CN107903065A - A kind of tribo-luminescence ceramic material and preparation method thereof - Google Patents

A kind of tribo-luminescence ceramic material and preparation method thereof Download PDF

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CN107903065A
CN107903065A CN201711061639.0A CN201711061639A CN107903065A CN 107903065 A CN107903065 A CN 107903065A CN 201711061639 A CN201711061639 A CN 201711061639A CN 107903065 A CN107903065 A CN 107903065A
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tribo
acid
luminescence
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CN107903065B (en
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杨道救
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Jiangxi Jinyang Ceramics Co., Ltd.
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Hangzhou Qingqing Science And Technology Co Ltd
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Abstract

The invention discloses a kind of tribo-luminescence ceramic material and preparation method thereof, it is desirable to provide a kind of pressure sensitive material with tribo-luminescent performance, belongs to luminescent ceramic technical field.The ceramic chemical composition general formula is Zn2‑x‑yOS:xMn2+,yRe3+, wherein Re is Y, the one or more combination in Gd and Nd, and the value range of x and y are respectively：0.01≤x≤0.1,0.01≤y≤0.1, the ceramic centre of luminescence are Mn2+Ion, by introducing Y3+, Gd3+And Nd3+It can effectively strengthen its tribo-luminescence effect Deng rare earth impurities ion.Ceramics provided by the invention have the features such as compression strength is high, tribo-luminescence positive effect, available for the pressure sensitive component in pressure sensor.

Description

A kind of tribo-luminescence ceramic material and preparation method thereof
Technical field
The invention belongs to ceramic technology field, more particularly to a kind of tribo-luminescence ceramic material and preparation method thereof.
Background technology
Luminescence phenomenon when tribo-luminescence refers to some solids by mechanical lapping, vibration or stress, this kind of luminescent substance can Mechanical energy is changed into luminous energy.Although the rupture of rock can cause to shine in 17th century is with regard to someone's record earthquake, arrive So far, triboluminescent mechanism is not studied also clear completely.Discovered in recent years triboluminescent material can be used for pressure-sensitive Shine sensory field, can be used for manufacturing pressure detecting sensors, is used in combination with photodetector, can the spy of development of new pressure Survey display element etc. in sensor, forecast monitor and some scientific instrument, it is this new friction pressure to be converted into light The sensing mode of degree, amount of electrons is converted into compared to old-fashioned by friction pressure, such as strain sensing and piezoelectric type sensing, is had non- Contact induction and the simpler advantage of electrical connection, thus the concern to it gradually increases, and can broadly be applied.
Tribo-luminescence material is increasingly subject to people to pay close attention in materials science field, external for triboluminescent research Since the 1980s, the material for being directed to finding or synthesizing excellent tribo-luminescence characteristic is answered for what pressure-sensitive shone With domestic last decade also increases the research of this respect, such as Changchun Applied Chemistry Research Inst., Chinese Academy of Sciences's rare earth chemistry and physics weight Point laboratory, photoelectron technology research institute of Northern Transportation University, Beijing Institute of Technology's photoelectric project center are all done in this respect Extensive work.The light emitting that tribo-luminescence is applied due to Solid Mechanics energy, spectral composition, mechanics and electrical property with solid Matter is associated.Document report mainly has seven kinds on triboluminescent source at present：The fluorescence of crystal, crystal phosphorescence, gas or its The shining of his gas, the shining of metal center, electric charge transfer shines, free atom group shines, black body radiation and conduction band to table The transition of face band.The material for being commonly used for research has：Sm3+ 、Eu3+ 、Tb3+Coordinate with the ternary of beta-diketon and organic phosphorous oxides Thing, Eu3+The mixture of ZnS etc. adulterated with the mixed ligand complexes of TTA and pyridines nitrogen oxides, Mn, they are both fine Fluorescent material, and tribo-luminescence material.For exciting triboluminescent mechanical energy to have diversified forms.Such as temperature vibration, it can To produce stress, crackle and crystal-phase transformation；Rapid crystallization, it can also produce stress and crack；Also by the crystal that collides, rubs And the anisotropic pressure and fluid produced is in surface of solids movement etc..Tribo-luminescence and other forms shine, such as thermoluminescence And chemiluminescence, often it is not easy to distinguish.For example in tribo-luminescence experiment, the mechanical energy acted on crystal can be converted into Thermal energy, and then cause thermoluminescence；Or there occurs a chemical reaction for generating excitation state product so as to cause to shine, these works With tribothermoluminescence is referred to alternatively as respectively, tribochemistry shines.
The content of the invention
The shortcomings of in order to overcome the luminous intensity of above-mentioned triboluminescent material in the prior art weaker, the present invention provides one The ceramic material of kind with higher tribo-luminescence efficiency and preparation method thereof, the ceramics have compression strength high, and tribo-luminescence is imitated The features such as fruit is obvious, available for the pressure sensitive component 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 tribo-luminescence ceramic material, the chemical composition general formula of the ceramic material is Zn2-x-yOS: xMn2+, yRe3+, its Middle Re is Y, the one or more combination in Gd and Nd, and the value range of x and y are respectively：0.01≤x≤0.1,0.01≤y≤ 0.1.Especially, the ceramic centre of luminescence is Mn2+Ion, by introducing rare earth ion Y3+、Gd3+And Nd3+In one kind or Several combinations provide trap level, can effectively strengthen its tribo-luminescence effect.
A kind of preparation method of tribo-luminescence ceramic material, it is characterised in that comprise the following steps：
（1）According to molar ratio 1:1 weighs the Zn (NO of certain mass respectively3)2And ZnSO4High pure raw material, it is dissolved at the same time In ionized water, certain density Zn (NO are obtained3)2And ZnSO4Mixed solution；
（2）H is continually fed into above-mentioned solution2S gases, when duration of ventilation is 0.5 ~ 1 small, obtain ZnS precipitations；
（3）The excessive NaOH solution of 1mol/L is added dropwise into above-mentioned solution again, obtains Zn (OH)2Precipitation；
（4）Above-mentioned turbid solution is loaded into autoclave, and reaction kettle is placed in baking oven and carries out heating reaction, heating-up temperature is 180 ~ 200 DEG C, when the reaction time is 2 ~ 4 small；
（5）The precipitation obtained after reaction is filtered, is dried, obtains a kind of forerunner's powder of nano-ZnO and ZnS mixing；
（6）With forerunner's powder of above-mentioned acquisition and high-purity MnCO3、Y2O3、Gd2O3、Nd2O3As raw material, according to chemical group Into Zn2-x-yOS: xMn2+, yRe3+The proportioning of middle each element, accurately weighs each raw material, and is uniformly mixed in agate mortar；
（7）The above-mentioned raw materials of certain mass are weighed, and it is dry-pressing formed in stainless steel mould, and pressure 10-15MPa, is justified Cylindricality greenwave；
（8）The greenwave is subjected to high temperature sintering under reducing atmosphere condition, heating rate is 10 DEG C/min, and sintering temperature is 1000 ~ 1400 DEG C, when sintering time is 4 ~ 10 small, taken out after cooling, up to the tribo-luminescence ceramic material.
Compared with prior art, the beneficial effects of the invention are as follows：
（1）Traditional ZnS: Mn2+The chemical stability of triboluminescent material is poor, its fluorescence emission peak is located at 580nm or so, people Class naked eyes are not easy to identify, and tribo-luminescence ceramic material provided by the invention has that tribo-luminescence is efficient, chemical stability is good The features such as, its luminous peak position is more advantageous to human eye identification in the green wavelength of 540nm or so；
（2）The preparation method of tribo-luminescence ceramic material provided by the invention is simple, is limited without harsh preparation process condition；
（3）The present invention is by introducing rare earth ion Y3+、Gd3+And Nd3+In one or more combination provide trap level, can Effectively strengthen its tribo-luminescence effect.
The invention also discloses a kind of stress irradiance element, using substrate made of above-mentioned tribo-luminescence 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, The pressure light-emitting film is above-mentioned tribo-luminescence ceramic powder or tribo-luminescence 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 tribo-luminescence ceramic powder or tribo-luminescence 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 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 tribo-luminescence ceramic powder particle as described above Suspension coated in substrate as described above.
Although suspension will be prepared into tribo-luminescence 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 tribo-luminescence ceramic powder particle can also change in a wider scope, preferable case Under, the suspension based on 100 parts by weight, the content of the tribo-luminescence ceramic powder particle is 0.5-10 weight Part, it is 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, carboxymethyl starch, acetic starch, hydroxymethyl cellulose and carboxymethyl cellulose.
According to the present invention, the content of the polymer substance can also change in a wider scope, under preferable case, base In the suspension of 100 parts by weight, the high molecular content is 1-10 parts by weight, is 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 tribo-luminescence ceramic powder particle coated on the substrate surface Method can be this area routine selection, can also be using printing it is for instance possible to use the painting method such as spraying, spin coating Technology.The suspension of tribo-luminescence 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 tribo-luminescence 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.
Tribo-luminescence ceramic powder particle of the present invention, pressure sensitive component 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, which includes high molecular material and described rubs Luminescent ceramic materials powder is wiped, tribo-luminescence ceramic powder is evenly distributed in high molecular material, tribo-luminescence ceramics material The addition at feed powder end is 1 ~ 90%；Preferably 10 ~ 80%.High molecular 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, which can also add coupling agent, lubricant, plasticizer etc..
The invention also discloses a kind of ink, which includes ink conventional ingredient and the tribo-luminescence ceramic material Powder, tribo-luminescence ceramic powder are evenly distributed in ink conventional ingredient, the addition of tribo-luminescence 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, which includes coating conventional ingredient and the tribo-luminescence ceramic material Powder, tribo-luminescence ceramic powder are evenly distributed in coating conventional ingredient, the addition of tribo-luminescence 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 tribo-luminescence 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 contain tribo-luminescence ceramic material in inside, 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 component or build-in components (engine components, tire, belt etc.), the bearing portion used in car, electric car, ship, aircraft etc. Link component 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 storage battery, valve seat, feed pipe, sprinkler head, be filled with electrolyte or polymer dielectric Nonaqueous electrolytic solution secondary battery leakage.Furthermore it is possible to make the adhesive layer of the bonding agent containing tribo-luminescence ceramic material Internal stress distribution visualization, can also hold the cracking of bonding agent.
During using tribo-luminescence 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 device, information processor, open The e-machines such as pass, operation button, input unit, finger-impu system and machine, can carry out the non-contact of device and system Control, automation process, straighforward operation.For example,：The elevation measurement device of the connection terminal of semiconductor device, hole The measurement device of phenomenon occurrence quantity, the measurement device of sound pressure distribution, using medical examination ultrasonic wave sound pressure The stress of the component effect such as the graft of distribution with energy density distribution measurement device, to being installed on organism bone or analog bone The dress of measurement device, transmission hawser, transmission device 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 transmit, using the light head by straighforward operation machinery device Remote-control switching system and using light head detection couple detecting system, 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, can detect with the installment state of paper carton and not The detection device 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, the operation device of distribution is not required, 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：Gasket, the measure of leakproofness 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 occurrence quantity.
Tactile sensor element application can also be used as.For example,：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 The luminous energy for acting on and producing, so as to can also expect the meter of metering and the exposure intensity distribution of the radiant exposure of radiation 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-common Mark, the mark of help instrument, signboard, display device；Safety guard, the anxiety hung on around shop building are restricted, animal Protective fence；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, the notification that shines antenna etc.)；The jewellery such as earrings, necklace；Support pillar, the railway of flag The exterior trim component 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 shine cloth, artificial luminous filament, artificial luminescent fibre etc.)；Packaging (case, stent, device, Envelope, ground paper, crust packaging, exterior overlay film), medical products (breathing assistance utensil, experimental study equipment) robot (manually hair Light hair structure body, artificial shiny skin, manually shine body) etc..As coating composition, ink composition, cement, surface Utilization example containing tribo-luminescence ceramic material in coverture, can enumerate：Financial institution, community organization, credit card company, stream The mailing such as crimping postcard sheet material containing tribo-luminescence 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 appearance can be produced by making tribo-luminescence ceramic material shine, therefore is also contemplated for toy, movable business Product etc. entertain the expansion of commodity, daily necessities.For example,：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 audio device 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 water plant with sink etc., container are viewed and admired in aquarium；Luminous wrist watch, shine sand timer or sand timer type Light-emitting device；Light emitting-type simulates candle device；The artificial plant that can be shone；Artificial eye；Makeup containing adhesion polymer Product composition, the printed article that can distinguish under visual state forgery 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 shining with stress, the photochemical catalyst for being attached to tribo-luminescence 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 shining.
By the way that with being mixed in resin, the tribo-luminescence ceramic material of the present invention can be formed 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, can also form the stress irradiance body of the present invention.
For example, in the case that resin is epoxy resin, acrylic resin etc., relative in the compounding of 100 mass parts of resin 1~200 part of tribo-luminescence ceramic material is stated, in the case that resin is polyvinyl resin, flexible vinyl chloride resin etc., relative to tree 100 mass parts of fat are compounded above-mentioned 30~300 mass parts of tribo-luminescence ceramic material.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 100 parts by weight of Corvic, it is compounded above-mentioned 50~200 mass parts of tribo-luminescence ceramic material, calcium-zinc system 3~5 mass parts of stabilizer, 30~100 mass parts of dioctyl phthalate as plasticizer, with two-roller mill 150~200 It is kneaded at DEG C, so as to obtain the stress irradiance body with flexible sheet.
When obtaining the stress irradiance body of film-form, such as relative to 100 mass parts of pet resin, Above-mentioned 20~50 mass parts of tribo-luminescence ceramic material 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 100 mass parts of acrylic resin, it is compounded tribo-luminescence 5~100 mass parts of ceramic material, are kneaded at 170~200 DEG C with double screw extruder, are molded, 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, shone due to mechanically deform.
As above-mentioned resin or other organic materials, can enumerate：Resin as thermoplastic resin, thermosetting resin. As thermoplastic resin, for example,：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, polyetherimide, polyurethane, polymethyl methacrylate, poly- acetic acid second The fluororesin such as enester, vinyl-vinyl acetate copolymer, polyvinylidene fluoride, polytetrafluoroethylene (PTFE), alkenyl aroma hydroxy-aromatic resin, gather The polyester such as ethylene glycol terephthalate, polybutylene terephthalate (PBT), polyethylene naphthalate, polylactic acid, 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, styrene-acrylonitrile copolymer (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, polyaminobismaleimide, 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, fungicide, antiseptic, curing catalyst, Photoepolymerizationinitiater initiater etc. and the tribo-luminescence ceramic material of the present invention It is mixed together, is shaped to bar-shaped, tabular, film-form, threadiness, membranaceous, needle-shaped, spherical, foil-like, graininess, sand shape, scale The arbitrary shapes such as shape, sheet, liquid, gelatinous, sol form, 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 aluminium 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 aluminium 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, bis- uncles of 3,5- 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, 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, the sub- phosphine of four (2,6- di-tert-butyl-phenyls) -3,3 '-biphenylene two 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, can enumerate：Benzophenone based compound, benzotriazole 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 benzotriazole based compound, can enumerate：2- (5- methyl -2- hydroxy phenyls) benzotriazole, 2- (3,5- bis- The tert-butyl group -2- hydroxy phenyls) benzotriazole, 2- (bis- tertiary pentyl -2- hydroxy phenyls of 3,5-) benzotriazole, 2- (3 ', 5 '-two uncles Butyl -4 '-methyl -2 '-hydroxy phenyl) benzotriazole, 2- (bis- tertiary pentyl -2- hydroxy phenyls of 3,5-) -5- chlorobenzotriazoles, 2- (the 5- tert-butyl group -2- hydroxy phenyls) benzotriazole, 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- benzotriazole and 2- (4 '-octyloxies -2 '-hydroxyl Phenyl) benzotriazole 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- butane tetracarboxylic acid and 1, 2,2,6,6- pentamethyl -4- hydroxy piperidines and β, β, β ', β '-tetramethyl -3,9- [tetra- oxaspiros (5,5) of 2,4,8,10- 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, be used as the polycarbonate oligomer of Material synthesis, two phthalimide chemical combination of bromination 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：Five cyclodecane of pentachloro-, 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, zinc borate, Boratex, Aluminium hydroxide, magnesium hydroxide and red phosphorus etc..
As fungicide, 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 fungicide, thiophanate-methyl, benomyl, carbendazim, thiabendazole etc. The acyls such as the dicarboximide system such as benzimidazole system fungicide, iprodione, vinclozolin, procymidone fungicide, furametpyr The morpholine system fungicide such as the phenylpyrrole such as amine system fungicide, fludioxonil system fungicide, dimethomorph, Fluoxastrobin, kresoxim-methyl, The anilino-pyrimidine system fungicide such as the methoxy acrylate such as ORIBRIGHT system fungicide, 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 molecular weight 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, 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 molecular weight, 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, two myristinate of pentaerythrite, 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 curing 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 azobisisovaleronitrile 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, dodecyl benzene sulfonic acid, 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, For example,：Mono-octyl phosphate, mono phosphoric acid ester propyl ester and mono phosphoric acid ester lauryl etc..As di-phosphate ester, for example,： 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 that answering for the present invention can also be made by the way that the tribo-luminescence 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 shone due to deformation.
In addition, the stress irradiance coating composition of the invention of the tribo-luminescence ceramic material containing the present invention shines 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, curing catalyst, fungicide 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, for example,：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, single ethyl of EG Ether, the single-butyl ether of EG, single ethylether of the monomethyl ether of PG and DEG), (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, dimethylacetylamide, 1-methyl-2-pyrrolidinone), 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, 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, aluminium 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 silicates 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, aluminium 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 polyether system, polyurethane resin system of polyether polyol system etc. are special The eggs such as the surfactant such as macromolecule nonionic thickener, nonionic system 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, three ester of anhydrous sorbitol stearic acid 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, isophorone diisocyanate, hydrogenated diphenyl methane diisocyanate, two isocyanide of diphenyl methane 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. Like that at normal temperatures being capable of cured isocyanates.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, one hydrogen magnesium of phosphoric acid, 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 component 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 component or calcium metasilicate component；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, for example,：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, curing catalyst, fungicide for antioxidant, comprising ultra-violet absorber and Antiseptic etc., can enumerate aforementioned substances.
Brief description of the drawings
Fig. 1 is the tribo-luminescence spectrogram of embodiment 1 ~ 3 provided by the invention and comparative example 1.
Fig. 2 is the tribo-luminescence spectrogram of embodiment 4 ~ 6 provided by the invention and comparative example 2.
Embodiment
1-2 and specific embodiment are described in further detail the present invention below in conjunction with the accompanying drawings.
Embodiment 1
A kind of tribo-luminescence ceramic material, chemical composition Zn1.96OS: 0.02Mn2+, 0.02Y3+。
According to molar ratio 1:1 weighs 1.89 grams of Zn (NO respectively3)2With 1.61 grams of ZnSO4High pure raw material, it is dissolved at the same time In deionized water, certain density Zn (NO are obtained3)2And ZnSO4Mixed solution；H is continually fed into above-mentioned solution2S gas Body, when duration of ventilation is 0.5 small, obtains ZnS precipitations；The excessive NaOH solution of 1mol/L is added dropwise into above-mentioned solution again, Obtain Zn (OH)2Precipitation；Above-mentioned turbid solution is loaded into autoclave, and reaction kettle is placed in baking oven and carries out heating reaction, Heating-up temperature is 200 DEG C, when the reaction time is 2 small；The precipitation obtained after reaction is filtered, is dried, obtains a kind of nanometer Forerunner's powder of ZnO and ZnS mixing；With forerunner's powder of above-mentioned acquisition and high-purity MnCO3、Y2O3As raw material, according to Chemical composition Zn1.96OS: 0.02Mn2+, 0.02Y3+The proportioning of middle each element, accurately weighs each raw material, and in agate mortar It is uniformly mixed；The above-mentioned raw materials of certain mass are weighed, and it is dry-pressing formed in stainless steel mould, and pressure 10MPa, obtains cylinder Shape greenwave；The greenwave is subjected to high temperature sintering under reducing atmosphere condition, heating rate is 10 DEG C/min, and sintering temperature is 1400 DEG C, when sintering time is 4 small, taken out after cooling, up to the tribo-luminescence ceramic material.
Embodiment 2
A kind of tribo-luminescence ceramic material, chemical composition Zn1.98OS: 0.01Mn2+, 0.01Gd3+。
According to molar ratio 1:1 weighs 1.89 grams of Zn (NO respectively3)2With 1.61 grams of ZnSO4High pure raw material, it is dissolved at the same time In deionized water, certain density Zn (NO are obtained3)2And ZnSO4Mixed solution；H is continually fed into above-mentioned solution2S gas Body, when duration of ventilation is 1 small, obtains ZnS precipitations；The excessive NaOH solution of 1mol/L is added dropwise into above-mentioned solution again, obtains Obtain Zn (OH)2Precipitation；Above-mentioned turbid solution is loaded into autoclave, and reaction kettle is placed in baking oven and carries out heating reaction, is added Hot temperature is 180, when the reaction time is 2 small；The precipitation obtained after reaction is filtered, is dried, obtain a kind of nano-ZnO and Forerunner's powder of ZnS mixing；With forerunner's powder of above-mentioned acquisition and high-purity MnCO3、Gd2O3As raw material, according to chemistry Form Zn1.98OS: 0.01Mn2+, 0.01Gd3+The proportioning of middle each element, accurately weighs each raw material, and is mixed in agate mortar Uniformly；The above-mentioned raw materials of certain mass are weighed, and it is dry-pressing formed in stainless steel mould, and pressure 15MPa, obtains cylindrical pottery Base；The greenwave is subjected to high temperature sintering under reducing atmosphere condition, heating rate is 10 DEG C/min, sintering temperature 1200 DEG C, when sintering time is 6 small, taken out after cooling, up to the tribo-luminescence ceramic material.
Embodiment 3
A kind of tribo-luminescence ceramic material, chemical composition Zn1.92OS: 0.04Mn2+, 0.04Nd3+。
According to molar ratio 1:1 weighs 1.89 grams of Zn (NO respectively3)2With 1.61 grams of ZnSO4High pure raw material, it is dissolved at the same time In deionized water, certain density Zn (NO are obtained3)2And ZnSO4Mixed solution；H is continually fed into above-mentioned solution2S gas Body, when duration of ventilation is 0.5 small, obtains ZnS precipitations；The excessive NaOH solution of 1mol/L is added dropwise into above-mentioned solution again, Obtain Zn (OH)2Precipitation；Above-mentioned turbid solution is loaded into autoclave, and reaction kettle is placed in baking oven and carries out heating reaction, Heating-up temperature is 200 DEG C, when the reaction time is 3 small；The precipitation obtained after reaction is filtered, is dried, obtains a kind of nanometer Forerunner's powder of ZnO and ZnS mixing；With forerunner's powder of above-mentioned acquisition and high-purity MnCO3、Nd2O3As raw material, press According to chemical composition Zn1.92OS: 0.04Mn2+, 0.04Nd3+The proportioning of middle each element, accurately weighs each raw material, and in agate mortar In be uniformly mixed；The above-mentioned raw materials of certain mass are weighed, and it is dry-pressing formed in stainless steel mould, and pressure 12MPa, is justified Cylindricality greenwave；The greenwave is subjected to high temperature sintering under reducing atmosphere condition, heating rate is 10 DEG C/min, sintering temperature For 1000 DEG C, when sintering time is 10 small, taken out after cooling, up to the tribo-luminescence ceramic material.
Embodiment 4
A kind of tribo-luminescence ceramic material, chemical composition Zn1.84OS: 0.08Mn2+, 0.04Y3+, 0.04Gd3+。
According to molar ratio 1:1 weighs 1.89 grams of Zn (NO respectively3)2With 1.61 grams of ZnSO4High pure raw material, it is dissolved at the same time In deionized water, certain density Zn (NO are obtained3)2And ZnSO4Mixed solution；H is continually fed into above-mentioned solution2S gas Body, when duration of ventilation is 1 small, obtains ZnS precipitations；The excessive NaOH solution of 1mol/L is added dropwise into above-mentioned solution again, obtains Obtain Zn (OH)2Precipitation；Above-mentioned turbid solution is loaded into autoclave, and reaction kettle is placed in baking oven and carries out heating reaction, is added Hot temperature is 180 DEG C, when the reaction time is 3 small；The precipitation obtained after reaction is filtered, is dried, obtains a kind of nano-ZnO With forerunner's powder of ZnS mixing；With forerunner's powder of above-mentioned acquisition and high-purity MnCO3、Y2O3、Gd2O3As raw material, press According to chemical composition Zn1.84OS: 0.08Mn2+, 0.04Y3+, 0.04Gd3+The proportioning of middle each element, accurately weighs each raw material, and It is uniformly mixed in agate mortar；The above-mentioned raw materials of certain mass are weighed, and it is dry-pressing formed in stainless steel mould, and pressure is 15MPa, obtains cylindrical greenwave；The greenwave is subjected to high temperature sintering under reducing atmosphere condition, heating rate for 10 DEG C/ Min, sintering temperature are 1200 DEG C, when sintering time is 8 small, are taken out after cooling, up to the tribo-luminescence ceramic material.
Embodiment 5
A kind of tribo-luminescence ceramic material, chemical composition Zn1.88OS: 0.06Mn2+, 0.03Y3+, 0.03Nd3+。
According to molar ratio 1:1 weighs 1.89 grams of Zn (NO respectively3)2With 1.61 grams of ZnSO4High pure raw material, it is dissolved at the same time In deionized water, certain density Zn (NO are obtained3)2And ZnSO4Mixed solution；H is continually fed into above-mentioned solution2S gas Body, when duration of ventilation is 0.5 small, obtains ZnS precipitations；The excessive NaOH solution of 1mol/L is added dropwise into above-mentioned solution again, Obtain Zn (OH)2Precipitation；Above-mentioned turbid solution is loaded into autoclave, and reaction kettle is placed in baking oven and carries out heating reaction, Heating-up temperature is 200 DEG C, when the reaction time is 2 small；The precipitation obtained after reaction is filtered, is dried, obtains a kind of nanometer Forerunner's powder of ZnO and ZnS mixing；With forerunner's powder of above-mentioned acquisition and high-purity MnCO3、Y2O3、Nd2O3As original Material, according to chemical composition Zn1.88OS: 0.06Mn2+, 0.03Y3+, 0.03Nd3+The proportioning of middle each element, accurately weighs each original Material, and be uniformly mixed in agate mortar；The above-mentioned raw materials of certain mass are weighed, and dry-pressing formed in stainless steel mould, pressure Power is 14MPa, obtains cylindrical greenwave；The greenwave is subjected to high temperature sintering under reducing atmosphere condition, heating rate is 10 DEG C/min, sintering temperature is 1300 DEG C, when sintering time is 6 small, is taken out after cooling, up to the tribo-luminescence ceramics material Material.
Embodiment 6
A kind of tribo-luminescence ceramic material, chemical composition Zn1.8OS: 0.1Mn2+, 0.04Y3+, 0.04Gd3+, 0.02Nd3 +。
According to molar ratio 1:1 weighs 1.89 grams of Zn (NO respectively3)2With 1.61 grams of ZnSO4High pure raw material, it is dissolved at the same time In deionized water, certain density Zn (NO are obtained3)2And ZnSO4Mixed solution；H is continually fed into above-mentioned solution2S gas Body, when duration of ventilation is 1 small, obtains ZnS precipitations；The excessive NaOH solution of 1mol/L is added dropwise into above-mentioned solution again, obtains Obtain Zn (OH)2Precipitation；Above-mentioned turbid solution is loaded into autoclave, and reaction kettle is placed in baking oven and carries out heating reaction, is added Hot temperature is 180 DEG C, when the reaction time is 2 small；The precipitation obtained after reaction is filtered, is dried, obtains a kind of nano-ZnO With forerunner's powder of ZnS mixing；With forerunner's powder of above-mentioned acquisition and high-purity MnCO3、Y2O3、Gd2O3、Nd2O3As Raw material, according to chemical composition Zn1.8OS: 0.1Mn2+, 0.04Y3+, 0.04Gd3+, 0.02Nd3+The proportioning of middle each element, accurately Each raw material is weighed, and is uniformly mixed in agate mortar；Weigh the above-mentioned raw materials of certain mass, and the dry-pressing in stainless steel mould Shaping, pressure 14MPa, obtains cylindrical greenwave；The greenwave is subjected to high temperature sintering under reducing atmosphere condition, is heated up Speed is 10 DEG C/min, and sintering temperature is 1300 DEG C, when sintering time is 5 small, is taken out after cooling, up to the tribo-luminescence Ceramic material.
Comparative example 1
A kind of tribo-luminescence ceramic material, chemical composition Zn1.98OS: 0.02Mn2+。
According to molar ratio 1:1 weighs 1.89 grams of Zn (NO respectively3)2With 1.61 grams of ZnSO4High pure raw material, it is dissolved at the same time In deionized water, certain density Zn (NO are obtained3)2And ZnSO4Mixed solution；H is continually fed into above-mentioned solution2S gas Body, when duration of ventilation is 0.5 small, obtains ZnS precipitations；The excessive NaOH solution of 1mol/L is added dropwise into above-mentioned solution again, Obtain Zn (OH)2Precipitation；Above-mentioned turbid solution is loaded into autoclave, and reaction kettle is placed in baking oven and carries out heating reaction, Heating-up temperature is 200 DEG C, when the reaction time is 2 small；The precipitation obtained after reaction is filtered, is dried, obtains a kind of nanometer Forerunner's powder of ZnO and ZnS mixing；With forerunner's powder of above-mentioned acquisition and high-purity MnCO3As raw material, according to chemistry Form Zn1.98OS: 0.02Mn2+The proportioning of middle each element, accurately weighs each raw material, and is uniformly mixed in agate mortar；Weigh The above-mentioned raw materials of certain mass, and it is dry-pressing formed in stainless steel mould, and pressure 10MPa, obtains cylindrical greenwave；By described in Greenwave carry out high temperature sintering under reducing atmosphere condition, heating rate is 10 DEG C/min, and sintering temperature is 1400 DEG C, during sintering Between for 4 it is small when, taken out after cooling, up to the tribo-luminescence ceramic material.
Comparative example 2
A kind of tribo-luminescence ceramic material, chemical composition Zn1.92OS: 0.08Mn2+。
According to molar ratio 1:1 weighs 1.89 grams of Zn (NO respectively3)2With 1.61 grams of ZnSO4High pure raw material, it is dissolved at the same time In deionized water, certain density Zn (NO are obtained3)2And ZnSO4Mixed solution；H is continually fed into above-mentioned solution2S gas Body, when duration of ventilation is 1 small, obtains ZnS precipitations；The excessive NaOH solution of 1mol/L is added dropwise into above-mentioned solution again, obtains Obtain Zn (OH)2Precipitation；Above-mentioned turbid solution is loaded into autoclave, and reaction kettle is placed in baking oven and carries out heating reaction, is added Hot temperature is 180 DEG C, when the reaction time is 3 small；The precipitation obtained after reaction is filtered, is dried, obtains a kind of nano-ZnO With forerunner's powder of ZnS mixing；With forerunner's powder of above-mentioned acquisition and high-purity MnCO3As raw material, according to chemical group Into Zn1.92OS: 0.08Mn2+The proportioning of middle each element, accurately weighs each raw material, and is uniformly mixed in agate mortar；Weigh one Determine the above-mentioned raw materials of quality, and it is dry-pressing formed in stainless steel mould, and pressure 15MPa, obtains cylindrical greenwave；Will be described Greenwave carries out high temperature sintering under reducing atmosphere condition, and heating rate is 10 DEG C/min, and sintering temperature is 1200 DEG C, sintering time For 8 it is small when, taken out after cooling, up to the tribo-luminescence ceramic material.
Fig. 1 show the preparation of the tribo-luminescence spectrogram, wherein comparative example 1 and example 1 of embodiment 1 ~ 3 and comparative example 1 Condition is identical, it, which is differed only in, does not introduce Y in comparative example 13+、Gd3+And Nd3+Deng impurity rare earth ion.Can be with from figure Find out, embodiment 1 ~ 3 is respectively provided with obvious tribo-luminescence phenomenon, its luminous peak position is near the green light of 540nm, active ions Mn2+With impurity energy level ion Y3+、Gd3+And Nd3+Doping concentration there is material impact to the tribo-luminescence intensity of sample, pass through Introduce rare earth ion Y3+、Gd3+And Nd3+In one or more combination provide trap level, can effectively strengthen tribo-luminescence effect Fruit.
Fig. 2 show the preparation of the tribo-luminescence spectrogram, wherein comparative example 2 and example 4 of embodiment 4 ~ 6 and comparative example 2 Condition is identical, it, which is differed only in, does not introduce Y in comparative example 23+、Gd3+And Nd3+Deng impurity rare earth ion.Can be with from figure Find out, embodiment 4 ~ 6 also has obvious tribo-luminescence phenomenon, its luminous peak position is near the green light of 540nm, but it is sent out Luminous intensity is less than embodiment 1 ~ 3 on the whole, illustrates active ions Mn2+Preferred doping concentration be about 0.02, by introducing rare earth Ion Y3+、Gd3+And Nd3+In one or more combination provide trap level, can effectively strengthen tribo-luminescence effect.
Triboluminescent phenomenon is observed very early, but to the source of its excitation mechanism and excitation state, is not had also so far Determining completely, field personnel generally only do phenomenon description to tribo-luminescence, its light sources and mechanism are not all illustrated but, Simply think to influence that triboluminescent factor is very much, even if the material of same element, in different preparation conditions（Such as concentration of element Proportioning, refine material when sintering temperature, sintering time）, different pressure, under different frictional strengths, tribo-luminescent performance Difference it is also very big.Therefore, it is actually related with which factor to study tribo-luminescence, how to select most suitable experiment condition, has Synthesize to target tribo-luminescence body, there is important theoretical and practical significance.Some attempt from the angle of crystal structure with And friction excites air to explain and disclose tribo-luminescence mechanism, but scientific circles there is no this final conclusion so far.Since friction is sent out The mechanism of light is unclear so far, so on the one hand people are directed to the developmental research of practical application, on the other hand makes great efforts to explore Triboluminescent mechanism and its dynamic process, seek the relation between tribo-luminescent performance and structure, establish triboluminescent Prediction theory, studies triboluminescent mechanism, particularly the triboluminescent mechanism of complex, becomes chemist and physicist is closed The hot spot of note.For these reasons, the present invention has been prepared and rubbed with higher by optimizing preparation condition and matrix chemical composition Wipe the Zn of luminous efficiency2-x-yOS: xMn2+, yRe3+Triboluminescent material, has higher actual application value.

Claims (2)

1. a kind of tribo-luminescence ceramic material, it is characterised in that the ceramic chemical composition general formula is Zn2-x-yOS: xMn2+,yRe3+, wherein Re is Y, the one or more combination in Gd and Nd, and the value range of x, y and z are respectively：0.01≤x≤0.1, 0.01≤y≤0.1。
2. a kind of preparation method of tribo-luminescence ceramic material, it is characterised in that comprise the following steps：
（1）According to molar ratio 1:1 weighs the Zn (NO of certain mass respectively3)2And ZnSO4High pure raw material, it is dissolved at the same time In ionized water, certain density Zn (NO are obtained3)2And ZnSO4Mixed solution；
（2）H is continually fed into above-mentioned solution2S gases, when duration of ventilation is 0.5 ~ 1 small, obtain ZnS precipitations；
（3）The excessive NaOH solution of 1mol/L is added dropwise into above-mentioned solution again, obtains Zn (OH)2Precipitation；
（4）Above-mentioned turbid solution is loaded into autoclave, and reaction kettle is placed in baking oven and carries out heating reaction, heating-up temperature is 180 ~ 200 DEG C, when the reaction time is 2 ~ 4 small；
（5）The precipitation obtained after reaction is filtered, is dried, obtains a kind of forerunner's powder of nano-ZnO and ZnS mixing；
（6）With forerunner's powder of above-mentioned acquisition and high-purity MnCO3、Y2O3、Gd2O3、Nd2O3As raw material, according to chemical composition Zn2-x-yOS: xMn2+, yRe3+The proportioning of middle each element, accurately weighs each raw material, and is uniformly mixed in agate mortar；
（7）The above-mentioned raw materials of certain mass are weighed, and it is dry-pressing formed in stainless steel mould, and pressure 10-15MPa, is justified Cylindricality greenwave；
（8）The greenwave is subjected to high temperature sintering under reducing atmosphere condition, heating rate is 10 DEG C/min, and sintering temperature is 1000 ~ 1400 DEG C, when sintering time is 4 ~ 10 small, taken out after cooling, up to the tribo-luminescence ceramic material.
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109176590A (en) * 2018-10-18 2019-01-11 山东大学 A kind of flexible finger tip, device and method with the sliding feel perception of pressure
CN110591701A (en) * 2019-10-09 2019-12-20 厦门大学 Multiband elastic stress luminescent material and preparation method thereof
WO2023175224A1 (en) * 2022-03-14 2023-09-21 Colorobbia España, S.A. Luminescent ink and ceramic product with a label printed with luminescent ink

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1668720A (en) * 2002-07-12 2005-09-14 独立行政法人科学技术振兴机构 Highly bright mechanoluminescence material and process for producing the same
CN101429432A (en) * 2008-12-12 2009-05-13 江苏苏博特新材料股份有限公司 Superfine grain size high light efficiency long afterglow fluorescent powder and its production method
CN102408891A (en) * 2010-09-26 2012-04-11 海洋王照明科技股份有限公司 Fluoborate fluorescent powder and preparation method thereof
CN103468258A (en) * 2013-09-05 2013-12-25 青岛大学 Red high-brightness elastic stress luminescent material and preparation method thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1668720A (en) * 2002-07-12 2005-09-14 独立行政法人科学技术振兴机构 Highly bright mechanoluminescence material and process for producing the same
CN101429432A (en) * 2008-12-12 2009-05-13 江苏苏博特新材料股份有限公司 Superfine grain size high light efficiency long afterglow fluorescent powder and its production method
CN102408891A (en) * 2010-09-26 2012-04-11 海洋王照明科技股份有限公司 Fluoborate fluorescent powder and preparation method thereof
CN103468258A (en) * 2013-09-05 2013-12-25 青岛大学 Red high-brightness elastic stress luminescent material and preparation method thereof

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109176590A (en) * 2018-10-18 2019-01-11 山东大学 A kind of flexible finger tip, device and method with the sliding feel perception of pressure
CN109176590B (en) * 2018-10-18 2020-08-25 山东大学 Flexible fingertip with pressure and slip feeling perception, device and method
CN110591701A (en) * 2019-10-09 2019-12-20 厦门大学 Multiband elastic stress luminescent material and preparation method thereof
WO2023175224A1 (en) * 2022-03-14 2023-09-21 Colorobbia España, S.A. Luminescent ink and ceramic product with a label printed with luminescent ink

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