CN107903065B - 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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CN107903065B
CN107903065B CN201711061639.0A CN201711061639A CN107903065B CN 107903065 B CN107903065 B CN 107903065B CN 201711061639 A CN201711061639 A CN 201711061639A CN 107903065 B CN107903065 B CN 107903065B
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tribo
acid
luminescence
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ceramic material
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CN107903065A (en
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杨道救
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Jiangxi Jinyang Ceramics Co., Ltd.
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Abstract

The invention discloses a kind of tribo-luminescence ceramic materials 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 chemical composition general formula of the ceramics is Zn2‑x‑yOS:xMn2+,yRe3+, wherein Re is Y, and one or more of Gd and Nd are combined, and the value range of x and y are respectively as follows: 0.01≤x≤0.1,0.01≤y≤0.1, and the centre of luminescence of the ceramics is Mn2+Ion, by introducing Y3+, Gd3+And Nd3+Equal rare earth impurities ion can effectively enhance its tribo-luminescence effect.Ceramics provided by the invention have the features such as compression strength is high, and tribo-luminescence effect is obvious, the pressure sensitive component that can be used in pressure sensor.

Description

A kind of tribo-luminescence ceramic material and preparation method thereof
Technical field
The invention belongs to ceramic technology fields, more particularly to a kind of tribo-luminescence ceramic material and preparation method thereof.
Background technique
Tribo-luminescence refers to luminescence phenomenon of certain solids by mechanical lapping, vibration or stress when, and this kind of luminescent substance can Mechanical energy is changed into luminous energy.Although will lead to luminous early in the rupture that 17th century records rock in earthquake with regard to someone, arrive So far, triboluminescent mechanism is studied clear completely not yet.Discovered in recent years triboluminescent material can be used for pressure-sensitive Shine sensory field, can be used to manufacture pressure detecting sensors, be used in combination with photodetector, can the spy of development of new pressure Survey the display element etc. in sensor, forecast monitor and certain scientific instrument, it is this novel friction pressure to be converted into light The sensing mode of degree converts amount of electrons for friction pressure compared to old-fashioned, if strain sensing and piezoelectric type sense, has non- Contact induction and the simpler advantage of electrical connection, thus its concern is gradually increased, it can broadly be applied.
Tribo-luminescence substance is increasingly paid close attention to by people in materials science field, external for triboluminescent research Since the 1980s, the material for being dedicated 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, 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 about 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 substance for being commonly used for research has: Sm3+ 、Eu3+ 、Tb3+Cooperate with the ternary of beta-diketon and organic phosphorous oxides Object, 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 substance.For exciting triboluminescent mechanical energy, there are many forms.Such as temperature vibration, it can To generate stress, crackle and crystal-phase transformation；Crystallization rapidly, it also can produce stress and crack；There are also by the crystal that collides, rubs And the anisotropic pressure and fluid generated 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 the chemical reaction of a generation excitation state product has occurred so as to cause shining, these are made With tribothermoluminescence is referred to alternatively as respectively, tribochemistry shines.
Summary of the invention
The disadvantages of in order to overcome the luminous intensity of above-mentioned triboluminescent material in the prior art weaker, the present invention provides one Kind has the ceramic material and preparation method thereof of higher tribo-luminescence efficiency, which has compression strength high, and tribo-luminescence is imitated The features such as fruit is obvious, the pressure sensitive component that can be used 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 are Zn2-x-yOS: xMn2+, yRe3 +, wherein Re is Y, one or more of Gd and Nd combination, and the value range of x and y are respectively as follows: 0.01≤x≤0.1,0.01≤ y≤0.1.Particularly, the centre of luminescence of the ceramics is Mn2+Ion, by introducing rare earth ion Y3+、Gd3+And Nd3+In one Kind or several combinations provide trap level, can effectively enhance its tribo-luminescence effect.
A kind of preparation method of tribo-luminescence ceramic material, it is characterised in that the following steps are included:
(1) Zn (NO of certain mass is weighed respectively according to molar ratio 1:13)2And ZnSO4High pure raw material dissolves it simultaneously In deionized water, certain density Zn (NO is obtained3)2And ZnSO4Mixed solution；
(2) H is continually fed into Xiang Shangshu solution2S gas, duration of ventilation are 0.5 ~ 1 hour, obtain ZnS precipitating；
(3) the excessive NaOH solution of 1mol/L is added dropwise into above-mentioned solution again, obtains Zn (OH)2Precipitating；
(4) above-mentioned turbid solution is packed into autoclave, and reaction kettle is placed in baking oven and carries out heating reaction, heating temperature Degree is 180 ~ 200 DEG C, and the reaction time is 2 ~ 4 hours；
(5) precipitating obtained after reaction is filtered, dried, obtain the predecessor powder of a kind of nano-ZnO and ZnS mixing Body；
(6) with forerunner's powder of above-mentioned acquisition and high-purity MnCO3、Y2O3、Gd2O3、Nd2O3As raw material, according to change Learn composition Zn2-x-yOS: xMn2+, yRe3+The proportion of middle each element accurately weighs each raw material, and mixing is equal in the agate mortar It is even；
(7) above-mentioned raw materials of certain mass are weighed, and dry-pressing formed in stainless steel mould, pressure 10-15MPa is obtained To cylindrical greenwave；
(8) greenwave is subjected to high temperature sintering under reducing atmosphere condition, heating rate is 10 DEG C/min, sintering temperature Degree is 1000 ~ 1400 DEG C, and sintering time is 4 ~ 10 hours, is taken out after cooling to get the tribo-luminescence ceramic material.
Compared with prior art, the beneficial effects of the present invention are:
(1) tradition ZnS:Mn2+The chemical stability of triboluminescent material is poor, and fluorescence emission peak is located at the left side 580nm The right side, human eye is not easy to identify, and tribo-luminescence ceramic material provided by the invention has that tribo-luminescence is high-efficient, chemical stabilization Property it is good the features such as, luminous peak position is more advantageous to human eye identification in the green wavelength of 540nm or so；
(2) preparation method of tribo-luminescence ceramic material provided by the invention is simple, not harsh preparation process condition Limitation；
(3) present invention is by introducing rare earth ion Y3+、Gd3+And Nd3+One or more of combination provide trap level, Its tribo-luminescence effect can effectively be enhanced.
The invention also discloses a kind of stress irradiance elements, 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 being 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 the pressure light-emitting film that a kind of stress irradiance element includes substrate and is attached in substrate, institutes The pressure light-emitting film stated is tribo-luminescence ceramic powder or tribo-luminescence ceramic material thin slice.
Preferably, pressure light-emitting film with a thickness of 1-10mm.
Substrate of the invention can be rigid basement, or flexible substrates.Preferably, the rigid basement can To be selected from glass, silicon, steel, ceramics, cement, timber and stone, the flexible substrates can be selected from PDMS (polydimethylsiloxanes 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, comprising: by tribo-luminescence ceramic powder particle as described above Suspension be coated on substrate as described above on.
Although by suspension is prepared into tribo-luminescence ceramic powder particle suspension liquid solvent as described above, then Coated on can be prepared in the substrate meet the present invention claims sensor, but also contain macromolecule in the suspension When substance, the sensitivity of final prepared sensor and precision can be promoted 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, 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 of glue, carboxymethyl starch, acetic starch, hydroxymethyl cellulose and carboxymethyl cellulose are a variety of.
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, 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 of butanone, repefral and D-sorbite are a variety of.
According to the present invention, the suspension of the tribo-luminescence ceramic powder particle is coated on the substrate surface Method can be the selection of this field routine, for example, can also use and print using the coating methods such as spraying, spin coating Technology.The suspension of tribo-luminescence ceramic powder particle is imprinted on the surface of substrate to the present invention by preferred printing technique herein On, so that the sensitivity for the sensor being prepared and precision are further promoted.Wherein, the printing technique can Selected from one of dispensing, inkjet printing, water transfer, silk-screen printing and roll-to-roll printing.When use printing technique will be described 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 are by obtaining the suspension blending and stirring or blending ultrasonic disperse.
Tribo-luminescence ceramic powder particle of the present invention, pressure sensitive component as described above and as described above Method preparation application of the pressure sensor in wind tunnel experiment.
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 additional amount 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 be added 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 Amount is 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 is also possible to 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 Amount is 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 is also possible to water paint.
In addition, by the way that common paper, synthetic paper or epoxy resin, poly- second will be formed in comprising tribo-luminescence ceramic material The macromolecules 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 their combination and their fabricated product Deng exterior trim surface, or by containing tribo-luminescence ceramic material in inside, so as to detect exception, or by applying impact Wave and the deterioration (stress-strain detection, stress distribution measurement) for diagnosing various works, component.Such as are as follows: 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 used in vehicle, electric car, ship, aircraft etc. (engine components, tire, belt etc.), bearing portion Connections component such as part, bearing retainer and bearing, screw, screw rod, nut, washer with optical sensor etc..In addition, As its application, can expect: detection battery, water supplying pipe, sprinkler head, is filled with electrolyte or polymer dielectric at valve seat 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.
When 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, optical waveguide, optical waveguide device, mechanical optics device, detection device, information processing unit, is opened impact force detector part 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, remote control operation.For example: the elevation measurement device of the connection terminal of semiconductor component, hole The measurement device of phenomenon occurrence quantity, the measurement device of sound pressure distribution, using medical examination ultrasonic wave sound pressure Distribution and energy density distribution measurement device, the stress that the components such as the graft for being installed on organism bone or analog bone are acted on The measurement device of the distribution of strain, the dress for transmitting hawser, transmission device and laser processing device, the amount of bow for detecting steering shaft It sets, 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 generate stress corresponding with the thermal energy of infrared light and image solid-state imaging apparatus, by frictional force, shearing force, impact The mechanical external forces such as power, pressure be converted into optical signal and transmit light head, using the light head by remote control operation machinery device Remote-control switching system and using light head detection couple detection system, be removably installed in it is electrical, electronics, machinery The dismounting body of the main part of various machines, such as ink-jet printer print cartridge, be able to detect with the installation condition of paper carton and not The detection device and dismounting body of the dismounting body of installation condition；It can check that the ultraviolet light for remaining on bump is solid in a short time The imprinting apparatus for changing resin, the operating device for not needing wiring, can be directed into organism, dark place it is small-sized and radio-type Light source (stress irradiance particle), the check device for having it and inspection method, stress placement file system etc..In addition, can also To be used for: gasket, the measurement of the leakproofness of sealing element, the ground plane shape of tire, the measurement of earth contact pressure distribution, gear division bite force Measurement, the grounding parts tools for measurement of tire, the measuring method of cavitation occurrence quantity etc..
It can also be used as tactile sensor element application.For example: people coordinates humanoid robot, artificial hand vacation refers to Artificial limb, the distinctor of diagnosis, hardness pliability detector of various industry etc..In addition, by measurement due to radiation The luminous energy of effect and generation, to can also expect the meter of metering and the exposure intensity distribution of the radiant exposure of radiation Amount.
Other than said determination device, it is also contemplated that as illumination, for safety display utilization.Such as Are as follows: device vibrates the luminaires such as lamp, wind power lamp；Promptly, abnormal notification, very apparatus, dangerous display, very lamp, non-common Mark, the mark of help tool, signboard, display device；Safety guard hangs on nervous rope around shop building, animal Protective fence；Use filament to the pedal of ladder, handrail and the mesh that is arranged in the state ofs being partly embedded in road etc.；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 the road the Deng Jie road Ji Jie stick, 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 of the domestic animals such as the pets such as people, dog, cat, ox, pig, sheep, chicken etc. is shown；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, bracket, device, Envelope, ground paper, crust packaging, external overlay film), medical products (breathing assistance utensil, experimental study equipment) robot (artificial 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 Crimping postcard sheet material containing tribo-luminescence ceramic material etc. is posted used in logical industry etc., in the bonding agent of stickup Object；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 operating 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..
It can produce new appearance and making tribo-luminescence ceramic material shine, therefore also consider to toy, movable quotient The expansion of the amusement commodity, daily necessity such as product.For example: it is the wind long narrow flag 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 The windmill of photosphere (golf, the ball of baseball, table tennis ball, ball of billiard ball etc.), luminous mechanism；Balloon；Laminated structure object For paper, batch flute, paper folding, paper balloon, folding fan, New Year card, draw this；(jumping pole, fencing, bow and arrow are isometric for sporting goods Size objects etc.)；The score confirmation pressure sensitive sealant part of golf club, dynamic ornamentation body, moves tennis court line tester 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 of the ornamental sink in aquarium etc., container；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 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 sealing element etc..
Using shining along with stress, obtain the photochemical catalyst for being attached to tribo-luminescence ceramic material surfaces activation , stress irradiance body-photochemical catalyst complex can be used for: antibacterial, sterilization, to the handrail of the treatment of non-human animal, vehicle, The dirt purification of the antibacterial articles such as handle, using the internal wall surface of the piping etc. for being located at dark place fluid energy of flow it is net Change.Stress irradiance substance activates the photocrosslinking agent in macromolecule resin, can also promote to be crosslinked by shining.
By the way that tribo-luminescence ceramic material of the invention with being mixed in resin, can be formed resin combination of the invention Object.
In addition, being formed again by the way that other inorganic material or organic material are further added in resin combination of the invention Condensation material can also form stress irradiance body of the 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 rouge are compounded above-mentioned 30~300 mass parts of tribo-luminescence ceramic material.Blend can be by using tapered mixing The mixing machines such as machine, V-Mixer, ribbon mixer, Henschel mixer, banbury mixers, triple-roller mill make resin Composition.
In addition, in the case where 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, formed, so as to obtain 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 formed, so as to obtain band Shape, plate, rodlike, partical stress irradiance body.In addition, by using injection (mo(u)lding) machine to partical at 170~200 DEG C Stress irradiance body carry out machine-shaping, the stress irradiance body of available three-dimensional shape.
When applying mechanical external force to the stress irradiance body, shone due to mechanically deform.
It 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), gather alkenyl aroma hydroxy-aromatic resin The polyester such as ethylene glycol terephthalate, polybutylene terephthalate (PBT), polyethylene naphthalate, polylactic acid, bisphenol-A Be the polycarbonate such as polycarbonate, polyacetals, polyphenylene sulfide, polymethylpentene, cellulose, polyvinyl alcohol, polyvinyl acetate, The polyacrylic acid such as polyacrylonitrile, polyphenylene oxide (PPE), MODIFIED PP E, polyarylate, gather at styrene-acrylonitrile copolymer (AS resin) Diphenyl sulfide, polysulfones, polyether sulfone, polyethers nitrile, polyether-ketone, polyketone, liquid crystal polymer ethylene and propylene copolymer, ethylene or propylene With copolymer, ethylene and other olefinic insatiable hungers of other alpha-olefins (1- butylene, 1- amylene, 1- hexene, 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 It can be the copolymer of any forms such as random copolymer, block copolymer when object.As thermosetting resin, can enumerate: phenol Urea formaldehyde, urea resin, melamine resin, 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 light, the resin of radiation curing.
In turn, it can enumerate: natural rubber, polyisoprene rubber, butadiene-styrene rubber, polybutadiene rubber, ethylene-the third The rubber-based materials such as alkene-diene rubber, butyl rubber, neoprene, acrylonitrile butadiene rubber, silicon rubber.
It in addition to this, can be by pigment, dyestuff, lubricant, antioxidant, ultraviolet absorbing agent, light stabilizer, antistatic Agent, fire retardant, fungicide, antibacterial agent, solidification catalyst, Photoepolymerizationinitiater initiater etc. and tribo-luminescence ceramic material of the invention It is mixed together, is shaped to rodlike, plate, film-form, threadiness, membranaceous, needle-shaped, spherical, foil-like, graininess, sand shape, scale The arbitrary shapes such as shape, sheet, liquid, gel, 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, the glass flake, holographic pigment covered by titanium oxide, iron oxide Deng.In addition to this, it 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.
It 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 system azophloxine, anthanthrone, anthraquinone is red, pyrene is reddish brown, quinoline The red pigments such as acridone is red, diketopyrrolopyrrolecocrystals are red, permanent red；The purples face such as cobalt violet, quinacridone violet, dioxazine violet 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 dye, thiazine dye), thiazole dye, first alkynes dyestuff, nitro dye and nitroso-dyes etc..
It as antioxidant, can enumerate: hindered phenolic compound, phosphite ester based compound, phosphinate system chemical combination Object and thioether based compound etc..
It as hindered phenolic compound, can enumerate: alpha-tocopherol, butylated hydroxytoluene, sinapinic alcohol, vitamin E, positive ten Eight alkyl-β-(4 '-hydroxyls -3 ', 5 '-di-tert-butyl-phenyls) propionic ester, 2- tert-butyl -6- (3 '-tert-butyls -5 '-methyl -2 ' - Hydroxybenzyl) -4- aminomethyl phenyl acrylate, 2,6- di-t-butyl -4- (N, N- dimethylaminomethyl) phenol, bis- uncle of 3,5- Butyl -4- benzylphosphonic acid diethyl ester, 2,2 '-di-2-ethylhexylphosphine oxides (4- methyl-6-tert-butylphenol), 2,2 '-di-2-ethylhexylphosphine oxides (4- ethyl -6- tert-butyl phenol), 4,4 '-methylene-bis(2,6-di-t-butyl phenol)s, 2,2 '-di-2-ethylhexylphosphine oxides (4- methyl -6- Cyclohexylphenol), 2,2 '-dimethylenes-bis- (6- Alpha-Methyl-benzyl-paracresol) 2,2 '-ethidines-bis- (4,6- di-t-butyl Phenol), 2,2 '-butanes-bis- (4- methyl-6-tert-butylphenol), 4,4 '-butanes bis- (3 methy 6 tert butyl phenols), Triethylene glycol-N- double -3- (3- tertiary butyl-4-hydroxy -5- aminomethyl phenyl) propionic esters, bis- [3- (the tertiary fourths of 3,5- bis- of 1,6-HD Base -4- hydroxy phenyl) propionic ester], bis- [2- tert-butyl -4- methyl 6- (3- tert-butyl -5- methyl -2- hydroxybenzyl) phenyl] it is right Bis- { 2- [3- (3- tertiary butyl-4-hydroxy -5- aminomethyl phenyl) propiono the oxygroup] -1,1- dimethyl second of phthalic acid ester, 3,9- Base } -2,4,8,10- four oxaspiro [5,5] hendecane, 4,4 '-thiobis (6- tert-butyl-metacresol), 4,4 '-thiobis (3- Methyl-6-tert-butylphenol), 2,2 '-thiobis (4- methyl-6-tert-butylphenol), bis- (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- Thiodiethylene pair-[3- (3,5- di-tert-butyl-hydroxy phenyl) propionic ester], bis- (just pungent sulfenyl) -6- (4- hydroxyls of 2,4- Base -3 ', 5 '-di-tert-butyl amidos) -1,3,5- triazine, N, N '-hexamethylene bis-(3,5- di-t-butyl -4- hydroxy group Cinnamamide), N, bis- [3- (3,5- di-tert-butyl-hydroxy phenyl) propiono] hydrazines of N ' -, (2- methyl -4- hydroxyl of 1,1,3- tri- Base -5- tert-butyl-phenyl) butane, 1,3,5- trimethyl -2,4,6- three (3,5- di-tert-butyl-4-hydroxyl benzyl) benzene, three (3,5- Di-tert-butyl-hydroxy phenyl) isocyanuric acid ester, three (3,5- di-tert-butyl-4-hydroxyl benzyl) isocyanuric acid esters, 1,3,5- tri- (4- tert-butyl -3- hydroxyl -2,6- dimethyl benzyl) isocyanuric acid ester, the [3- (3,5- di-t-butyl -4- hydroxy benzenes of 1,3,5- 32 Base) propiono oxygroup] 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-phenyl) ester, phosphorous acid three (2,6- di-tert-butyl-phenyl) ester, two Stearyl pentaerythritol diphosphites, bis- (2,4- di-tert-butyl-phenyl) pentaerythritol diphosphites, bis- (tertiary fourths of 2,6- bis- Base -4- aminomethyl phenyl) pentaerythritol diphosphites, bis- (2,6- di-t-butyl -4- ethylphenyl) pentaerythrite diphosphorous acids Ester, bis- { bis- (1- methyl-1-phenylethyl) phenyl of 2,4- } pentaerythritol diphosphites, phenyl bisphenol-A pentaerythrite two are sub- Phosphate, bis- (nonyl phenyl) pentaerythritol diphosphites and dicyclohexyl pentaerythritol diphosphites etc..As other Phosphite ester based compound can be enumerated and be reacted with dihydric phenol class 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 are sub- Phosphonate ester, four (2,4- di-tert-butyl-phenyl) -4,3 '-biphenylens, four (2,4- di-tert-butyl-phenyls) -3, 3 '-biphenylens, four (2,6- di-tert-butyl-phenyl) -4,4 '-biphenylens, four (2,6- bis- Tert-butyl-phenyl) -4,3 '-biphenylens, the sub- phosphine of four (2,6- di-tert-butyl-phenyl) -3,3 '-biphenylene two Acid esters, bis- (2,4- di-tert-butyl-phenyl) -4- phenyl-phenyl phosphinates, bis- (2,4- di-tert-butyl-phenyl) -3- phenyl-benzene Base phosphinate, bis- (2,6- di-n-butyl phenyl) -3- phenyl-phenyl phosphinates, bis- (2,6- di-tert-butyl-phenyl) -4- benzene Base-phenylphosphite ester and bis- (2,6- di-tert-butyl-phenyl) -3- phenyl-phenyl phosphinates etc..
It 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 acid of pentaerythrite-four Ester), pentaerythrite-four (3- laurylthiopropionate), pentaerythrite-four (3- octadecyl thiopropionate), season penta Tetrol four (3- myristyl thiopropionate) and pentaerythrite-four (3- stearyl-thio propionic ester) etc..As comprising ultraviolet The light stabilizer of light absorbers can be enumerated: 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..
It as benzophenone based compound, can enumerate: benzophenone, 2,4-DihydroxyBenzophenone, 2,2 '-dihydroxy Benzophenone, 2,2 ', 4,4 '-tetrahydroxybenzophenones, ESCALOL 567,2,2 '-dihydroxy -4,4 '-two Methoxy benzophenone, 2,2 '-dihydroxy -4,4 '-dimethoxy -5- sulfonyl benzophenone, 2- hydroxyl -4- octyloxy hexichol Ketone, 2- hydroxyl -4- dodecyloxy benzophenones, 2- hydroxyl -4- octyloxybenzophenone, 2- hydroxyl -4- methoxyl group -5- sulphur Acyl group benzophenone, 5- chlorine-2-hydroxyl benzophenone, 2- hydroxyl -4- octyloxybenzophenone, 2- hydroxyl -4- methoxyl group -2 ' - Carboxyl benzophenone and 2- hydroxyl -4- (2- hydroxy-3-methyl-acryloxy isopropoxy) benzophenone etc..
It as benzotriazole based compound, can enumerate: 2- (5- methyl -2- hydroxy phenyl) benzotriazole, 2- (3,5- bis- Tert-butyl -2- hydroxy phenyl) benzotriazole, 2- (bis- tertiary pentyl -2- hydroxy phenyl of 3,5-) benzotriazole, 2- (3 ', 5 '-two uncles Butyl -4 '-methyl -2 '-hydroxy phenyl) benzotriazole, 2- (bis- tertiary pentyl -2- hydroxy phenyl of 3,5-) -5- chlorobenzotriazole, 2- (5- tert-butyl -2- hydroxy phenyl) benzotriazole, 2- [2 '-hydroxyls -3 ', 5 '-bis- (bis (alpha, alpha-dimethylbenzyl) base) phenyl] benzo three Azoles, 2- [2 '-hydroxyls -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 Salicylic acids alkyl phenyl esters such as phenylester etc..
It as oxanilide based compound, can enumerate: 2- ethyoxyl -2 '-ethyloxanilide, 2- ethyoxyl -5- Tert-butyl -2 '-ethyloxanilide and 2- ethyoxyl -3 '-dodecyl butoxanilide etc..
It as cyanoacrylate based compound, can enumerate: cyano -3 ethyl -2-, 3 '-diphenylacrylate esters, 2- Ethylhexyl-cyano -3,3 '-diphenylacrylate ester etc..
It as the amine compound that is obstructed, can enumerate: 4- acetoxyl group -2,2,6,6- tetramethyl piperidines, 4- stearoyl keto Base -2,2,6,6- tetramethyl piperidine, 4- acryloxy -2,2,6,6- tetramethyl piperidine, 4- (phenylacetyl oxygroup) -2,2,6, 6- tetramethyl piperidine, 4 benzoyloxy 2,2,6,6 tetramethyl piperidine, 4- methoxyl group -2,2,6,6- tetramethyl piperidine, 4- ten Eight alkyl oxy -2,2,6,6- tetramethyl piperidines, 4- cyclohexyl oxygroup -2,2,6,6- tetramethyl piperidine, 4- benzyl oxygroup -2,2, 6,6- tetramethyl piperidine, 4- phenoxy group -2,2,6,6- tetramethyl piperidine, 4- (ethylcarbamoyl oxygroup) -2,2,6,6- tetramethyl Phenylpiperidines, 4- (cyclohexyl carboxyamide oxygroup) -2,2,6,6- tetramethyl piperidine, 4- (phenylcarbamoyl oxygroup) -2,2,6, 6- tetramethyl piperidine, bis- (2,2,6,6- tetramethyl -4- piperidyl) carbonic esters, bis- (2,2,6,6- tetramethyl -4- piperidyls) grass Acid esters, bis- (2,2,6,6- tetramethyl -4- piperidyl) malonates, bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, Bis- (2,2,6,6- tetramethyl -4- piperidyl) adipate esters, bis- (2,2,6,6- tetramethyl -4- piperidyl) terephthalates, 1,2- bis- (2,2,6,6- tetramethyl -4- piperidyl oxygroup)-ethane, α, the bis- (2,2,6,6- tetramethyl -4- piperidyl oxygen of α ' - Base)-paraxylene, bis- (2,2,6,6- tetramethyl -4- piperidyl)-toluylene -2,4- diurethanes, it is bis- (2,2, 6,6- tetramethyl -4- piperidyl)-hexa-methylene -1,6- diurethane, three (2,2,6,6- tetramethyl -4- piperidyls) - Benzene -1,3,5- tricarboxylic ester, three (2,2,6,6- tetramethyl -4- piperidyl)-benzene -1,3,4- tricarboxylic esters, 1,2- { 3- (3,5- Di-tert-butyl-hydroxy phenyl) propiono oxygroup } -2,2,6,6- tetramethyl piperidine and 1,2,3,4- butane tetracarboxylic acid and 1, 2,2,6,6- pentamethyl -4- hydroxy piperidine and β, β, β ', β '-tetramethyl -3,9- [tetra- oxaspiro (5,5) of 2,4,8,10- 11 Alkane] dimethanol condensation product etc..
As antistatic agent, can enumerate: the toner bodies such as carbon black, graphite, tin antimony composite oxides, antimony indium tin are multiple 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 agent such as the various metallic particles such as compound, copper, nickel, silver, gold, aluminium (powder) or metallic fiber and (β-laurel Amide propiono) the quaternary ammonium salts system, sulfonate based compound, alkyl phosphate such as trimethyl ammonium sulfate, neopelex The antistatic agent etc. of the organic systems such as based compound.
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 type epoxy resin, brominated bisphenol a type epoxy resin molecule chain end glycidyl part or all by envelope The modifier at end, using brominated bisphenol A as the polycarbonate oligomer of Material synthesis, two phthalimide chemical combination of bromination The compounds such as the brominated diphenyls base alkane such as object, 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, bis- (tribromophenoxy) ethane, 1,2- bis- (five Bromophenyl) ethane, ethylene-is bis--(tetrabromo phthalimide), tetrabromobisphenol A, brominated polycarbonate oligomer, poly- tribromo The brominated Polystyrenes such as styrene, 1,2- bis- (penta-bromophenyl) ethane etc..
It 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 naphthalene ester, tricresyl phosphate base diphenyl, phosphoric acid diformazan Phenyl diphenyl, diphenyl phosphate (2- ethylhexyl) ester, di(2-ethylhexyl)phosphate (isopropyl phenyl) phenylester, mono phosphoric acid ester isodecyl Ester, 2- acryloyl-oxyethyl phosphate ester acid, 2- methacryloxyethyl phosphate ester acid, diphenyl -2- acryloyl Oxygroup ethyl phosphonic acid ester, diphenyl -2- methacryloxyethyl 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- phenylene bis- (2,6- dimethylphenylphosphates), resorcinol 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 condensations phosphate such as phosphate and their condensation product etc..
It as chlorine-based flame retardant, can enumerate: five cyclodecane of pentachloro-, hexachloro-benzene, toluene pentachloride, tetrachlorobisphenol A and polychlorostyrene Styrene etc..It as triazine flame retardant, can enumerate: melamine, methyl guanamines, benzoguanamine, acryloyl guanamines, 2,4- Diamino -6- nonyl -1,3,5- triazine, 2,4- diamino -6- hydroxyl -1,3,5- triazine, dihydroxy -1,3 2- amino -4,6-, 5- triazine, 2,4- diamino -6- methoxyl group -1,3,5- triazine, 2,4- diamino -6- ethyoxyl -1,3,5- triazine, 2,4- diamino Base -6- propoxyl group -1,3,5- triazine, 2,4- diamino -6- isopropoxy -1,3,5- triazine, sulfydryl -1 2,4- diamino -6-, 3,5- triazine and 2- amino -4,6- dimercapto -1,3,5- triazine etc..
It as the salt of phosphoric acid and 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 organochlorines such as machine thiophanate fungicide, captan, Bravo system fungicide, thiophanate-methyl, benomyl, carbendazim, thiabendazole etc. The acyls such as the dicarboximides system such as benzimidazole system fungicide, iprodione, vinclozolin, procymidone fungicide, furametpyr The morpholines system fungicide such as the phenylpyrroles such as amine system fungicide, fludioxonil system fungicide, dimethomorph, Fluoxastrobin, kresoxim-methyl, The anilino-pyrimidines system fungicide such as the methoxy acrylates 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 Bis- (acetyl bromide oxygroup) ethane of amine, o-phenyl phenol (OPP), diphenyl, chlorodiphenyl base, cresols, 1,2-, cinnamic acid, acetic acid benzene Ester, allyl isothiocyanate, Alpha-Methyl acetophenone, thymol, full-chloro-cyclopentadiene, bromoacetic acid, the bromo- 3- itrile group propionyl of 2,2- bis- Amine, ethyl chloroacetate, butyl chloroacetate, methyl chloroacetate, 5- chloro-2-methyl isothiazoline -3- ketone, glutaraldehyde and Hinokitiol Deng.
It as antibacterial agent, can enumerate: make silver, zinc, one kind of copper or antibiotic property Metal Supported of more than two kinds in inorganization Close inorganic system's powder obtained from object.It as load, can enumerate: zeolite, apatite, basic zirconium phosphate, titanium oxide, silica Gel, aluminum sulfate hydroxide, calcium phosphate, calcium silicates etc..In addition it can enumerate: with phosphate, boric acid system, silicic acid system Be respectively in one kind or two or more glass as glass forming constituents of glass containing silver, zinc, copper one kind or two or more Antibiotic property metal obtained from antibacterial glass powder.
As lubricant, can enumerate: fatty acid, fatty acid metal salts, oxo fatty acid, paraffin, low molecular weight it is poly- Alkene, fatty acid amide, alkylenebisfatty amide, aliphatic ketone, fatty acid part are saponified ester, fatty acid low-carbon-ester, fat Acid polyol ester, fatty acid polyglycol ethyl alcohol ester and modified organic silicon etc..
As fatty acid, can enumerate: oleic acid, stearic acid, lauric acid, hydroxy stearic acid, behenic acid, arachidonic acid, The fatty acid of the carbon numbers 6~40 such as linoleic acid, linolenic acid, ricinoleic acid, palmitinic acid, montanic acid and their mixture.As rouge Fat acid metal salt can be enumerated: 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 acid Alkali (soil) gold of the fatty acid of carbon numbers 6~40 such as magnesium, behenic acid calcium, behenic acid zinc, behenic acid barium, montanic acid sodium and montanic acid calcium Belong to salt.
It as oxo fatty acid, can enumerate: 1,2- stearoxylic acid etc..
It as paraffin, can enumerate: the paraffin of 18 or more the carbon numbers such as atoleine, natural paraffin wax, microwax and vaseline.
It as the polyolefin of low molecular weight, can enumerate: polyethylene wax, maleic acid modified polyethylene wax, the poly- second of oxidized form Alkene wax, haloflex wax and the polyolefin below of polypropylene wax equimolecular quantity 5000.It, specifically can be with as fatty acid amide It enumerates: the fatty acid amide of 6 or more the carbon numbers such as oleamide, erucic amide, Shan Yu amide.
It as alkylenebisfatty amide, can enumerate: methylene bis stearamide, ethylenebisstearamide and N, N- The alkylenebisfatty amide of 6 or more the carbon numbers such as bis- (2- hydroxyethyl) stearmides.
It as aliphatic ketone, can enumerate: the aliphatic ketone of 6 or more the carbon numbers such as higher aliphatic ketone.As fatty acid moieties Divide saponification ester, can enumerate: partly-hydrolysed ester of montanic acid etc..
It as fatty acid low-carbon-ester, can enumerate: stearate, oleate, linoleate, linolenate, adipic acid Ester, behenic acid ester, arachidonate, montanate and isostearate etc..
It 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 ester etc..
As fatty acid polyglycol ethyl alcohol 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 contains Having organosilicon, high-grade aliphatic ester modified organic silicon, methacrylic modified organic silicon and the fluorine richness of higher fatty acids has Machine silicon etc..
It as solidification catalyst, can enumerate: (peroxidized t-butyl perbenzoate, benzoyl peroxide, peroxidating first and second Ketone etc.) and the organic peroxides, octyl acid tin, 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 fatty acid salt, 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 amines, 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..In turn, it can enumerate: single (2- (methyl) acryloxy second Base) phosphate cpds, diazabicyclo endecatylene series catalysts, lewis acid and the acid anhydrides such as phosphate ester acid etc..
It as Photoepolymerizationinitiater initiater, can enumerate: (2-hydroxybenzoyl) compound (2- hydroxy-2-methyl -1- phenyl-propane - 1- ketone, 1- hydroxycyclohexylphenylketone, 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 oxide etc.) and benzil dimethyl ketal etc..
In turn, by the way that of the invention answer can also be made with coating is mixed in tribo-luminescence ceramic material of the invention Power photism coating composition.
Stress irradiance coating composition of the 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 containing tribo-luminescence ceramic material of the invention shines Brightness is high, therefore can carry out visual high coating.
As coating composition, the coating composition containing overlay film formative resin can be used.In coating composition, root According to need can also contain: solvent, dispersing agent, filler, thickener, levelling agent, curing agent, crosslinking agent, pigment, defoaming agent, The coating such as antioxidant, the light stabilizer comprising ultraviolet absorbing agent, fire retardant, solidification catalyst, fungicide and antibacterial agent Use additive.
As material used in coating composition, thermosetting resin, normal temperature cure resin, ultraviolet light also can 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..
It as ink film forming material, can enumerate: polyurethane resin, acrylic resin, polyamide, vinyl chloride- Vinyl acetate resin and propylene dichloride resin etc..
It 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 (single ethyl of C4~10, such as tetrahydrofuran, EG Ether, the single-butyl ether of EG, the monomethyl ether of PG 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, ethyl alcohol, normal propyl alcohol and isopropanol, n-butanol, isobutanol, sec-butyl alcohol and the tert-butyl alcohol, 2- ethylhexyl alcohol), amide (C3~6, such as dimethylformamide, dimethyl acetamide, N-Methyl pyrrolidone), sulfoxide (C2~4, such as dimethyl sulfoxide) and their mixed solvent of more than two kinds, water or aforementioned mixed solvent.As dispersion Agent can enumerate: the formal of naphthalene sulfonate [alkali metal (Na and K etc.) salt, ammonium salt etc.] as long as being macromolecule dispersing agent Woods condensation product, poly styrene sulfonate (same as described above), polyacrylate (same as described above), poly- (2~4) carboxylic acid (Malaysia Acid/glycerol/monoallyl ether copolymer etc.) salt (same as described above), carboxymethyl cellulose (Mn2000~10000) and polyethylene Alcohol (Mn2000~100000) etc..
As low molecule dispersing agent, 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) 1~30 mole of addition product of AO (C2~4) of amide.
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 fatty acid (lauric acid, stearic acid etc.) of C4~30 and polynary (2~6 or its more than) alcohol (such as GR, PE, sorb Sugar alcohol and anhydrous sorbitol) monoester compound.
(3) carboxylic acid type
Alkali metal (same as described above) salt of the fatty acid (same as described above) of C4~30.
(4) sulfuric acid ester type
The sulphur of AO (C2~4) 1~30 mole of addition product of the aliphatic alcohol (same as described above) and aliphatic alcohol of C4~30 Acid esters 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 list of AO (C2~4) 1~30 mole of addition product of the aliphatic alcohol (same as described above) and aliphatic alcohol of C4~30 The salt [alkali metal (same as described above) salt, quaternary ammonium salt etc.] of phosphate or bisphosphate.
(7) primary~tertiary amine salt form
Aliphatic amine [primary amine (lauryl amine etc.), secondary amine (dibutylamine etc.) and tertiary amine (the dimethyl stearyl of C4~30 Amine etc.)] inorganic acid (hydrochloric acid, sulfuric acid, the nitre of the monoesters of hydrochloride, triethanolamine and the fatty acid of C4~30 (same as described above) Acid and phosphoric acid etc.) salt.
(8) quaternary
The nothing of the quaternary ammonium (butyl trimethyl ammonium, diethyl lauryl methyl ammonium, dimethyl distearyl ammonium etc.) of C4~30 Machine acid (same as described above) salt etc..
It as inorganic dispersant, can enumerate: alkali metal (same as described above) salt and phosphate dispersing agent (phosphorus of polyphosphoric acid Acid, monoalkyl phosphoric acid esters and dialkyl phosphate etc.) etc..
It as filler, can enumerate: 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 substances based inorganic material such as object, silicon carbide, silicon nitride.Separately Outside, the metal powders such as aluminium, zinc, copper can also be added depending on the application.In turn, it as the concrete example of filler, can enumerate: dioxy SiClx colloidal sol, zirconia sol, alumina sol, TiO 2 sol isosol；Silica sand, quartz, close quartzy salt, diatomite Etc. silica-based substance；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 substances based inorganic material such as boron, aluminium nitride, aluminium carbide, silicon nitride, silicon carbide, 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 powders such as aluminium, bronze, lead, stainless steel, zinc；With carbon black, coke, graphite, thermally decomposed carbon, hollow carbon balls Equal carbon body etc..
It as thickener, can enumerate: montmorillonite system clay mineral, the bentonite comprising these mineral, colloidal oxidation The inorganic fillers 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 epoxy-modified object of polyethers The association thickeners such as rouge system thickener, urethane-modified polyether system, polyurethane resin system, polyether polyol system etc. are special The eggs such as the surfactants 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 type 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 At object, perfluoroalkyl carboxylate, perfluoroalkyl betain etc.) and modified silicon oil [polyether modified silicon oil, (methyl) acrylate Modified silicon oil etc.] etc..
Curing agent can be enumerated as the curing agent of polyalcohols: 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 body of polyisocyanate compound, buret body, polyisocyanic acid The addition body of polyalcohol as ester compounds and ethylene glycol, propylene glycol, 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. It like that at normal temperature being capable of cured isocyanates.It as the curing agent of epoxy resin, can enumerate: acid anhydrides, phenolic aldehyde tree Rouge, polyamide, amine additives, urea resin, melamine resin and isocyanates etc..
It as crosslinking agent, can enumerate: melamine resin, urea resin, polyisocyanate compound, block polyisocyanate cyanogen Ester compound, epoxide or resin, carboxylated compound or resin, acid anhydrides, based compound containing alkoxy silane or tree Rouge 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..
It as pigment, other than aforesaid pigments, can also enumerate: vanadium pentoxide, calcium vanadate, vanadic acid magnesium and ammonium metavanadate Equal vfanadium compound；Magnesium phosphate, ammonium magnesium phosphate eutectoid object, one hydrogen magnesium of phosphoric acid, magnesium dihydrogen phosphate, magnesium phosphate calcium eutectoid object, phosphorus Sour magnesium cobalt eutectoid object, magnesium phosphate nickel eutectoid object, phosphorous acid magnesium, phosphorous acid magnesium calcium eutectoid object, 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 object；The rust resisting pigment containing zinc ingredient 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 ingredient or calcium metasilicate ingredient；Calcium from The metal ion exchangeds silica such as son exchange silica, magnesium ion exchange silica；With preventing comprising Cr VI, lead etc. Become rusty pigment etc..
As defoaming agent, for example: silicone oil, dimethyl polysiloxane, organic modified polyorganosiloxane, fluorine richness are poly- The organic silicon-types such as siloxanes defoaming agent, mineral oil system defoaming agent, non-organic silicon polymer system defoaming agent, comprising changing selected from organic At least one kind of defoaming agent in property fluorine compounds and poly (oxyalkylene) based compound and the aliphatic alcohol comprising 18 or more carbon number Defoaming agent etc..
For antioxidant, the light stabilizer comprising ultraviolet absorbing agent, fire retardant, solidification catalyst, fungicide and Antibacterial agent etc. can enumerate aforementioned substances.
Detailed description of the invention
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.
Specific embodiment
Invention is further described in detail for 1-2 and specific embodiment with reference to the accompanying drawing.
Embodiment 1
A kind of tribo-luminescence ceramic material, chemical composition Zn1.96OS: 0.02Mn2+, 0.02Y3+。
1.89 grams of Zn (NO are weighed respectively according to molar ratio 1:13)2With 1.61 grams of ZnSO4High pure raw material dissolves it simultaneously In deionized water, certain density Zn (NO is obtained3)2And ZnSO4Mixed solution；H is continually fed into above-mentioned solution2S gas Body, duration of ventilation are 0.5 hour, obtain ZnS precipitating；The excessive NaOH solution of 1mol/L is added dropwise into above-mentioned solution again, It obtains Zn (OH)2Precipitating；Above-mentioned turbid solution is packed into autoclave, and reaction kettle is placed in baking oven and carries out heating reaction, Heating temperature is 200 DEG C, and the reaction time is 2 hours；The precipitating obtained after reaction is filtered, is dried, a kind of nanometer is obtained Forerunner's powder of ZnO and ZnS mixing；With the forerunner's powder and high-purity MnCO of above-mentioned acquisition3、Y2O3As raw material, according to Chemical composition Zn1.96OS: 0.02Mn2+, 0.02Y3+The proportion of middle each element accurately weighs each raw material, and in the agate mortar It is uniformly mixed；The above-mentioned raw materials of certain mass are weighed, and dry-pressing formed in stainless steel mould, 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, sintering time is 4 hours, is taken out after cooling to get the tribo-luminescence ceramic material.
Embodiment 2
A kind of tribo-luminescence ceramic material, chemical composition Zn1.98OS: 0.01Mn2+, 0.01Gd3+。
1.89 grams of Zn (NO are weighed respectively according to molar ratio 1:13)2With 1.61 grams of ZnSO4High pure raw material dissolves it simultaneously In deionized water, certain density Zn (NO is obtained3)2And ZnSO4Mixed solution；H is continually fed into above-mentioned solution2S gas Body, duration of ventilation are 1 hour, obtain ZnS precipitating；The excessive NaOH solution of 1mol/L is added dropwise into above-mentioned solution again, obtains It obtains Zn (OH)2Precipitating；Above-mentioned turbid solution is packed into autoclave, and reaction kettle is placed in baking oven and carries out heating reaction, is added Hot temperature is 180, and the reaction time is 2 hours；The precipitating obtained after reaction is filtered, is dried, obtain a kind of nano-ZnO and Forerunner's powder of ZnS mixing；With the forerunner's powder and high-purity MnCO of above-mentioned acquisition3、Gd2O3As raw material, according to chemistry Form Zn1.98OS: 0.01Mn2+, 0.01Gd3+The proportion of middle each element accurately weighs each raw material, and mixes in the agate mortar Uniformly；The above-mentioned raw materials of certain mass are weighed, and dry-pressing formed in stainless steel mould, 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, sintering time is 6 hours, is taken out after cooling to get the tribo-luminescence ceramic material.
Embodiment 3
A kind of tribo-luminescence ceramic material, chemical composition Zn1.92OS: 0.04Mn2+, 0.04Nd3+。
1.89 grams of Zn (NO are weighed respectively according to molar ratio 1:13)2With 1.61 grams of ZnSO4High pure raw material dissolves it simultaneously In deionized water, certain density Zn (NO is obtained3)2And ZnSO4Mixed solution；H is continually fed into above-mentioned solution2S gas Body, duration of ventilation are 0.5 hour, obtain ZnS precipitating；The excessive NaOH solution of 1mol/L is added dropwise into above-mentioned solution again, It obtains Zn (OH)2Precipitating；Above-mentioned turbid solution is packed into autoclave, and reaction kettle is placed in baking oven and carries out heating reaction, Heating temperature is 200 DEG C, and the reaction time is 3 hours；The precipitating obtained after reaction is filtered, is dried, a kind of nanometer is obtained Forerunner's powder of ZnO and ZnS mixing；With the forerunner's powder and high-purity MnCO of above-mentioned acquisition3、Nd2O3As raw material, press According to chemical composition Zn1.92OS: 0.04Mn2+, 0.04Nd3+The proportion 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 dry-pressing formed in stainless steel mould, 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 It is 1000 DEG C, sintering time is 10 hours, is taken out after cooling to get the tribo-luminescence ceramic material.
Embodiment 4
A kind of tribo-luminescence ceramic material, chemical composition Zn1.84OS: 0.08Mn2+, 0.04Y3+, 0.04Gd3+。
1.89 grams of Zn (NO are weighed respectively according to molar ratio 1:13)2With 1.61 grams of ZnSO4High pure raw material dissolves it simultaneously In deionized water, certain density Zn (NO is obtained3)2And ZnSO4Mixed solution；H is continually fed into above-mentioned solution2S gas Body, duration of ventilation are 1 hour, obtain ZnS precipitating；The excessive NaOH solution of 1mol/L is added dropwise into above-mentioned solution again, obtains It obtains Zn (OH)2Precipitating；Above-mentioned turbid solution is packed into autoclave, and reaction kettle is placed in baking oven and carries out heating reaction, is added Hot temperature is 180 DEG C, and the reaction time is 3 hours；The precipitating obtained after reaction is filtered, is dried, a kind of nano-ZnO is obtained With forerunner's powder of ZnS mixing；With the forerunner's powder and high-purity MnCO of above-mentioned acquisition3、Y2O3、Gd2O3As raw material, press According to chemical composition Zn1.84OS: 0.08Mn2+, 0.04Y3+, 0.04Gd3+The proportion of middle each element accurately weighs each raw material, and It is uniformly mixed in the agate mortar；The above-mentioned raw materials of certain mass are weighed, and dry-pressing formed in stainless steel mould, pressure is 15MPa obtains cylindrical greenwave；The greenwave is subjected to high temperature sintering under reducing atmosphere condition, heating rate is 10 DEG C/ Min, sintering temperature are 1200 DEG C, and sintering time is 8 hours, are taken out after cooling to get the tribo-luminescence ceramic material.
Embodiment 5
A kind of tribo-luminescence ceramic material, chemical composition Zn1.88OS: 0.06Mn2+, 0.03Y3+, 0.03Nd3+。
1.89 grams of Zn (NO are weighed respectively according to molar ratio 1:13)2With 1.61 grams of ZnSO4High pure raw material dissolves it simultaneously In deionized water, certain density Zn (NO is obtained3)2And ZnSO4Mixed solution；H is continually fed into above-mentioned solution2S gas Body, duration of ventilation are 0.5 hour, obtain ZnS precipitating；The excessive NaOH solution of 1mol/L is added dropwise into above-mentioned solution again, It obtains Zn (OH)2Precipitating；Above-mentioned turbid solution is packed into autoclave, and reaction kettle is placed in baking oven and carries out heating reaction, Heating temperature is 200 DEG C, and the reaction time is 2 hours；The precipitating obtained after reaction is filtered, is dried, a kind of nanometer is obtained Forerunner's powder of ZnO and ZnS mixing；With the forerunner's powder and high-purity MnCO of above-mentioned acquisition3、Y2O3、Nd2O3As original Material, according to chemical composition Zn1.88OS: 0.06Mn2+, 0.03Y3+, 0.03Nd3+The proportion of middle each element accurately weighs each original Material, and be uniformly mixed in the agate mortar；The above-mentioned raw materials of certain mass are weighed, and dry-pressing formed in stainless steel mould, pressed 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, and sintering time is 6 hours, is taken out after cooling to get 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+。
1.89 grams of Zn (NO are weighed respectively according to molar ratio 1:13)2With 1.61 grams of ZnSO4High pure raw material dissolves it simultaneously In deionized water, certain density Zn (NO is obtained3)2And ZnSO4Mixed solution；H is continually fed into above-mentioned solution2S gas Body, duration of ventilation are 1 hour, obtain ZnS precipitating；The excessive NaOH solution of 1mol/L is added dropwise into above-mentioned solution again, obtains It obtains Zn (OH)2Precipitating；Above-mentioned turbid solution is packed into autoclave, and reaction kettle is placed in baking oven and carries out heating reaction, is added Hot temperature is 180 DEG C, and the reaction time is 2 hours；The precipitating obtained after reaction is filtered, is dried, a kind of nano-ZnO is obtained With forerunner's powder of ZnS mixing；With the forerunner's powder and high-purity MnCO of above-mentioned acquisition3、Y2O3、Gd2O3、Nd2O3As Raw material, according to chemical composition Zn1.8OS: 0.1Mn2+, 0.04Y3+, 0.04Gd3+, 0.02Nd3+The proportion of middle each element, accurately Each raw material is weighed, and is uniformly mixed in the agate mortar；Weigh the above-mentioned raw materials of certain mass, and the dry-pressing in stainless steel mould Molding, pressure 14MPa obtain cylindrical greenwave；The greenwave is subjected to high temperature sintering under reducing atmosphere condition, is heated up Rate is 10 DEG C/min, and sintering temperature is 1300 DEG C, and sintering time is 5 hours, is taken out after cooling to get the tribo-luminescence Ceramic material.
Comparative example 1
A kind of tribo-luminescence ceramic material, chemical composition Zn1.98OS: 0.02Mn2+。
1.89 grams of Zn (NO are weighed respectively according to molar ratio 1:13)2With 1.61 grams of ZnSO4High pure raw material dissolves it simultaneously In deionized water, certain density Zn (NO is obtained3)2And ZnSO4Mixed solution；H is continually fed into above-mentioned solution2S gas Body, duration of ventilation are 0.5 hour, obtain ZnS precipitating；The excessive NaOH solution of 1mol/L is added dropwise into above-mentioned solution again, It obtains Zn (OH)2Precipitating；Above-mentioned turbid solution is packed into autoclave, and reaction kettle is placed in baking oven and carries out heating reaction, Heating temperature is 200 DEG C, and the reaction time is 2 hours；The precipitating obtained after reaction is filtered, is dried, a kind of nanometer is obtained Forerunner's powder of ZnO and ZnS mixing；With the forerunner's powder and high-purity MnCO of above-mentioned acquisition3As raw material, according to chemistry Form Zn1.98OS: 0.02Mn2+The proportion of middle each element accurately weighs each raw material, and is uniformly mixed in the agate mortar；It weighs The above-mentioned raw materials of certain mass, and it is dry-pressing formed in stainless steel mould, and pressure 10MPa obtains cylindrical greenwave；It will be described Greenwave carry out high temperature sintering under reducing atmosphere condition, heating rate is 10 DEG C/min, and sintering temperature is 1400 DEG C, when sintering Between be 4 hours, take out after cooling to get the tribo-luminescence ceramic material.
Comparative example 2
A kind of tribo-luminescence ceramic material, chemical composition Zn1.92OS: 0.08Mn2+。
1.89 grams of Zn (NO are weighed respectively according to molar ratio 1:13)2With 1.61 grams of ZnSO4High pure raw material dissolves it simultaneously In deionized water, certain density Zn (NO is obtained3)2And ZnSO4Mixed solution；H is continually fed into above-mentioned solution2S gas Body, duration of ventilation are 1 hour, obtain ZnS precipitating；The excessive NaOH solution of 1mol/L is added dropwise into above-mentioned solution again, obtains It obtains Zn (OH)2Precipitating；Above-mentioned turbid solution is packed into autoclave, and reaction kettle is placed in baking oven and carries out heating reaction, is added Hot temperature is 180 DEG C, and the reaction time is 3 hours；The precipitating obtained after reaction is filtered, is dried, a kind of nano-ZnO is obtained With forerunner's powder of ZnS mixing；With the forerunner's powder and high-purity MnCO of above-mentioned acquisition3As raw material, according to chemical group At Zn1.92OS: 0.08Mn2+The proportion of middle each element accurately weighs each raw material, and is uniformly mixed in the agate mortar；Weigh one Determine the above-mentioned raw materials of quality, and dry-pressing formed in stainless steel mould, pressure 15MPa obtains cylindrical greenwave；It 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 It is 8 hours, takes out after cooling to get the tribo-luminescence ceramic material.
Fig. 1 show the tribo-luminescence spectrogram of embodiment 1 ~ 3 and comparative example 1, wherein the preparation of comparative example 1 and example 1 Condition is identical, and difference is only that in comparative example 1 that there is no introduce Y3+、Gd3+And Nd3+Equal impurity rare earth ion.It can be with from figure Find out, embodiment 1 ~ 3 all has apparent tribo-luminescence phenomenon, and 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 great influence to the tribo-luminescence intensity of sample, pass through Introduce rare earth ion Y3+、Gd3+And Nd3+One or more of combination provide trap level, can effectively enhance tribo-luminescence effect Fruit.
Fig. 2 show the tribo-luminescence spectrogram of embodiment 4 ~ 6 and comparative example 2, wherein the preparation of comparative example 2 and example 4 Condition is identical, and difference is only that in comparative example 2 that there is no introduce Y3+、Gd3+And Nd3+Equal impurity rare earth ion.It can be with from figure Find out, embodiment 4 ~ 6 also has apparent tribo-luminescence phenomenon, and luminous peak position is near the green light of 540nm, but it is sent out Luminous intensity is lower than embodiment 1 ~ 3 on the whole, illustrates active ions Mn2+Preferred doping concentration be about 0.02, pass through introduce rare earth Ion Y3+、Gd3+And Nd3+One or more of combination provide trap level, can effectively enhance tribo-luminescence effect.
The phenomenon that tribo-luminescence, is observed very early, but to the source of its excitation mechanism and excitation state, does not have also so far It determining completely, field personnel generally only do phenomenon description to tribo-luminescence, do not illustrate but its light sources and mechanism, Only think to influence that there are many triboluminescent factor, even if the substance of same element, in different preparation condition (such as concentration of element Proportion, sintering temperature, sintering time when refining substance), different pressure, under different frictional strengths, tribo-luminescent performance Difference it is also very big.Therefore, research tribo-luminescence is actually related with which factor, 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 final conclusion to this so far.Since friction is sent out The mechanism of light is unclear so far, so on the one hand people are dedicated to the developmental research of practical application, on the other hand makes great efforts to explore Triboluminescent mechanism and its dynamic process seek the relationship between tribo-luminescent performance and structure, establish triboluminescent Prediction theory studies the triboluminescent mechanism of triboluminescent mechanism, especially complex, becomes chemist and physicist is closed The hot spot of note.For these reasons, for the present invention by optimization preparation condition and matrix chemical composition, having prepared has higher rub Wipe the Zn of luminous efficiency2-x-yOS: xMn2+, yRe3+Triboluminescent material, practical application value with higher.

Claims (2)

1. a kind of tribo-luminescence ceramic material, which is characterized in that the chemical composition general formula of the ceramics is Zn2-x-yOS: xMn2+,yRe3+, wherein Re is Y, and one or more of Gd and Nd are combined, and the value range of x and y are respectively as follows: 0.01≤x≤0.1, 0.01≤y≤0.1；The preparation method of the tribo-luminescence ceramic material the following steps are included:
(1) Zn (NO of certain mass is weighed respectively according to molar ratio 1:13)2And ZnSO4It is dissolved in by high pure raw material simultaneously In ionized water, certain density Zn (NO is obtained3)2And ZnSO4Mixed solution；
(2) H is continually fed into Xiang Shangshu solution2S gas, duration of ventilation are 0.5 ~ 1 hour, obtain ZnS precipitating；
(3) the excessive NaOH solution of 1mol/L is added dropwise into above-mentioned solution again, obtains Zn (OH)2Precipitating；
(4) ZnS and Zn (OH) will be contained simultaneously2The turbid solution of precipitating is packed into autoclave, and by reaction kettle be placed in baking oven into Row heating reaction, heating temperature are 180 ~ 200 DEG C, and the reaction time is 2 ~ 4 hours；
(5) precipitating obtained after reaction is filtered, dried, obtain forerunner's powder of a kind 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 proportion of middle each element, wherein Re is Y, one or more of Gd and Nd combination, x and y's Value range is respectively as follows: 0.01≤x≤0.1, and 0.01≤y≤0.1 accurately weighs each raw material, and mixing is equal in the agate mortar It is even；
(7) above-mentioned raw materials of certain mass are weighed, and dry-pressing formed in stainless steel mould, pressure 10-15MPa is justified Cylindricality greenwave；
(8) 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, sintering time is 4 ~ 10 hours, is taken out after cooling to get the tribo-luminescence ceramic material.
2. a kind of preparation method of tribo-luminescence ceramic material, it is characterised in that the following steps are included:
(1) Zn (NO of certain mass is weighed respectively according to molar ratio 1:13)2And ZnSO4It is dissolved in by high pure raw material simultaneously In ionized water, certain density Zn (NO is obtained3)2And ZnSO4Mixed solution；
(2) H is continually fed into Xiang Shangshu solution2S gas, duration of ventilation are 0.5 ~ 1 hour, obtain ZnS precipitating；
(3) the excessive NaOH solution of 1mol/L is added dropwise into above-mentioned solution again, obtains Zn (OH)2Precipitating；
(4) ZnS and Zn (OH) will be contained simultaneously2The turbid solution of precipitating is packed into autoclave, and by reaction kettle be placed in baking oven into Row heating reaction, heating temperature are 180 ~ 200 DEG C, and the reaction time is 2 ~ 4 hours；
(5) precipitating obtained after reaction is filtered, dried, obtain forerunner's powder of a kind 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 proportion of middle each element, wherein Re is Y, one or more of Gd and Nd combination, x and y's Value range is respectively as follows: 0.01≤x≤0.1, and 0.01≤y≤0.1 accurately weighs each raw material, and mixing is equal in the agate mortar It is even；
(7) above-mentioned raw materials of certain mass are weighed, and dry-pressing formed in stainless steel mould, pressure 10-15MPa is justified Cylindricality greenwave；
(8) 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, sintering time is 4 ~ 10 hours, is taken out after cooling to get the tribo-luminescence ceramic material.
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