward operation.Such as it can enumerate：The elevation measurement device of the connection terminal of semiconductor device, hole Phenomenon generating capacity measure device, sound pressure distribution measure device, using medical examination ultrasonic wave sound pressure The stress of the component effects such as graft of the distribution with energy density distribution measure device, to being installed on organism bone or analog bone The dress of measure device, transmission hawser, conveyer and the laser processing device of the distribution of strain, the amount of bow of detection steering spindle Put, the radiation camera of the position of specific photographed region, the depth of parallelism check device of flow rate detector mould pressurizing machine, energy Enough make solid camera head that stress corresponding with the thermal energy of infrared light produces and image, by frictional force, shearing force, impact Light head that the mechanical external forces such as power, pressure are converted into optical signal and transmitted, using the light head by straighforward operation machinery device Remote-control switching system and using the light head detect the detecting system of couple, be removably installed in electrically, electronics, machinery The dismounting body of the main part of various machines, the print cartridge of such as ink-jet printer, it can detect with the installment state of paper carton and not The detection means and dismounting body of the dismounting body of installment state；It can check that the ultraviolet for residuing in jog is consolidated in a short time Change the imprinting apparatus of resin, do not need the operation device of distribution, can be directed into organism, dark place it is small-sized and radio-type Light source (stress irradiance particle), the check device for possessing it and inspection method, stress placement file system etc..In addition, also may be used For：Pad, the measure of sealing of seal, the ground plane shape of tire, measure, the gear division snap-in force of earth contact pressure distribution Measure, the grounding parts tools for measurement of tire, the assay method etc. of cavitation generating capacity.
Tactile sensor element application can also be used as.Such as it can enumerate：People coordinates humanoid robot, vacation of doing evil through another person refers to Artificial limb, the distinctor of diagnosis, various industrial hardness pliability detectors etc..In addition, by measure due to radiation Act on and caused luminous energy, so as to which the meter of the metering of the radiant exposure of radiation and exposure intensity distribution can also be expected Amount.
In addition to said determination device, it is also contemplated that as illumination, for safety display utilization.Such as For：The ligthing paraphernalias such as device vibration lamp, wind power lamp；Promptly, abnormal notification, very apparatus, very dangerous display, lamp, non-conventional Mark, the mark of help instrument, signboard, display device；Safety guard, the nervous rope hung on around shop building, animal Guard rail；Use filament the pedal of ladder, handrail and the mesh that is set in the state of road etc. is partly embedded in；Health promoting appliance, Walking assisting device tool (walking auxiliary walking stick, luminous notification antenna etc.)；The jewellery such as earrings, necklace；Support pillar, the railway of flag The exterior trim part or build-in components, fishing tackle of Deng Jie roads Ji Jie roads rod, bicycle, automobile, electric car, ship, aircraft etc. (simulation bait, fishing rod, fishing net etc.；Photism fiber construct, photism fishing gear, fishing line, fishing net etc.), buoy it is (float, floating Mark)；The position display of the domestic animals such as the pets such as people, dog, cat, ox, pig, sheep, chicken etc.；Fan (the blade of wind-power electricity generation, ventilating fan etc. Deng), clothes (shoes, gym suit, manually light cloth, artificial luminous filament, artificial luminescent fibre etc.)；Packaging (case, support, device, Envelope, ground paper, crust packaging, outside overlay film), medical products (breathing assistance utensil, experimental study equipment) robot (artificial hair Light hair structure body, artificial shiny skin, manually light body) etc..As coating composition, ink composition, cement, surface Utilization example containing mechanoluminescence ceramic material in coverture, can be enumerated：Financial institution, community organization, credit card company, stream The mailing such as crimping postcard sheet material containing mechanoluminescence ceramic material in bonding agent used in logical industry etc., stickup Thing；The furniture such as chair, bed；Flooring material, ceramic tile, wall material, prefabricated board material, paveio(u)r, timber steel coagulation The building materials such as soil；It is equipped on the automated navigation system device of vehicle；For operating the operation device of audio devices and air-conditioning etc.；Household electrical appliances The input units such as product, portable machine, electronic computer；The images such as digital camera, CCD camera, film, photo, image are deposited Storage means etc..
New outward appearance can be produced by making mechanoluminescence ceramic material luminous, therefore is also contemplated for toy, movable business Product etc. entertain the expansion of commodity, daily necessities.Such as it can enumerate：It is the wind long narrow flags such as dynamic toy, kite, carp shape flag, swing, fast Ski-running driving, carrousel, bow and arrow etc.；Pass through wind-force while the Powerless type light-emitting device (windbell etc.) of generation sound and light.Hair Photosphere (golf, the ball of baseball, table tennis ball, the ball etc. of billiard ball), the windmill of luminous mechanism；Balloon；Laminated structure thing For paper, batch flute, paper folding, paper balloon, folding fan, New Year card, paint this；(jumping pole, fencing, bow and arrow are isometric for sporting goods Size objects etc.)；It is the score confirmation pressure sensitive sealant part of golf club, tennis court line tester, dynamic ornamentation body, dynamic State engraving, dynamic souvenir；Dynamic Display device；Shock-wave luminescence decoration device；The PA-systems such as loudspeaker, musical instrument (violin, The diaphragms such as the wind instruments such as the percussion instruments such as the stringed musical instruments such as guitar, xylophone, drum, trumpet, flute, glass), tuning fork etc.；Lipuid goods Deng amusement commodity；The pasture and water with tank etc., container are viewed and admired in aquarium；Luminous wrist watch, luminous sand timer or sand timer type Light-emitting device；Light emitting-type simulates candle device；The artificial plant that can be lighted；Artificial eye；Cosmetic containing tack polymer Product composition, the printed article that forgery can be distinguished under visual state and marketable securities, the printer's ink containing stress irradiance particle, The admission of bill, check, stock, bond, various security, exchange ticket, books certificate, the ticket of traffic organization, toll facility, project Middle lottery ticket of ballot certificate that certificate, lottery ticket, Public Physical Education are competed etc., bank note, identity card, ticket, the pass etc., passport, writing are organic The printed article of ciphertext book seals seal etc..
Using along with the luminous of stress, the photochemical catalyst for being attached to mechanoluminescence ceramic material surfaces is set to activate and obtain , stress irradiance body-photochemical catalyst complex can be used for：Antibacterial, sterilization, the treatment to non-human animal, vehicle handrail, The dirt purification of the antibacterial articles such as handle, using the internal wall such as pipe arrangement positioned at dark place fluid energy of flow it is net Change.Stress irradiance material activates the photocrosslinking agent in macromolecule resin, can also promote to be crosslinked by lighting.
By the way that with being mixed in resin, the mechanoluminescence ceramic material of the present invention can be formed into the resin combination of the present invention Thing.
In addition, formed again by further adding other inorganic material or organic material in the resin combination of the present invention Condensation material, the stress irradiance body of the present invention can also be formed.
For example, in the case that resin is epoxy resin, acrylic resin etc., relative in the compounding of the mass parts of resin 100 1~200 part of mechanoluminescence ceramic material is stated, in the case that resin is polyvinyl resin, flexible vinyl chloride resin etc., relative to tree The mass parts of fat 100 are compounded the above-mentioned mass parts of mechanoluminescence ceramic material 30~300.Blend can be by using tapered mixing The mixers such as machine, V-Mixer, ribbon mixer, Henschel mixer, banbury mixers, triple-roller mill make resin Composition.
In addition, in the case of forming stress irradiance body by the resin combination, such as when obtaining the stress irradiance body of sheet, Such as relative to the parts by weight of Corvic 100, it is compounded the above-mentioned mass parts of mechanoluminescence ceramic material 50~200, calcium-zinc system The mass parts of stabilizer 3~5, the mass parts of dioctyl phthalate 30~100 as plasticizer, with two-roller mill 150~200 It is kneaded at DEG C, so as to obtain the stress irradiance body of the sheet with pliability.
When obtaining the stress irradiance body of film-form, such as relative to the mass parts of pet resin 100, The above-mentioned mass parts of mechanoluminescence ceramic material 20~50 are compounded, with double screw extruder, inflation processing machine at 250~300 DEG C It is kneaded, is molded, so as to obtains the stress irradiance body of film-form.
When obtaining the stress irradiance body of other shapes, such as relative to the mass parts of acrylic resin 100, it is compounded mechanoluminescence The mass parts of ceramic material 5~100, it is kneaded, is molded at 170~200 DEG C with double screw extruder, so as to obtain band Shape, tabular, bar-shaped, partical stress irradiance body.In addition, by using injection (mo(u)lding) machine at 170~200 DEG C to partical Stress irradiance body be processed shaping, the stress irradiance body of three-dimensional shape can be obtained.
When applying mechanical external force to the stress irradiance body, lighted due to mechanically deform.
As above-mentioned resin or other organic materials, can enumerate：Resin as thermoplastic resin, thermosetting resin. As thermoplastic resin, such as can enumerate：Low density polyethylene (LDPE), medium density polyethylene, high density polyethylene (HDPE), linear, low density The polyethylene such as polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyvinyl fluoride, polyvinylidene chloride, acrylonitrile-butadiene- The polyamide such as the styrene polymers such as styrol copolymer (ABS resin) or copolymer, 6- nylon, 66- nylon, 12- nylon, gather The acrylic resins such as amide imide, polyimides, PEI, polyurethane, polymethyl methacrylate, poly- acetic acid second The fluororesin such as alkene ester, vinyl-vinyl acetate copolymer, polyvinylidene fluoride, polytetrafluoroethylene (PTFE), alkenyl aroma hydroxy-aromatic resin, gather The polyester such as ethylene glycol terephthalate, polybutylene terephthalate (PBT), PEN, PLA, bisphenol-A Be the makrolon such as makrolon, polyacetals, polyphenylene sulfide, polymethylpentene, cellulose, polyvinyl alcohol, polyvinyl acetate, It is the polyacrylic acid such as polyacrylonitrile, SAN (AS resins), polyphenylene oxide (PPE), MODIFIED PP E, polyarylate, poly- Diphenyl sulfide, polysulfones, polyether sulfone, polyethers nitrile, polyether-ketone, polyketone, copolymer, ethene or the propylene of liquid crystal polymer ethene and propylene With copolymer, ethene and other olefinic insatiable hungers of other alpha-olefins (1- butylene, 1- amylenes, 1- hexenes, 4-methyl-1-pentene etc.) With the copolymer of monomer (vinyl acetate, acrylic acid, acrylate, methacrylic acid, methacrylate, vinyl alcohol etc.) Deng.
Thermoplastic resin can be used alone or in combination of two or more kinds.It should be noted that thermoplastic resin is copolymerization Can be the copolymer of any forms such as random copolymer, block copolymer during thing.As thermosetting resin, can enumerate：Phenol Urea formaldehyde, urea resin, melmac, unsaturated polyester resin, diallyl phthalate resin, epoxy resin, Organic siliconresin, alkyd resin, polyimides, PABM, casein resin, furane resins, polyurethane resin Deng.It can additionally enumerate：Utilize ultraviolet, the resin of radiation curing.
And then it can enumerate：Natural rubber, polyisoprene rubber, butadiene-styrene rubber, polybutadiene rubber, ethene-the third The rubber-based materials such as alkene-diene rubber, butyl rubber, neoprene, acrylonitrile butadiene rubber, silicon rubber.
In addition, can be by pigment, dyestuff, lubricant, antioxidant, ultra-violet absorber, light stabilizer, antistatic Agent, fire retardant, bactericide, antiseptic, solidification catalyst, Photoepolymerizationinitiater initiater etc. and the mechanoluminescence ceramic material of the present invention It is mixed together, is shaped to bar-shaped, tabular, film-form, threadiness, membranaceous, needle-like, spherical, foil-like, graininess, sand shape, scale The arbitrary shapes such as shape, sheet, liquid, gel, colloidal sol shape, suspension, aggregation, capsule-type.
As pigment, inorganic pigment, organic pigment can be enumerated.
As inorganic pigment, can enumerate：Titanium oxide, barium sulfate, calcium carbonate, zinc oxide, lead sulfate, yellow lead, zinc yellow, Kermes (red iron oxide (III)), cadmium red, ultramarine, dark blue, chrome oxide green, cobalt green, chocolate, titanium is black, synthesis is iron black, carbon black, Mica, the aluminum oxide covered by titanium oxide, iron oxide, mica, glass flake, the holographic pigment covered by titanium oxide, iron oxide Deng.In addition, as metallic powdery pigment, can enumerate：Aluminium powder, copper powders, powder of stainless steel, metallic colloid, conduct There are transparent emerylite, coloring mica, interference mica, interference aluminum oxide, the interference silica (interference glass) of interference effect Deng.
As organic pigment, can enumerate：Azo pigment (monoazo yellow, condensation azophosphine, azomethine Huang etc.), Huang Color iron oxide, titan yellow, pucherite, benzimidazolone, isoindolinone, isoindoline, quinophthalone, benzidine yellow, permanent Huang etc. Yellow uitramarine；The orange pigments such as permanent orange；Red iron oxide, naphthols AS systems azophloxine, anthanthrone, anthraquinone is red, pyrene is reddish brown, quinoline The red pigments such as acridone is red, diketopyrrolopyrrolecocrystals are red, permanent red；The purple face such as cobalt violet, quinacridone violet, dioxazine violets Material；The blue pigments such as cobalt blue, phthualocyanine pigment (phthalocyanine blue etc.), anthracene indigo plant；The viridine greens such as phthalocyanine green, azo system disperse dyes, Organic dyestuff such as anthraquinone system disperse dyes etc..
As dyestuff, can enumerate：Azo dyes, anthraquinone dye, bipseudoindoxyl dye, sulfur dye, triphenhlmethane dye, Pyrazolone dye, Stilbene dyestuff, diphenylmethane dye, Xanthene dyes, alizarin dyes, acridine dye, quinoneimine dye (piperazine Dyestuff, oxazine dyes, thiazine dye), thiazole dye, first alkynes dyestuff, nitro dye and nitroso-dyes etc..
As antioxidant, can enumerate：Hindered phenol series compound, phosphite ester based compound, phosphinate system chemical combination Thing and thioether based compound etc..
As hindered phenol series compound, can enumerate：Alpha-tocopherol, butylated hydroxytoluene, sinapinic alcohol, vitamin E, positive ten Eight alkyl-β-(4 '-hydroxyl -3 ', 5 '-di-tert-butyl-phenyl) propionic ester, the 2- tert-butyl groups -6- (3 '-tert-butyl group -5 '-methyl -2 ' - Hydroxybenzyl) -4- aminomethyl phenyls acrylate, 2,6- di-t-butyls -4- (N, N- dimethylaminomethyl) phenol, the uncles of 3,5- bis- Butyl -4- benzylphosphonic acids diethyl ester, 2,2 '-di-2-ethylhexylphosphine oxide (4- methyl-6-tert-butylphenols), 2,2 '-di-2-ethylhexylphosphine oxide (4- ethyl -6- tert-butyl phenols), 4,4 '-methylene-bis(2,6-di-t-butyl phenol), 2,2 '-di-2-ethylhexylphosphine oxide (4- methyl -6- Cyclohexylphenol), 2,2 '-dimethylene-bis- (6- Alpha-Methyls-benzyl-paracresol) 2,2 '-ethidine-bis- (4,6- di-t-butyls Phenol), 2,2 '-butane-bis- (4- methyl-6-tert-butylphenols), 4,4 '-butane double (3 methy 6 tert butyl phenol), Double -3- (3- tertiary butyl-4-hydroxy -5- aminomethyl phenyls) propionic esters of triethylene glycol-N-, double [3- (the bis- tertiary fourths of 3,5- of 1,6-HD Base -4- hydroxy phenyls) propionic ester], double [the 2- tert-butyl group -4- methyl 6- (the 3- tert-butyl group -5- methyl -2- hydroxybenzyls) phenyl] it is right Double { 2- [3- (3- tertiary butyl-4-hydroxy -5- aminomethyl phenyls) propiono the epoxide] -1,1- dimethyl second of phthalic acid ester, 3,9- Base } -2,4,8,10- four oxaspiro [5,5] hendecane, 4,4 '-thiobis (the 6- tert-butyl groups-metacresol), 4,4 '-thiobis (3- Methyl-6-tert-butylphenol), 2,2 '-thiobis (4- methyl-6-tert-butylphenols), double (3,5- di-t-butyl -4- hydroxyl benzyls Base) thioether, 4,4 '-two thio bis(2,6-di-butyl phenol)s, 4,4 '-three thio bis(2,6-di-butyl phenol)s, 2,2- Double (just pungent sulfenyl) -6- (the 4- hydroxyls of thiodiethylene pair-[3- (3,5- di-tert-butyl-hydroxy phenyls) propionic ester], 2,4- Base -3 ', 5 '-di-tert-butyl amido) -1,3,5- triazines, N, N '-hexamethylene bis-(3,5- di-t-butyl -4- hydroxy groups Cinnamamide), N, N '-bis- [3- (3,5- di-tert-butyl-hydroxy phenyls) propionos] hydrazine, (2- methyl -4- the hydroxyls of 1,1,3- tri- Base -5- tert-butyl-phenyls) butane, 1,3,5- trimethyls -2,4,6- three (3,5- di-tert-butyl-4-hydroxyl benzyls) benzene, three (3,5- Di-tert-butyl-hydroxy phenyl) isocyanuric acid ester, three (3,5- di-tert-butyl-4-hydroxyl benzyls) isocyanuric acid esters, 1,3,5- tri- (the 4- tert-butyl group -3- hydroxyl -2,6- dimethyl benzyls) isocyanuric acid ester, the [3- (3,5- di-t-butyl -4- hydroxy benzenes of 1,3,5- 32 Base) propiono epoxide] ethyl isocyanurate and four [methylene -3- (3 ', 5 '-di-tert-butyl-hydroxy phenyl) propionic esters] Methane etc..
As phosphite ester based compound, triphenyl phosphite, phosphorous acid three (nonyl phenyl) ester, phosphorous acid can be enumerated Three decyl esters, phosphorous acid trioctylphosphine ester, phosphorous acid three (octadecyl) ester, phosphorous acid didecyl list phenylester, phosphorous acid two are pungent Base mono-phemyol ester, phosphorous acid diisopropyl list phenylester, phosphorous acid monobutyl diphenyl, phosphorous acid list decyl diphenyl, Phosphorous acid list octyl diphenyl, phosphorous acid three (diethyl phenyl) ester, phosphorous acid three (diisopropyl phenyl) ester, phosphorous acid three (di-n-butyl phenyl) ester, phosphorous acid three (2,4- di-tert-butyl-phenyls) ester, phosphorous acid three (2,6- di-tert-butyl-phenyls) ester, two Stearyl pentaerythritol diphosphites, double (2,4- di-tert-butyl-phenyls) pentaerythritol diphosphites, double (bis- tertiary fourths of 2,6- Base -4- aminomethyl phenyls) pentaerythritol diphosphites, double (2,6- di-t-butyl -4- ethylphenyls) pentaerythrite diphosphorous acids Ester, double { double (1- methyl isophthalic acids-phenylethyl) phenyl of 2,4- } pentaerythritol diphosphites, phenyl bisphenol-A pentaerythrite two are sub- Phosphate, double (nonyl phenyl) pentaerythritol diphosphites and dicyclohexyl pentaerythritol diphosphites etc..It is used as other Phosphite ester based compound, it can enumerate and be reacted with dihydric phenol class so as to the phosphite ester based compound with cyclic structure.
As phosphinate based compound, can enumerate：Four (2,4- di-tert-butyl-phenyls) -4,4 '-biphenylene two is sub- Phosphonate ester, four (2,4- di-tert-butyl-phenyls) -4,3 '-biphenylens, four (2,4- di-tert-butyl-phenyls) -3, 3 '-biphenylen, four (2,6- di-tert-butyl-phenyls) -4,4 '-biphenylens, four (2,6- bis- Tert-butyl-phenyl) -4,3 '-biphenylen, four (2,6- di-tert-butyl-phenyls) -3,3 '-biphenylenes, two sub- phosphine Acid esters, double (2,4- di-tert-butyl-phenyls) -4- phenyl-phenyls phosphinates, double (2,4- di-tert-butyl-phenyls) -3- phenyl-benzene Base phosphinate, double (2,6- di-n-butyls phenyl) -3- phenyl-phenyls phosphinates, double (2,6- di-tert-butyl-phenyls) -4- benzene Base-phenylphosphite ester and double (2,6- di-tert-butyl-phenyls) -3- phenyl-phenyl phosphinates etc..
As thioether based compound, can enumerate：Thiodipropionate dilauryl, thio-2 acid two (tridecyl) Ester, thio-2 acid myristyl ester, thio-2 acid distearyl base ester, (the 3- lauryl propane thioic acids of pentaerythrite-four Ester), pentaerythrite-four (3- laurylthiopropionates), pentaerythrite-four (3- octadecyls thiopropionate), season penta Tetrol four (3- myristyls thiopropionate) and pentaerythrite-four (3- stearyl-thios propionic ester) etc..As comprising ultraviolet The light stabilizer of light absorbers, it can enumerate：Benzophenone based compound, BTA based compound, aromatic series benzoic ether Based compound, oxanilide based compound, cyanoacrylate based compound and the amine compound that is obstructed etc..
As benzophenone based compound, can enumerate：Benzophenone, 2,4 dihydroxyl benzophenone, 2,2 '-dihydroxy Benzophenone, 2,2 ', 4,4 '-tetrahydroxybenzophenone, ESCALOL 567,2,2 '-dihydroxy -4,4 '-two Methoxy benzophenone, 2,2 '-dihydroxy -4,4 '-dimethoxy -5- sulfonyls benzophenone, 2- hydroxyl -4- octyloxy hexichol Ketone, 2- hydroxyl -4- dodecyloxy benzophenones, 2- hydroxyl -4- octyloxybenzophenones, 2- hydroxyl -4- methoxyl group -5- sulphurs Acyl group benzophenone, 5- chlorine-2-hydroxyls benzophenone, 2- hydroxyl -4- octyloxybenzophenones, 2- hydroxyl -4- methoxyl groups -2 ' - Carboxyl benzophenone and 2- hydroxyls -4- (2- hydroxy-3-methyls-acryloxy isopropoxy) benzophenone etc..
As BTA based compound, can enumerate：2- (5- methyl -2- hydroxy phenyls) BTA, 2- (3,5- bis- The tert-butyl group -2- hydroxy phenyls) BTA, 2- (tertiary pentyl -2- hydroxy phenyls of 3,5- bis-) BTA, 2- (3 ', 5 '-two uncles Butyl -4 '-methyl -2 '-hydroxy phenyl) BTA, 2- (tertiary pentyl -2- hydroxy phenyls of 3,5- bis-) -5- chlorobenzotriazoles, 2- (the 5- tert-butyl group -2- hydroxy phenyls) BTA, 2- [2 '-hydroxyl -3 ', 5 '-bis- (bis (alpha, alpha-dimethylbenzyl) base) phenyl] benzo three Azoles, 2- [2 '-hydroxyl -3 ', 5 '-bis- (bis (alpha, alpha-dimethylbenzyl) base) phenyl] -2H- BTAs and 2- (4 '-octyloxies -2 '-hydroxyl Phenyl) BTA etc..
As aromatic series benzoic ether based compound, can enumerate：Salicylic acid is to tert-butyl benzene base ester, salicylic acid to octyl group Salicylic acid alkyl phenyl esters such as phenylester etc..
As oxanilide based compound, can enumerate：2- ethyoxyls -2 '-ethyloxanilide, 2- ethyoxyls -5- The tert-butyl group -2 '-ethyloxanilide and 2- ethyoxyls -3 '-dodecyl butoxanilide etc..
As cyanoacrylate based compound, can enumerate：Ethyl -2- cyano group -3,3 '-diphenylacrylate ester, 2- Ethylhexyl-cyano group -3,3 '-diphenylacrylate ester etc..
As the amine compound that is obstructed, can enumerate：4- acetoxyl group -2,2,6,6- tetramethyl piperidines, 4- stearoyl ketos Base -2,2,6,6- tetramethyl piperidines, 4- acryloxy -2,2,6,6- tetramethyl piperidines, 4- (phenylacetyl epoxide) -2,2,6, 6- tetramethyl piperidines, 4 benzoyloxy 2,2,6,6 tetramethyl piperidine, 4- methoxyl group -2,2,6,6- tetramethyl piperidines, 4- ten Eight alkyl oxy -2,2,6,6- tetramethyl piperidines, 4- cyclohexyl epoxide -2,2,6,6- tetramethyl piperidines, 4- benzyls epoxide -2,2, 6,6- tetramethyl piperidines, 4- phenoxy group -2,2,6,6- tetramethyl piperidines, 4- (ethylcarbamoyl epoxide) -2,2,6,6- tetramethyls Phenylpiperidines, 4- (cyclohexyl carboxyamide epoxide) -2,2,6,6- tetramethyl piperidines, 4- (phenylcarbamoyl epoxide) -2,2,6, 6- tetramethyl piperidines, double (2,2,6,6- tetramethyl -4- piperidyls) carbonic esters, double (2,2,6,6- tetramethyl -4- piperidyls) grass Acid esters, double (2,2,6,6- tetramethyl -4- piperidyls) malonates, bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, Double (2,2,6,6- tetramethyl -4- piperidyls) adipate esters, double (2,2,6,6- tetramethyl -4- piperidyls) terephthalates, 1,2- double (2,2,6,6- tetramethyl -4- piperidyls epoxide)-ethane, α, α '-bis- (2,2,6,6- tetramethyl -4- piperidyl oxygen Base)-paraxylene, double (2,2,6,6- tetramethyl -4- piperidyls)-toluylene -2,4- diurethanes, it is double (2,2, 6,6- tetramethyl -4- piperidyls)-hexa-methylene -1,6- diurethanes, three (2,2,6,6- tetramethyl -4- piperidyls) - Benzene -1,3,5- tricarboxylic esters, three (2,2,6,6- tetramethyl -4- piperidyls)-benzene -1,3,4- tricarboxylic esters, 1,2- { 3- (3,5- Di-tert-butyl-hydroxy phenyl) propiono epoxide } -2,2,6,6- tetramethyl piperidines and 1,2,3,4- BTCAs and 1, 2,2,6,6- pentamethyl -4- hydroxy piperidines and β, β, β ', the β '-tetramethyl -3,9- [oxaspiros (5,5) of 2,4,8,10- tetra- 11 Alkane] dimethanol condensation product etc..
As antistatic additive, can enumerate：The toner bodies such as carbon black, graphite, tin antimony composite oxides, antimony indium tin are answered Close the metal oxygens such as oxide, indium tin composite oxides, the electric conductivity indium oxide for being doped with Sn, F, Cl etc., tin oxide, zinc oxide Inorganic system's antistatic additive such as the various metallic particles such as compound, copper, nickel, silver, gold, aluminium (powder) or metallic fiber and (β-bay Acid amides propiono) quaternary ammonium salt system, sulfonate based compound, the alkyl phosphate such as trimethyl ammonium sulfate, neopelex Antistatic additive of the organic systems such as based compound etc..
As fire retardant, can enumerate：Bromide fire retardant, phosphorus flame retardant, chlorine-based flame retardant, triazine flame retardant, with And other inorganic flame retardants such as salt of phosphoric acid and piperazine etc..
As bromide fire retardant, can enumerate：Brominated Polystyrene, brominated polyacrylate, brominated polyphenylether, bromination are double Phenol A types epoxy resin, brominated bisphenol a type epoxy resin molecule chain end glycidyl part or all by envelope The modifier at end, the polycarbonate oligomer of Material synthesis, the phthalimide chemical combination of bromination two are used as using brominated bisphenol A The compounds such as the brominated diphenyl base alkane such as thing, bromination Biphenyl Ether and 1,2- bis- (penta-bromophenyl) ethane.Wherein it is possible to enumerate：Poly- three The brominated Polystyrenes such as bromstyrol, poly- (dibromobenzene aether), decabrominated dipheny base ether, double (tribromophenoxy) ethane, 1,2- bis- (five Bromophenyl) ethane, ethene-bis--(tetrabromo phthalimide), tetrabromobisphenol A, brominated polycarbonate oligomer, poly- tribromo The brominated Polystyrenes such as styrene, 1,2- bis- (penta-bromophenyl) ethane etc..
As phosphorus flame retardant, can enumerate：Trimethyl phosphate, triethyl phosphate, tributyl phosphate, tricresyl phosphate (2- second Base hexyl) ester, tributoxyethyl phosphate, triphenyl phosphate, lindol, tricresyl phosphate (xylyl) ester, phosphoric acid Three (isopropyl phenyl) esters, tricresyl phosphate (phenyl) ester, tricresyl phosphate naphthyl ester, tricresyl phosphate base diphenyl, phosphoric acid diformazan Phenyl diphenyl, diphenyl phosphate (2- ethylhexyls) ester, di(2-ethylhexyl)phosphate (isopropyl phenyl) phenylester, mono phosphoric acid ester isodecyl Ester, 2- acryloyl-oxyethyls phosphate ester acid, 2- methacryloxyethyls phosphate ester acid, diphenyl -2- acryloyls Epoxide ethyl phosphonic acid ester, diphenyl -2- methacryloxyethyls phosphate, melamine phosphate, two (melamines) Phosphate, melamine pyrophosphoric ester, triphenylphosphine oxide, trimethylphenyl phosphine oxide, methanephosphonic acid diphenyl ester, phenyl-phosphonic acid two The phosphates such as ethyl ester, resorcinol Polyphenyl phosphate, 1,3- phenylenes double (2,6- dimethylphenylphosphates), resorcinols Poly- (two -2,6- xylyls) phosphate, polymer with bis phenol A tolyl phosphate, bisphenol-A Polyphenyl phosphate, the poly- (2,6- bis- of quinhydrones Tolyl) condensed phosphoric acid esters such as the aromatic condensation phosphate such as phosphate and their condensation product etc..
As chlorine-based flame retardant, can enumerate：The cyclodecane of pentachloro- five, hexachloro-benzene, toluene pentachloride, tetrachlorobisphenol A and polychlorostyrene Styrene etc..As triazine flame retardant, can enumerate：Melamine, methyl guanamines, benzoguanamine, acryloyl guanamines, 2,4- Diaminourea -6- nonyl -1,3,5- triazines, 2,4- diaminourea -6- hydroxyl -1,3,5- triazines, 2- amino -4,6- dihydroxy -1,3, 5- triazines, 2,4- diaminourea -6- methoxyl group -1,3,5- triazines, 2,4- diaminourea -6- ethyoxyl -1,3,5- triazines, 2,4- diaminos Base -6- propoxyl group -1,3,5- triazines, 2,4- diaminourea -6- isopropoxy -1,3,5- triazines, 2,4- diaminourea -6- sulfydryl -1, 3,5- triazines and 2- amino -4,6- dimercapto -1,3,5- triazines etc..
As phosphoric acid and the salt of piperazine, can enumerate：Orthophosphoric acid piperazine, piperazine pyrophosphate and polyphosphoric acid piperazine etc..
As inorganic flame retardant, can enumerate：The antimonials such as antimony trioxide, Antimony pentachloride, Firebrake ZB, Boratex, Aluminium hydroxide, magnesium hydroxide and red phosphorus etc..
As bactericide, can enumerate：The copper fungicides such as copper 8-hydroxyquinolinate, zineb (Zineb), maneb (Maneb) etc. have The organochlorine such as machine thiophanate fungicide, captan, Bravo system bactericide, thiophanate-methyl, benomyl, carbendazim, thiabendazole etc. The acyls such as the dicarboximide system such as benzimidazole system bactericide, iprodione, vinclozolin, procymidone bactericide, furametpyr The morpholine system bactericide such as the phenylpyrrole such as amine system bactericide, fludioxonil system bactericide, dimethomorph, Fluoxastrobin, kresoxim-methyl, The anilino-pyrimidine system bactericide such as the methoxy acrylate such as ORIBRIGHT system bactericide, mepanipyrim, cyprodinil, pyrimethanil, The soil fungicides such as the ergosterol biosynthesis inhibitors such as triazolone, fluorine bacterium azoles, trichloronitromethane, PCNB and fluorine pyridine Amine, o-phenyl phenol (OPP), diphenyl, chlorodiphenyl base, cresols, 1,2- double (acetyl bromide epoxide) ethane, cinnamic acid, acetic acid benzene The bromo- 3- itrile groups propionyl of ester, allyl isothiocyanate, Alpha-Methyl acetophenone, thymol, full-chloro-cyclopentadiene, bromoacetic acid, 2,2- bis- Amine, ethyl chloroacetate, butyl chloroacetate, methyl chloroacetate, 5- chloro-2-methyl isothiazoline -3- ketone, glutaraldehyde and Hinokitiol Deng.
As antiseptic, can enumerate：Make silver, zinc, one kind of copper or antibiotic property Metal Supported of more than two kinds in inorganization Inorganic system's powder obtained from compound.As load, can enumerate：Zeolite, apatite, basic zirconium phosphate, titanium oxide, silica Gel, aluminum sulfate hydroxide, calcium phosphate, calcium silicates etc..It can in addition contain enumerate：With phosphate, boric acid system, silicic acid system Be respectively glass one kind or two or more glass as glass forming constituents in containing silver, zinc, copper one kind or two or more Antibiotic property metal obtained from antibacterial glass powder.
As lubricant, can enumerate：Aliphatic acid, fatty acid metal salts, oxo aliphatic acid, paraffin, low molecule amount it is poly- Alkene, fatty acid amide, alkylenebisfatty acid amides, aliphatic ketone, fatty acid part saponification ester, aliphatic acid low-carbon-ester, fat Acid polyol ester, fatty acid polyglycol ethanol ester and modified organic silicon etc..
As aliphatic acid, can enumerate：Oleic acid, stearic acid, laurate, hydroxy stearic acid, behenic acids, arachidonic acid, The aliphatic acid of the carbon numbers 6~40 such as linoleic acid, leukotrienes, ricinoleic acid, palmitic acid, montanic acid and their mixture.As fat Fat acid metal salt, it can enumerate：It is sodium laurate, potassium laurate, Magnesium dilaurate, calcium laurate, zinc laurate, barium laurate, hard Resin acid sodium, potassium stearate, magnesium stearate, calcium stearate, zinc stearate, barium stearate, behenic acid sodium, behenic acid potassium, behenic acids Alkali (soil) gold of the aliphatic acid of carbon number 6~40 such as magnesium, behenic acid calcium, behenic acid zinc, behenic acids barium, montanic acid sodium and montanic acid calcium Belong to salt.
As oxo aliphatic acid, can enumerate：1,2- stearoxylic acids etc..
As paraffin, can enumerate：The paraffin of the carbon numbers such as atoleine, natural paraffin wax, microwax and vaseline more than 18.
As the polyolefin of low molecule amount, can enumerate：Tissuemat E, maleic acid modified Tissuemat E, the poly- second of oxidized form The polyolefin of alkene wax, haloflex wax and polypropylene wax equimolecular quantity below 5000., specifically can be with as fatty acid amide Enumerate：The fatty acid amide of the carbon numbers more than 6 such as oleamide, erucic amide, Shan Yu acid amides.
As alkylenebisfatty acid amides, can enumerate：Methylene bis stearamide, ethylenebisstearamide and N, N- The alkylenebisfatty acid amides of the carbon numbers more than 6 such as double (2- hydroxyethyls) stearmides.
As aliphatic ketone, can enumerate：The aliphatic ketone of the carbon numbers such as higher aliphatic ketone more than 6.As fatty acid moieties Divide saponification ester, can enumerate：Partly-hydrolysed ester of montanic acid etc..
As aliphatic acid low-carbon-ester, can enumerate：Stearate, oleate, linoleate, linolenate, adipic acid Ester, behenic acids ester, arachidonate, montanate and isostearate etc..
As polyol esters of fatty acids, can enumerate：Glycerine tristearate, glycerine distearate, glycerine Monostearate, pentaerythritol tetrastearate, pentaerythrite tristearate, the myristinate of pentaerythrite two, Ji Wusi Alcohol monostearate, pentaerythritol adipate stearate and anhydrous sorbitol Dan behenic acid esters etc..
As fatty acid polyglycol ethanol ester, can enumerate：Cithrol, polytrimethylene diol fatty acid ester and Polypropylene glycol fatty acid esters etc..
As modified organic silicon, can enumerate：The alkoxy-modified organosilicon of organic silicon modified by polyether, higher fatty acids, contain Organosilicon, high-grade aliphatic ester modified organic silicon, methacrylic modified organic silicon and the fluorine richness for having higher fatty acids have Machine silicon etc..
As solidification catalyst, can enumerate：(peroxidized t-butyl perbenzoate, benzoyl peroxide, peroxidating first and second Ketone etc.) and organic peroxide, octyl group acid tin, the dibutyl such as azo-compound (azodiisobutyronitrile and AMBN etc.) Tin two (2 ethyl hexanoic acid ester), dioctyl tin two (2 ethyl hexanoic acid ester), dioctyl tin diacetate esters, dibutyltindilaurylmercaptide cinnamic acid Ester, dioctyl tin dilaurate, Dibutyltin oxide, dioctyl tin oxide, dibutyl tin soap, 2 ethyl hexanoic acid Lead, zinc octoate, zinc naphthenate, fatty acid zinc class, cobalt naphthenate, calcium octoate, copper naphthenate, 2 ethyl hexanoic acid lead lead octoate and four The inorganic acids such as Organometallic derivatives, hydrochloric acid, nitric acid, the sulfuric acid such as the metals such as n-butyl titanate and organic and inorganic acid salt, The sulfoacid compounds such as p-methyl benzenesulfonic acid, DBSA, dinonylnaphthalene sulfonic acid, dinonylnaphthalene disulfonic acid, sulfoacid compound Amine corrective, organic amine, phosphoric acid, the pyrophosphoric acid such as triethylamine etc., phosphate monoester or di-phosphate ester etc..As phosphate monoester, Such as it can enumerate：Mono-octyl phosphate, mono phosphoric acid ester propyl ester and mono phosphoric acid ester lauryl etc..As di-phosphate ester, such as can enumerate： Dioctylphosphoric acid ester, phosphoric acid dipropyl and didodecyl phosphate etc..And then it can enumerate：Single (2- (methyl) acryloxy second Base) phosphate cpd, diazabicyclo endecatylene series catalysts, lewis acid and the acid anhydrides such as phosphate ester acid etc..
As Photoepolymerizationinitiater initiater, can enumerate：(2-hydroxybenzoyl) compound (2- hydroxy-2-methyl -1- phenyl-propanes - 1- ketone, 1- hydroxycyclohexylphenylketones, benzoin alkylether etc.), benzoyl formic acid ester compounds (methylbenzoyl formate Deng), thioxanthone compounds (isopropyl thioxanthone etc.), benzophenone cpd (benzophenone etc.), phosphate compound (1,3, 5- trimethylbenzoyl diphenyl phosphine oxides etc.) and benzil dimethyl ketal etc..
And then coating is mixed in so as to which answering for the present invention can also be made by the way that the mechanoluminescence ceramic material of the present invention is matched somebody with somebody Power photism coating composition.
The stress irradiance coating composition of the present invention can be coated with the surface of other materials, to being coated with the luminescent material Material apply mechanical external force when, the luminous material layer of material surface is lighted due to deformation.
In addition, the stress irradiance coating composition of the invention of the mechanoluminescence ceramic material containing the present invention is luminous Brightness is high, therefore can carry out visual high application.
As coating composition, the coating composition containing overlay film formative resin can be used.In coating composition, root It can also contain according to needs：Solvent, dispersant, filler, thickener, levelling agent, curing agent, crosslinking agent, pigment, defoamer, The coating such as antioxidant, the light stabilizer comprising ultra-violet absorber, fire retardant, solidification catalyst, bactericide and antiseptic Use additive.
As the material used in coating composition, thermosetting resin, normal temperature cure resin, ultraviolet can also be used The various resins such as curable resin, radiation curing resin, such as can enumerate：Acrylic resin, alkyd resin, poly- ammonia Ester resin, polyester resin, amino resins etc., organosilicon acid esters, organic titanate etc..
As black film formation material, can enumerate：Polyurethane resin, acrylic resin, polyamide, vinyl chloride- Vinyl acetate resin and propylene dichloride resin etc..
As solvent, can enumerate：Aliphatic hydrocarbon, aromatic hydrocarbon (C7~10, such as toluene, dimethylbenzene and ethyl Benzene), ester or ether-ether (C4~10, such as methoxybutyl acetic acid esters), ether (C4~10, such as tetrahydrofuran, EG single ethyl Ether, EG single-butyl ether, PG monomethyl ether and DEG single ethylether), (C3~10, such as methyl iso-butyl ketone (MIBK), two are just for ketone Butyl ketone), alcohol (C1~10, such as methanol, ethanol, normal propyl alcohol and isopropanol, n-butanol, isobutanol, sec-butyl alcohol and the tert-butyl alcohol, 2- ethylhexyl alcohols), acid amides (C3~6, such as dimethylformamide, dimethyl acetamide, 1-METHYLPYRROLIDONE), sulfoxide (C2~4, such as dimethyl sulfoxide (DMSO)) and their mixed solvent of more than two kinds, water or foregoing mixed solvent.As scattered Agent, as long as being macromolecule dispersing agent, it can enumerate：The formal of naphthalene sulfonate [alkali metal (Na and K etc.) salt, ammonium salt etc.] Woods condensation product, poly styrene sulfonate (same as described above), polyacrylate (same as described above), poly- (2~4) carboxylic acid (Malaysia Acid/glycerine/monoallyl ether copolymer etc.) salt (same as described above), carboxymethyl cellulose (Mn2000~10000) and polyethylene Alcohol (Mn2000~100000) etc..
As low molecule dispersant, following substances can be enumerated.
(1) poly (oxyalkylene) fundamental mode
Aliphatic alcohol (C4~30), [alkyl (C1~30)] phenol, aliphatic (C4~30) amine and aliphatic (C4~30) acid amides 1~30 mole of addition product of AO (C2~4).
As aliphatic alcohol, there are n-butanol, isobutanol, sec-butyl alcohol and the tert-butyl alcohol, octanol, dodecanol etc.；As (alkane Base) phenol, there are phenol, methylphenol and nonyl phenol etc.；As aliphatic amine, there are lauryl amine and methyl stearic amine etc.； With as aliphatic amide, there is stearmide etc..
(2) polyol type
The aliphatic acid (laurate, stearic acid etc.) of C4~30 and polynary (2~6 or its more than) alcohol (such as GR, PE, D-sorbite And anhydrous sorbitol) monoester compound.
(3) carboxylic acid type
Alkali metal (same as described above) salt of the aliphatic acid (same as described above) of C4~30.
(4) sulfuric acid ester type
The sulfuric ester of the aliphatic alcohol (same as described above) of C4~30 and AO (C2~4) 1~30 mole of addition product of aliphatic alcohol Alkali metal (same as described above) salt etc..
(5) sulfonate type
Sulfonate alkali metal (same as described above) salt of [alkyl (C1~30)] phenol (same as described above).
(6) phosphate type
The monophosphate of the aliphatic alcohol (same as described above) of C4~30 and AO (C2~4) 1~30 mole of addition product of aliphatic alcohol The salt of ester or bisphosphate [alkali metal (same as described above) salt, quaternary ammonium salt etc.].
(7) primary~tertiary amine salt form
Aliphatic amine [primary amine (lauryl amine etc.), secondary amine (dibutylamine etc.) and the tertiary amine (dimethylstearamine of C4~30 Deng)] inorganic acid (hydrochloric acid, sulfuric acid, the nitric acid of the monoesters of hydrochloride, triethanolamine and the aliphatic acid of C4~30 (same as described above) With phosphoric acid etc.) salt.
(8) quaternary
The inorganic acid of the quaternary ammonium (butyl trimethyl ammonium, diethyl lauryl methyl ammonium, dimethyl distearyl ammonium etc.) of C4~30 (same as described above) salt etc..
As inorganic dispersant, can enumerate：Alkali metal (same as described above) salt and phosphate dispersant (phosphorus of polyphosphoric acid Acid, monoalkyl phosphoric acid esters and dialkyl phosphate etc.) etc..
As filler, can enumerate：It is inorganic as the oxide system of representative using silica, aluminum oxide, zirconium oxide, mica The organic compounds such as the micro mist or acrylic resin, fluororesin of the non-oxidized substance based inorganic material such as thing, carborundum, silicon nitride.Separately Outside, the metal dusts such as aluminium, zinc, copper can also be added according to purposes.And then as the concrete example of filler, it can enumerate：Dioxy SiClx colloidal sol, zirconia sol, alumina sol, TiO 2 sol isosol；Silica sand, quartz, close quartzy salt, diatomite Etc. silica-based material；Synthesize amorphous silica；Kaolinite, mica, talcum, wollastonite, asbestos, calcium silicates, silicic acid The silicate such as aluminium；The vitreums such as glass powder, glass marble, hollow glass ball, glass flake, bulb glass ball；Boron nitride, carbonization The non-oxidized substance based inorganic material such as boron, aluminium nitride, aluminium carbide, silicon nitride, carborundum, titanium boride, titanium nitride, titanium carbide；Calcium carbonate； The metal oxides such as zinc oxide, aluminum oxide, magnesia, titanium oxide, beryllium oxide：Barium sulfate, molybdenum disulfide, tungsten disulfide, fluorination The inorganic matters such as carbon；The metal dusts such as aluminium, bronze, lead, stainless steel, zinc；With carbon black, coke, graphite, thermally decomposed carbon, hollow carbon balls Deng carbon body etc..
As thickener, can enumerate：Montmorillonite system clay mineral, the bentonite comprising these mineral, colloidal oxidation The inorganic filler such as aluminium system thickener, methylcellulose, carboxymethyl cellulose, hexyl methyl cellulose, hydroxyethyl cellulose, hydroxyl The cellulose-based thickeners such as propyl cellulose, polyurethane resin system thickener, polyvinyl alcohol, polyvinylpyrrolidone, polyethylene The polyethers trees such as the polyethylene-based thickener such as benzyl ether copolymer, polyethers dialkyl ester, polyethers dialkyl ether, the epoxide modified thing of polyethers The association thickeners such as fat system thickener, urethane-modified polyethers system, polyurethane resin system of PPG system etc. are special The eggs such as the surfactant system such as macromolecule nonionic thickener, nonionic system thickener, casein, casein acid sodium, casein acid ammonium Acrylic thickeners such as white matter system thickener and mosanom etc..
As levelling agent, can enumerate：PEG types nonionic surfactant (nonyl phenol EO1~40 mole addition product, Stearic acid EO1~40 mole addition product etc.), polyol-based non-ionic surfactant (anhydrous sorbitol palm acid monoester, dehydration Sorbierite stearate monoesters, the ester of anhydrous sorbitol stearic acid three etc.), fluorine-containing surfactant (perfluoroalkyl EO1~50 mole plus Into thing, perfluoroalkyl carboxylate, perfluoroalkyl betain etc.) and modified silicon oil [polyether modified silicon oil, (methyl) acrylate Modified silicon oil etc.] etc..
For curing agent, as the curing agent of polyalcohols, can enumerate：Hexamethylene diisocyanate, trimethyl six Methylene diisocyanate, IPDI, hydrogenated diphenyl methane diisocyanate, the isocyanide of diphenyl methane two Acid esters, xylylene diisocyanate, hydrogenation xylylene diisocyanate, toluylene diisocya-nate, hydrogenation first generation Phenylene vulcabond, lysine diisocyanate, the nurate bodies of polyisocyanate compound, buret bodies, polyisocyanic acid The addition body of polyalcohol as ester compounds and ethylene glycol, propane diols, trimethylolpropane, by blocked polyisocyanic acid The monomers such as ester curing agent or mixture of more than two kinds, their polyalcohol addition product, their copolymer, block polymer etc. The isocyanates that can solidify at normal temperatures like that.As the curing agent of epoxy resin, can enumerate：Acid anhydrides, phenolic aldehyde tree Fat, polyamide, amine additives, urea resin, melmac and isocyanates etc..
As crosslinking agent, can enumerate：The more isocyanides of melmac, urea resin, polyisocyanate compound, block Ester compound, epoxide or resin, carboxylated compound or resin, acid anhydrides, based compound containing alkoxy silane or tree Fat and hexamethoxy methylated melamine, N, N, N ', N '-tetrakis hydroxymethyl phosphonium succinamide, tetramethoxymethylization urine Element, 2,4,6- tetrakis hydroxymethyl phosphonium phenol etc. have the compound of hydroxymethyl and methoxy or ethoxyl methyl etc..
As pigment, in addition to aforesaid pigments, can also enumerate：Vanadium pentoxide, calcium vanadate, vanadic acid magnesium and ammonium metavanadate Deng vfanadium compound；Magnesium phosphate, ammonium magnesium phosphate eutectoid thing, the hydrogen magnesium of phosphoric acid one, magnesium dihydrogen phosphate, magnesium phosphate calcium eutectoid thing, phosphorus Sour magnesium cobalt eutectoid thing, magnesium phosphate nickel eutectoid thing, phosphorous acid magnesium, phosphorous acid magnesium calcium eutectoid thing, three polyphosphoric acid aluminum dihydrogens, three The phosphate metals such as polyphosphoric acid magnesium, the magnesia processed material of three polyphosphoric acid aluminum dihydrogens, the magnesia processed material of three polyphosphoric acid dihydro zinc The silica modified chemical combination of magnesium phosphate as the processed material of the magnesium-containing compound of salt and then silica modified magnesium phosphate etc. The phosphate-based rust resisting pigment such as thing；The rust resisting pigment containing zinc composition such as trbasic zinc phosphate, magnesium handle three polyphosphoric acid aluminum dihydrogens, Calcium treatment Calcium phosphate etc. is without zinc rust resisting pigment；The calcium silicates such as the composite calcium silicate comprising calcium orthosilicate composition or calcium metasilicate composition；Calcium from Son exchanges silica, magnesium ion exchanges the metal ion exchanged silica such as silica；With preventing comprising Cr VI, lead etc. Become rusty pigment etc..
As defoamer, such as can enumerate：Silicone oil, dimethyl polysiloxane, organic modified polyorganosiloxane, fluorine richness gather The silicon-type such as siloxanes defoamer, mineral oil system defoamer, non-organic silicon polymer system defoamer, comprising changing selected from organic At least one kind of defoamer in property fluorine compounds and poly (oxyalkylene) based compound and the aliphatic alcohol for including carbon number more than 18 Defoamer etc..
Light stabilizer, fire retardant, solidification catalyst, bactericide for antioxidant, comprising ultra-violet absorber and Antiseptic etc., aforementioned substances can be enumerated.
Brief description of the drawings
Fig. 1 is the mechanoluminescence spectrogram of the sample of embodiment 1 ~ 6 provided by the invention.
Fig. 2 is relative luminous brightness and the pressure graph of a relation of the sample of embodiment 1 ~ 6 provided by the invention.
Embodiment
1-2 and specific embodiment are described in further detail to the present invention below in conjunction with the accompanying drawings.
Embodiment 1
A kind of yellow green mechanoluminescence ceramic material, chemical composition Sr1.98Si7O4N8: 0.01Eu2+, 0.01Gd3+。
With the SrCO of high-purity3、SiO2、Si3N4、Eu2O3And Gd2O3As raw material, according to chemical composition formula Sr1.98Si7O4N8: 0.01Eu2+, 0.01Gd3+The proportioning of middle each element, accurately weighs raw material；Using agate ball as mill ball, Using absolute ethyl alcohol as ball-milling medium, agate ball, absolute ethyl alcohol and raw material are put into ball grinder simultaneously, in planetary ball mill Upper ball mill mixing 10 hours, pulp-like mixture is formed, the mass ratio of the absolute ethyl alcohol and raw material is 2:3；By the slurry of acquisition Material shape mixture is placed in baking oven, insulation drying 4 hours under the conditions of 80 DEG C, then the raw material obtained after drying is crossed into 200 mesh sieves Son, obtain well mixed raw material；A certain amount of well mixed raw material is weighed, is put into dry-pressing formed in stainless steel mould, pressure For 10MPa, cylindrical greenwave is obtained；The greenwave of acquisition is subjected to high temperature sintering, sintering atmosphere 5% under reducing atmosphere condition H2/95%N2Hydrogen nitrogen mixed gas, heating rate is 5 DEG C/min, and sintering temperature is 1500 DEG C, and sintering time is 8 hours, after cooling Take out and produce a kind of yellow green mechanoluminescence ceramic material.
Embodiment 2
A kind of yellow green mechanoluminescence ceramic material, chemical composition Sr1.96Si7O4N8: 0.02Eu2+, 0.02Lu3+。
With the SrCO of high-purity3、SiO2、Si3N4、Eu2O3And Lu2O3As raw material, according to chemical composition formula Sr1.96Si7O4N8: 0.02Eu2+, 0.02Lu3+The proportioning of middle each element, accurately weighs raw material；Using agate ball as mill ball, Using absolute ethyl alcohol as ball-milling medium, agate ball, absolute ethyl alcohol and raw material are put into ball grinder simultaneously, in planetary ball mill Upper ball mill mixing 5 hours, pulp-like mixture is formed, the mass ratio of the absolute ethyl alcohol and raw material is 2:3；By the slurry of acquisition Shape mixture is placed in baking oven, insulation drying 6 hours under the conditions of 80 DEG C, then the raw material obtained after drying is crossed into 200 mesh sieve, Obtain well mixed raw material；A certain amount of well mixed raw material is weighed, is put into dry-pressing formed in stainless steel mould, pressure is 15MPa, obtain cylindrical greenwave；The greenwave of acquisition is subjected to high temperature sintering, sintering atmosphere 5%H under reducing atmosphere condition2/ 95%N2Hydrogen nitrogen mixed gas, heating rate is 5 DEG C/min, and sintering temperature is 1600 DEG C, and sintering time is 6 hours, is taken after cooling Go out to produce a kind of yellow green mechanoluminescence ceramic material.
Embodiment 3
A kind of yellow green mechanoluminescence ceramic material, chemical composition Sr1.92Si7O4N8: 0.04Eu2+, 0.02Gd3+, 0.02Lu3+。
With the SrCO of high-purity3、SiO2、Si3N4、Eu2O3、Gd2O3And Lu2O3As raw material, according to chemical composition formula Sr1.92Si7O4N8: 0.04Eu2+, 0.02Gd3+, 0.02Lu3+The proportioning of middle each element, accurately weighs raw material；Made with agate ball For mill ball, using absolute ethyl alcohol as ball-milling medium, agate ball, absolute ethyl alcohol and raw material are put into ball grinder simultaneously, are expert at Ball mill mixing 15 hours on planetary ball mill, pulp-like mixture is formed, the mass ratio of the absolute ethyl alcohol and raw material is 2:3； The pulp-like mixture of acquisition is placed in baking oven, insulation drying 5 hours under the conditions of 80 DEG C, then the raw material that will be obtained after drying 200 mesh sieve are crossed, obtain well mixed raw material；A certain amount of well mixed raw material is weighed, is put into dry-pressing in stainless steel mould Shaping, pressure 15MPa, obtains cylindrical greenwave；The greenwave of acquisition is subjected to high temperature sintering under reducing atmosphere condition, sintered Atmosphere is 5%H2/95%N2Hydrogen nitrogen mixed gas, heating rate is 5 DEG C/min, and sintering temperature is 1550 DEG C, and sintering time is 9 small When, taken out after cooling and produce a kind of yellow green mechanoluminescence ceramic material.
Embodiment 4
A kind of yellow green mechanoluminescence ceramic material, chemical composition Sr1.88Si7O4N8: 0.06Eu2+, 0.04Gd3+, 0.02Lu3+。
With the SrCO of high-purity3、SiO2、Si3N4、Eu2O3、Gd2O3And Lu2O3As raw material, according to chemical composition formula Sr1.88Si7O4N8: 0.06Eu2+, 0.04Gd3+, 0.02Lu3+The proportioning of middle each element, accurately weighs raw material；Made with agate ball For mill ball, using absolute ethyl alcohol as ball-milling medium, agate ball, absolute ethyl alcohol and raw material are put into ball grinder simultaneously, are expert at Ball mill mixing 20 hours on planetary ball mill, pulp-like mixture is formed, the mass ratio of the absolute ethyl alcohol and raw material is 2:3； The pulp-like mixture of acquisition is placed in baking oven, insulation drying 5 hours under the conditions of 80 DEG C, then the raw material that will be obtained after drying 200 mesh sieve are crossed, obtain well mixed raw material；A certain amount of well mixed raw material is weighed, is put into dry-pressing in stainless steel mould Shaping, pressure 10MPa, obtains cylindrical greenwave；The greenwave of acquisition is subjected to high temperature sintering under reducing atmosphere condition, sintered Atmosphere is 5%H2/95%N2Hydrogen nitrogen mixed gas, heating rate is 5 DEG C/min, and sintering temperature is 1400 DEG C, and sintering time is 10 small When, taken out after cooling and produce a kind of yellow green mechanoluminescence ceramic material.
Embodiment 5
A kind of yellow green mechanoluminescence ceramic material, chemical composition Sr1.84Si7O4N8: 0.08Eu2+, 0.05Gd3+, 0.03Lu3+。
With the SrCO of high-purity3、SiO2、Si3N4、Eu2O3、Gd2O3And Lu2O3As raw material, according to chemical composition formula Sr1.84Si7O4N8: 0.08Eu2+, 0.05Gd3+, 0.03Lu3+The proportioning of middle each element, accurately weighs raw material；Made with agate ball For mill ball, using absolute ethyl alcohol as ball-milling medium, agate ball, absolute ethyl alcohol and raw material are put into ball grinder simultaneously, are expert at Ball mill mixing 10 hours on planetary ball mill, pulp-like mixture is formed, the mass ratio of the absolute ethyl alcohol and raw material is 2:3； The pulp-like mixture of acquisition is placed in baking oven, insulation drying 6 hours under the conditions of 80 DEG C, then the raw material that will be obtained after drying 200 mesh sieve are crossed, obtain well mixed raw material；A certain amount of well mixed raw material is weighed, is put into dry-pressing in stainless steel mould Shaping, pressure 12MPa, obtains cylindrical greenwave；The greenwave of acquisition is subjected to high temperature sintering under reducing atmosphere condition, sintered Atmosphere is 5%H2/95%N2Hydrogen nitrogen mixed gas, heating rate is 5 DEG C/min, and sintering temperature is 1500 DEG C, and sintering time is 6 small When, taken out after cooling and produce a kind of yellow green mechanoluminescence ceramic material.
Embodiment 6
A kind of yellow green mechanoluminescence ceramic material, chemical composition Sr1.7Si7O4N8: 0.1Eu2+, 0.1Gd3+, 0.1Lu3+。
With the SrCO of high-purity3、SiO2、Si3N4、Eu2O3、Gd2O3And Lu2O3As raw material, according to chemical composition formula Sr1.7Si7O4N8: 0.1Eu2+, 0.1Gd3+, 0.1Lu3+The proportioning of middle each element, accurately weighs raw material；Using agate ball as grinding Abrading-ball, using absolute ethyl alcohol as ball-milling medium, agate ball, absolute ethyl alcohol and raw material are put into ball grinder simultaneously, planetary Ball mill mixing 15 hours on ball mill, pulp-like mixture is formed, the mass ratio of the absolute ethyl alcohol and raw material is 2:3；It will obtain The pulp-like mixture obtained is placed in baking oven, insulation drying 4 hours under the conditions of 80 DEG C, then the raw material mistake that will be obtained after drying 200 mesh sieve, obtain well mixed raw material；Weigh a certain amount of well mixed raw material, be put into stainless steel mould dry-pressing into Type, pressure 12MPa, obtain cylindrical greenwave；The greenwave of acquisition is subjected to high temperature sintering under reducing atmosphere condition, sinters gas Atmosphere is 5%H2/95%N2Hydrogen nitrogen mixed gas, heating rate is 5 DEG C/min, and sintering temperature is 1450 DEG C, and sintering time is 7 hours, Taken out after cooling and produce a kind of yellow green mechanoluminescence ceramic material.
Fig. 1 is the mechanoluminescence spectrogram of the sample of embodiment 1 ~ 6 provided by the invention, and test pressure is 30MPa.From figure As can be seen that under certain pressure conditions, the sample of embodiment 1 ~ 6 has obvious mechanoluminescence effect, emission peak wavelength About 550nm green-yellow light.Fig. 2 is between the relative luminous brightness of the sample of embodiment 1 ~ 6 provided by the invention and pressure size Graph of a relation, it can be seen that when pressure is less than 30MPa, the luminous intensity and pressure size of sample are proportional, Show that the size of pressure can be characterized using the size of luminous intensity, and add the Eu of doping various concentrations2+、Gd3+And Lu3 +When, under identical pressure condition, its mechanoluminescence intensity is different, and wherein embodiment 3 is preferred result.
The performance of mechanoluminescence material depends primarily on the crystal structure, active ions and three, Assisted Activation ion of matrix Element.（1）The influence of matrix：In crystal, cavitation damage VM2+, electronic defects VO2-And Eu2+Deng in electrostatic field In the presence of attract each other close, and form the defective system that is mutually related.Under the exciting of excitaton source, electronics is excited Probability on the conduction band higher to energy is little, can only the transition in the defective system that is mutually related.So different substrates bonding Situation, lattice parameter and ionic radius difference are to Eu2+Luminescent properties influence it is very big.（2）The influence of active ions：Conventional swashs Ion living has Yb2+、Eu2+、Ce3+、Pr3+、Tm3+And Tb3+Deng because the atomic number of various rare earth ions, ionization energy, electricity are negative Property, the various aspects such as level structure gap be present, therefore in identical lattice environment, the general also not phase of its characteristics of luminescence Together, emitted luminescence intensity and launch wavelength do not have predictability, it is impossible to are obtained from the prior art by simply deriving.This hair It is bright with Eu2+For ion as active ions, chemical composition formula is Sr2-x-ySi7O4N8: xEu2+, yRe3+, the material can pass through Pressure sensitive sends bright green-yellow light.（3）The influence of Assisted Activation ion：Common Assisted Activation ion has Dy3+、Pr3+、Y3 +、Ce3+、La3+、Ho3+、Lu3+、Tb3+、Sm3+、Gd3+、Er3+、Yb3+、Tm3+With Lu3+ etc., it is brilliant due to the doping of auxiliary activator Lattice size and shape is changed, and this just produces impurity energy level, and this impurity energy level is due to Assisted Activation ion substituent Caused by the hole generated when matter cation, these impurity energy levels are in Eu2+Ground state level and excited level it Between.Under the irradiation of excitaton source, Eu2+Electronics in ground state is excited so as to transit to excitation state, during exciting, some The form that electronics returns low-lying level by transition releases energy in the form of light, and other electronics enter the impurity energy level in hole, excite After stopping, the electronics being stored in impurity energy level absorbs energy because matrix is produced stronger thermal agitation by ambient pressure, Into Eu2+Excited level, and transition return ground state level during release energy in the form of light.Mechanoluminescence is strong Spend the electron amount depended primarily in impurity energy level and return to Eu from impurity energy level with density and these electronics2+Excitation state The speed of energy level, therefore, select suitable Assisted Activation ion most important.The invention provides two kinds of suitable Assisted Activations Ion, i.e. Gd3+And Lu3+Ion, the mechanoluminescence performance of the material can be significantly improved.

Claims (3)

1. a kind of yellow green mechanoluminescence ceramic material, it is characterised in that the chemical composition formula of the ceramic material is Sr2-x- ySi7O4N8: xEu2+, yRe3+, wherein Re is one or both of Gd and Lu combination, and x and y span are respectively： 0.01≤x≤0.1,0.01≤y≤0.2.
2. a kind of yellow green mechanoluminescence ceramic material according to claim 1, it is characterised in that described ceramic lights Center is Eu2+Ion, by introducing Gd3+And Lu3+It can effectively strengthen its mechanoluminescence effect Deng rare earth impurities ion.
3. a kind of preparation method of yellow green mechanoluminescence ceramic material, it is characterised in that comprise the following steps：
（1）Dispensing：With the SrCO of high-purity3、SiO2、Si3N4、Eu2O3、Gd2O3And Lu2O3As raw material, lead to according to chemical composition Formula Sr2-x-ySi7O4N8: xEu2+, yRe3+The proportioning of middle each element, accurately weighs raw material；
（2）Batch mixing：Using agate ball as mill ball, using absolute ethyl alcohol as ball-milling medium, by agate ball, absolute ethyl alcohol and raw material It is put into simultaneously in ball grinder, ball mill mixing 5 ~ 20 hours on planetary ball mill, forms pulp-like mixture, the anhydrous second The mass ratio of alcohol and raw material is 2:3；
（3）Drying：The pulp-like mixture of acquisition is placed in baking oven, insulation drying 4 ~ 6 hours under the conditions of 80 DEG C, then will be dry The raw material obtained after dry crosses 200 mesh sieve, obtains well mixed raw material；
（4）Shaping：A certain amount of well mixed raw material is weighed, is put into dry-pressing formed in stainless steel mould, pressure is 10 ~ 15MPa, Obtain cylindrical greenwave；
（5）Sintering：Described greenwave is subjected to high temperature sintering, sintering atmosphere 5%H under reducing atmosphere condition2/95%N2Hydrogen Nitrogen mixed gas, heating rate are 5 DEG C/min, and sintering temperature is 1400 ~ 1600 DEG C, and sintering time is 6 ~ 10 hours, is taken after cooling Go out to produce a kind of yellow green mechanoluminescence ceramic material.
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