CN105349141A - Niobate luminescent material with elastic stress luminescence property and preparation method thereof - Google Patents
Niobate luminescent material with elastic stress luminescence property and preparation method thereof Download PDFInfo
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- CN105349141A CN105349141A CN201510874489.XA CN201510874489A CN105349141A CN 105349141 A CN105349141 A CN 105349141A CN 201510874489 A CN201510874489 A CN 201510874489A CN 105349141 A CN105349141 A CN 105349141A
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- 239000000463 material Substances 0.000 title claims abstract description 121
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 238000004020 luminiscence type Methods 0.000 title abstract description 16
- 239000000126 substance Substances 0.000 claims abstract description 15
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 8
- 229910052788 barium Inorganic materials 0.000 claims abstract description 5
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 5
- 229910052712 strontium Inorganic materials 0.000 claims abstract description 5
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 5
- 239000011159 matrix material Substances 0.000 claims abstract description 4
- 229910052693 Europium Inorganic materials 0.000 claims abstract description 3
- 229910052688 Gadolinium Inorganic materials 0.000 claims abstract description 3
- 229910052779 Neodymium Inorganic materials 0.000 claims abstract description 3
- 229910052772 Samarium Inorganic materials 0.000 claims abstract description 3
- 229910052769 Ytterbium Inorganic materials 0.000 claims abstract description 3
- 239000012190 activator Substances 0.000 claims abstract description 3
- 229910052793 cadmium Inorganic materials 0.000 claims abstract description 3
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 3
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 3
- 229910052709 silver Inorganic materials 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000002994 raw material Substances 0.000 claims description 46
- 238000000034 method Methods 0.000 claims description 17
- 238000001035 drying Methods 0.000 claims description 14
- 238000000227 grinding Methods 0.000 claims description 14
- 239000011812 mixed powder Substances 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 13
- 238000009826 distribution Methods 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 6
- -1 rare earth ions Chemical class 0.000 claims description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 4
- 239000002861 polymer material Substances 0.000 claims description 4
- 150000002910 rare earth metals Chemical group 0.000 claims description 4
- 150000003624 transition metals Chemical class 0.000 claims description 4
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 238000005245 sintering Methods 0.000 claims description 3
- 230000000007 visual effect Effects 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- 201000010099 disease Diseases 0.000 claims description 2
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 230000009467 reduction Effects 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- 229910019695 Nb2O6 Inorganic materials 0.000 abstract 1
- 238000010532 solid phase synthesis reaction Methods 0.000 abstract 1
- 239000011575 calcium Substances 0.000 description 29
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 12
- 239000012254 powdered material Substances 0.000 description 12
- 238000001228 spectrum Methods 0.000 description 9
- 238000012544 monitoring process Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 230000001066 destructive effect Effects 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 229930182556 Polyacetal Natural products 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 4
- 239000004743 Polypropylene Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000000695 excitation spectrum Methods 0.000 description 4
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 4
- 229920000573 polyethylene Polymers 0.000 description 4
- 239000004926 polymethyl methacrylate Substances 0.000 description 4
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- 238000000634 powder X-ray diffraction Methods 0.000 description 4
- 230000008859 change Effects 0.000 description 3
- 230000005489 elastic deformation Effects 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 2
- 238000002447 crystallographic data Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000002050 diffraction method Methods 0.000 description 2
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- 230000005284 excitation Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229920002379 silicone rubber Polymers 0.000 description 2
- 238000000904 thermoluminescence Methods 0.000 description 2
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 2
- 238000012800 visualization Methods 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229910003668 SrAl Inorganic materials 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000005166 mechanoluminescence Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 238000003836 solid-state method Methods 0.000 description 1
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- 239000002341 toxic gas Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7766—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7783—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals one of which being europium
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01L—MEASURING FORCE, STRESS, TORQUE, WORK, MECHANICAL POWER, MECHANICAL EFFICIENCY, OR FLUID PRESSURE
- G01L1/00—Measuring force or stress, in general
- G01L1/24—Measuring force or stress, in general by measuring variations of optical properties of material when it is stressed, e.g. by photoelastic stress analysis using infrared, visible light, ultraviolet
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- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Luminescent Compositions (AREA)
Abstract
The invention relates to a niobate luminescent material with elastic stress luminescence property and a preparation method thereof. The niobate luminescent material takes CaNb2O6 as a matrix and rare earth ion Pr<3+> as an activator, and has the following chemical expression: [(Ca(1-x)Mx)(1-z)]Nb2O6:(Pr(1-y)Ry)z(0<=x<=0.2, 0<=y<=0.5, 0<z<=0.1), wherein M represents a Ca-site substitute element and is selected from one or more of Mg, Sr and Ba; R represents a co-doped rare earth or transition metal element and is selected from one or more of La, Nd, Sm, Eu, Gd, Yb, Lu, Cr, Mn, Ag and Cd; x, y and z represent molar percentage contents. The niobate luminescent material is synthesized in air by the high-temperature solid-phase method. The niobate luminescent material and the preparation method thereof have the following advantages: (1) the material preparation method is simple, easy to operate and low in equipment demand; (2) the prepared material has strong elastic stress luminescence, allows naked eyes to clearly see the elastic stress luminescence in the dark, and is relatively good in heat and water resistance, excellent in workability and wide in application range; (3) the basic materials of the niobate luminescent material are all elements rich on the earth, and the niobate luminescent material belongs to environmental-friendly materials.
Description
Technical field
The invention belongs to stress irradiance functional materials science and technology field, relate to and a kind of there is niobate luminescent material of elastic stress luminescent properties and preparation method thereof.
Background technology
Stress irradiance (mechanoluminescence) refers to that object is being subject to various stress, as lower in the even effect such as sound vibrations of expanding, stretch, rupture, rub and emit beam, and namely changes mechanical energy is luminous energy.According to deformation degree during material generation stress irradiance, stress light emitting material can be divided into destructive stress luminescence and nondestructive stress irradiance, but not destructive stress luminescence can be divided into again, and elastic stress is luminous and plastic stress is luminous.Although only have the history of more than ten years to the research of elastic stress luminescent material, but due to the characteristic that elastic stress luminescent material has, such as in elastic deformation limit, its luminous light intensity and deformation degree are directly proportional, and inspected object is not damaged, sensor can be made into according to this feature of material, be used for the stress distribution situation of each position of monitoring component, realize stress distribution visualization real-time monitoring; When suffered stress intensity increase to exceed elastic properties of materials deformation range arrive plasticity and destructive deformation region time, the feature of plastic stress luminescent material and destructive stress luminescent material taken into account again by elastic stress luminescent material simultaneously, this will be conducive to detecting the elastic deformation of various different structure, plastic deformation and destructive distortion, can be used for the Real-Time Monitoring of the stressed and damage situations of object under test.
The stressing conditions of traditional electrical signal Measuring Object, needs point-to-point physical contact between electrode and object under test, and is subject to the restriction of object moving state and shape, cannot test, such as, engine etc. in working in a lot of situation.And when utilizing the stressing conditions of elastic stress luminescent material Measuring Object, these shortcomings can be overcome, and can remote monitoring be realized, improve the spatial resolution of stress distribution, have broad application prospects in the visualization measurement of dynamic object three-dimensional space stress distribution.In recent years, along with the synthesis of elastic stress luminescent material and the raising of development technique, developing rapidly of CCD camera and optical fiber technology, in the testing process of elastic stress luminescence sensor, can camera technique be utilized, visual for big area deformation, easy-to-look-up to hidden danger position, to repair in time, play the effect prevented trouble before it happens.Elastic stress luminescence sensor can react the stress deformation of object in real time, thus can carry out the degree of fatigue of inspected object dynamic process by development of new stress irradiance sensor.But because elastic stress luminescence is a kind of novel luminescence phenomenon, research is less at present, and known elastic stress luminescent material has the ZnS:Mn of Yellow light-emitting low temperature
2+, (Ba, the Ca) TiO glowed
3: Pr
3+, the SrAl of green light
2o
4: Eu
2+, the Sr of rubescent orange-colored light
3sn
2o
7: Sm
3+, the BaS of green light of turning blue
2o
2n
2: Eu
2+deng, but comparatively speaking, the elastic stress luminescent material kind developed is less, the wavelength of light limitednumber sent, and luminous intensity is difficult to the requirement reaching practical application, so this area is badly in need of developing the high elastic stress luminescent material of novel elastic stress light emitting material, particularly luminous intensity.
Summary of the invention
The object of the invention is to openly a kind of there is niobate luminescent material of elastic stress luminescent properties and preparation method thereof.This material is with calcium niobate CaNb
2o
6for matrix, with rare earth ion Pr
3+for activator, its chemical expression is [(Ca
1-xm
x)
1-z] Nb
2o
6: (Pr
1-yr
y)
z(0≤x≤0.2,0≤y≤0.5,0 < z≤0.1), wherein M represents Ca position substitute element, is selected from one or more in Mg, Sr, Ba; R represents rare earth or the transition metal of codoped, is selected from one or more in La, Nd, Sm, Eu, Gd, Yb, Lu, Cr, Mn, Ag, Cd; X, y, z represents molar content.
The niobate luminescent material with elastic stress luminescent properties disclosed in this invention adopts high temperature solid-state method to synthesize in atmosphere.Preparation process comprises the following steps:
A) get raw material by element chemistry metering score another name, add appropriate amount of deionized water or dehydrated alcohol, fully grinding post-drying obtains mixed powder;
B) by the powder pre-burning at 800 ~ 1000 DEG C in atmosphere of step a) gained, pre-burning soaking time is 3 ~ 6 hours;
C), after being ground by cooled pre-burning product, calcine at 1200 ~ 1500 DEG C in atmosphere, the sintering soak time is 3 ~ 8 hours;
D) by step c) namely pulverize after the cooling of the calcinate that obtains obtains having the niobate luminescent material of elastic stress luminescent properties.
Preparation has the niobate luminescent material method of elastic stress luminescent properties, it is characterized in that, Ca, Mg, Sr and Ba adopt its oxide compound or carbonate to be raw material, Nb adopts its oxide compound to be raw material, and the rare earth of Pr and codoped and transition metal adopt its oxide compound, nitrate or carbonate to be raw material.
The obtained niobate luminescent material powder with elastic stress luminescent properties and optically transparent organic elastomeric polymer material (as ABS resin, polyacetal (PA), polycarbonate (PC), polyethylene (PE), polystyrene (PS), polypropylene (PP), polymethylmethacrylate (PMMA), urethane resin, polyester, epoxy resin, silicon rubber etc.) are mixed and made into thin slice or cylinder shape resinite or are coated on UUT surface, mechanical stress suffered by these parts can be converted to luminous energy, realize stress distribution and detect.
The niobate luminescent material with elastic stress luminescent properties obtained by the present invention, is characterized in that, the elastic stress glow peak of this material is the wire peak be positioned near 610nm, and monochromaticity is good.
The niobate luminescent material with elastic stress luminescent properties obtained by the present invention, is characterized in that, material has strong elastic stress luminous intensity, can with the naked eye observe under dark surrounds.
The niobate luminescent material with elastic stress luminescent properties obtained by the present invention, is characterized in that, in elastic limit, the elastic stress luminous intensity of material is directly proportional to load intensity.
The niobate luminescent material with elastic stress luminescent properties obtained by the present invention, is characterized in that, material belongs to trap control type luminescent material, and its elastic stress luminous intensity can be recovered after ultraviolet light irradiation, belongs to nondestructive stress light emitting material.
Beneficial effect of the present invention is:
(1) material of the present invention preparation adopts traditional solid phase reaction method, preparation technology is simple, preparation under air atmosphere, condition easily controls, equipment requirements is low, with low cost, without toxic gas generation in preparation process, environmentally safe.
(2) obtained elastic stress luminescent material and optically transparent macromolecular material are mixed and made into thin slice or cylinder shape resinite, also or be coated on UUT surface, mechanical external force suffered by it (pressure, pulling force, frictional force, surging force, shearing force, distortion power, elastic force, ultrasonic etc.) can be converted to luminous energy and send.
(3) niobate luminescent material with elastic stress luminescent properties prepared by the present invention has stronger elastic stress luminous intensity, can directly be seen by human eye under comparatively dark situation.
(4) luminous intensity with the niobate luminescent material of elastic stress luminescent properties of the present invention, depends on the mechanical energy size of excitaton source.The luminous intensity of this material generally increases along with the rising of mechanicals efforts, thus cause in photoemissive mechanical interaction power exist minimum can value, or stress threshold, this threshold value is by the domination of material component change.The mechanical stress scope that this material can respond wide, is increased to the energy that can destroy material structure from the weak stress of a little newton it can be made to produce stress irradiance to executing.As long as niobate luminescent material and its matrix material of the present invention with elastic stress luminescent properties can be luminous from the external force that outside applying is very little, and in elastic deformation area, luminous intensity and stress intensity proportional, can realize stress distribution detect.
(5) the luminous decay of afterglow of the elastic stress with the niobate luminescent material of elastic stress luminescent properties of the present invention is fast.After stress applying terminates, stress irradiance twilight sunset rapidly disappears (millisecond magnitude), and without macroscopic stress irradiance halation and stressed track, this performance does not hinder material to the mensuration of follow-up weak stress.During this elastic stress luminescent material can be used for measuring in real time the stress distribution of parts and component and adhesive strength measures.
(6) niobate luminescent material with elastic stress luminescent properties of the present invention, can be widely used in that pressure transmitter, mechanical stress are visual, artificial skin, smart skins, self-diagnosable system, ultraprecise device fabrication, organism, buildings and machine stress distribution detects, City Building is taken precautions against natural calamities and disaster reduction system, prediction earthquake produce, detect the infringement, researching human body disease etc. of aircraft and automobile.
Accompanying drawing explanation
Fig. 1 is the embodiment of the present invention 1 products C a
0.999nb
2o
6: Pr
0.001x-ray diffractogram of powder.
Fig. 2 is the embodiment of the present invention 1 products C a
0.999nb
2o
6: Pr
0.001excitation spectrum (monitoring 605nm red emission).
Fig. 3 is the embodiment of the present invention 1 products C a
0.999nb
2o
6: Pr
0.001emmission spectrum (excitation wavelength 280nm).
Fig. 4 is the embodiment of the present invention 1 products C a
0.999nb
2o
6: Pr
0.001elastic stress luminescent spectrum.
Fig. 5 is the embodiment of the present invention 1 products C a
0.999nb
2o
6: Pr
0.001elastic stress luminous photo under pressure load effect.
Fig. 6 is the embodiment of the present invention 1 products C a
0.999nb
2o
6: Pr
0.001suffered relation curve between load and elastic stress luminous intensity.
Fig. 7 is the embodiment of the present invention 1 products C a
0.999nb
2o
6: Pr
0.001thermo-luminescence.
Embodiment
Below by way of particular specific embodiment, also the present invention will be described in more detail by reference to the accompanying drawings.Should be understood that one or more method stepss that the present invention mentions do not repel also there is other method steps before and after described combination step, or other method steps can also be inserted before these steps clearly mentioned; Should also be understood that these embodiments are only not used in for illustration of the present invention to limit the scope of the invention.And, except as otherwise noted, the numbering of various method steps is only the convenient tool differentiating various method steps, but not be ordering or the enforceable scope of restriction the present invention of restriction various method steps, the change of its relativeness or adjustment, when changing technology contents without essence, when being also considered as the enforceable category of the present invention.
Particularly, table 1 lists the material component of 12 specific embodiments of the present invention, raw material weight, calcining temperature and elastic stress luminescent properties.
The material component of table 1. embodiment 1-12 sample, raw material weight, sintering temperature and elastic stress luminescent properties
Embodiment 1
Preparation has the niobate luminescent material Ca of elastic stress luminescent properties
0.999nb
2o
6: Pr
0.001:
(1) take raw material according to table 1, above raw material is analytical pure, after abundant mixing raw material, dries in 60 DEG C of baking ovens;
(2) mixed powder after drying to be placed in alumina crucible in air atmosphere at 800 DEG C pre-burning 4 hours;
(3) preburning powdered material after grinding is calcined 4 hours in air atmosphere at 1300 DEG C;
(4) cooled product is pulverized namely to obtain chemical constitution be Ca
0.999nb
2o
6: Pr
0.001elastic stress luminescent material.
(5) the obtained niobate luminescent material powder with elastic stress luminescent properties is mixed with mass ratio 1: 10 with optically transparent organic elastomeric polymer material polyurethane resin, make the cylinder shape resinite that diameter and thickness are 1cm, for the elastic stress luminescent properties of measure sample.
The niobate elastic stress luminescent material outward appearance prepared of this embodiment in white, X-ray powder diffraction (XRD) test result as shown in Figure 1, the diffraction peak data of products obtained therefrom and CaNb
2o
6the diffraction data of powdery diffractometry standard card (00-039-1392) is consistent, and without dephasign, illustrates that gained luminescent material is the CaNb of pure phase
2o
6structure.As shown in Figure 2, the excitation spectrum of this material is made up of a series of peak the excitation spectrum of monitoring 605nm red emission within the scope of 250 ~ 550nm, and highest peak is positioned at 280nm, and other peak is positioned at 457nm, 476nm and 493nm place.Fig. 3 is the emmission spectrum of this material under 280nm optical excitation within the scope of 590-670nm, and this emmission spectrum comes from Pr primarily of near 610nm
3+wire peak composition.Fig. 4 is the elastic stress luminescent spectrum of this material, and this emmission spectrum comes from Pr by being positioned near 610nm
3+wire peak composition.Fig. 5 is the elastic stress luminous photo of this material under pressure load effect.Can find out, elastic stress luminescence is under pressure high-visible, the most obvious in the elastic stress luminescence of the most strength of pressure load.Fig. 6 is the change curve of elastic stress luminous intensity with pressure load of this material.The intensity of elastic stress luminescence applies the increase of pressure load and strengthens, and in the pressure range of 0-1000N, the increase of elastic properties of materials stress irradiance intensity pressure intensity presents linear functional relation accurately.In the dispose procedure of pressure load, the luminescence of material decays rapidly.Fig. 7 is the thermoluminescence spectrum of material, and the thermal glow peak that existence one is strong within the scope of 25-225 DEG C, show that material belongs to trap control type luminescent material, its elastic stress luminous intensity can be recovered after ultraviolet light irradiation, belongs to nondestructive stress light emitting material.
Embodiment 2
Preparation has the niobate luminescent material Ca of elastic stress luminescent properties
0.998nb
2o
6: Pr
0.002:
(1) take raw material according to table 1, above raw material is analytical pure, after abundant mixing raw material, dries in 60 DEG C of baking ovens;
(2) mixed powder after drying to be placed in alumina crucible in air atmosphere at 900 DEG C pre-burning 5 hours;
(3) preburning powdered material after grinding is calcined 5 hours in air atmosphere at 1200 DEG C;
(4) cooled product is pulverized namely to obtain chemical constitution be Ca
0.998nb
2o
6: Pr
0.002elastic stress luminescent material.
Embodiment 3
Preparation has the niobate luminescent material Ca of elastic stress luminescent properties
0.997nb
2o
6: Pr
0.003:
(1) take raw material according to table 1, above raw material is analytical pure, after abundant mixing raw material, dries in 60 DEG C of baking ovens;
(2) mixed powder after drying to be placed in alumina crucible in air atmosphere at 900 DEG C pre-burning 5 hours;
(3) preburning powdered material after grinding is calcined 6 hours in air atmosphere at 1350 DEG C;
(4) cooled product is pulverized namely to obtain chemical constitution be Ca
0.997nb
2o
6: Pr
0.003elastic stress luminescent material.
Embodiment 4
Preparation has the niobate luminescent material Ca of elastic stress luminescent properties
0.996nb
2o
6: Pr
0.004:
(1) take raw material according to table 1, above raw material is analytical pure, after abundant mixing raw material, dries in 60 DEG C of baking ovens;
(2) mixed powder after drying to be placed in alumina crucible in air atmosphere at 800 DEG C pre-burning 5 hours;
(3) preburning powdered material after grinding is calcined 6 hours in air atmosphere at 1400 DEG C;
(4) cooled product is pulverized namely to obtain chemical constitution be Ca
0.996nb
2o
6: Pr
0.004elastic stress luminescent material.
Embodiment 5
Preparation has the niobate luminescent material Ca of elastic stress luminescent properties
0.995nb
2o
6: Pr
0.005:
(1) take raw material according to table 1, above raw material is analytical pure, after abundant mixing raw material, dries in 60 DEG C of baking ovens;
(2) mixed powder after drying to be placed in alumina crucible in air atmosphere at 800 DEG C pre-burning 4 hours;
(3) preburning powdered material after grinding is calcined 4 hours in air atmosphere at 1450 DEG C;
(4) cooled product is pulverized namely to obtain chemical constitution be Ca
0.995nb
2o
6: Pr
0.005elastic stress luminescent material.
Embodiment 6
Preparation has the niobate luminescent material Ca of elastic stress luminescent properties
0.994nb
2o
6: Pr
0.006:
(1) take raw material according to table 1, above raw material is analytical pure, after abundant mixing raw material, dries in 60 DEG C of baking ovens;
(2) mixed powder after drying to be placed in alumina crucible in air atmosphere at 900 DEG C pre-burning 4 hours;
(3) preburning powdered material after grinding is calcined 5 hours in air atmosphere at 1400 DEG C;
(4) cooled product is pulverized namely to obtain chemical constitution be Ca
0.994nb
2o
6: Pr
0.006elastic stress luminescent material.
Embodiment 7
Preparation has the niobate luminescent material (Ca of elastic stress luminescent properties
0.95ba
0.05)
0.996nb
2o
6: Pr
0.004:
(1) take raw material according to table 1, above raw material is analytical pure, after abundant mixing raw material, dries in 60 DEG C of baking ovens;
(2) mixed powder after drying to be placed in alumina crucible in air atmosphere at 850 DEG C pre-burning 3 hours;
(3) preburning powdered material after grinding is calcined 3 hours in air atmosphere at 1350 DEG C;
(4) cooled product is pulverized namely obtain chemical constitution for (Ca
0.95ba
0.05)
0.996nb
2o
6: Pr
0.004elastic stress luminescent material.
Embodiment 8
Preparation has the niobate luminescent material (Ca of elastic stress luminescent properties
0.99mg
0.01)
0.995nb
2o
6: Pr
0.005:
(1) take raw material according to table 1, above raw material is analytical pure, after abundant mixing raw material, dries in 60 DEG C of baking ovens;
(2) mixed powder after drying to be placed in alumina crucible in air atmosphere at 850 DEG C pre-burning 4 hours;
(3) preburning powdered material after grinding is calcined 4 hours in air atmosphere at 1400 DEG C;
(4) cooled product is pulverized namely obtain chemical constitution for (Ca
0.99mg
0.01)
0.995nb
2o
6: Pr
0.005elastic stress luminescent material.
Embodiment 9
Preparation has the niobate luminescent material (Ca of elastic stress luminescent properties
0.97sr
0.02ba
0.01)
0.99nb
2o
6: Pr
0.01:
(1) take raw material according to table 1, above raw material is analytical pure, after abundant mixing raw material, dries in 60 DEG C of baking ovens;
(2) mixed powder after drying to be placed in alumina crucible in air atmosphere at 950 DEG C pre-burning 5 hours;
(3) preburning powdered material after grinding is calcined 4 hours in air atmosphere at 1450 DEG C;
(4) cooled product is pulverized namely obtain chemical constitution for (Ca
0.97sr
0.02ba
0.01)
0.99nb
2o
6: Pr
0.01elastic stress luminescent material.
Embodiment 10
Preparation has the niobate luminescent material Ca of elastic stress luminescent properties
0.997nb
2o
6: (Pr
0.7eu
0.3)
0.003:
(1) take raw material according to table 1, above raw material is analytical pure, after abundant mixing raw material, dries in 60 DEG C of baking ovens;
(2) mixed powder after drying to be placed in alumina crucible in air atmosphere at 1000 DEG C pre-burning 3 hours;
(3) preburning powdered material after grinding is calcined 3 hours in air atmosphere at 1500 DEG C;
(4) cooled product is pulverized namely obtain chemical constitution for (Ca
0.997nb
2o
6: (Pr
0.7eu
0.3)
0.003elastic stress luminescent material.
Embodiment 11
Preparation has the niobate luminescent material (Ca of elastic stress luminescent properties
0.97sr
0.03)
0.99nb
2o
6: (Pr
0.8mn
0.2)
0.01:
(1) take raw material according to table 1, above raw material is analytical pure, after abundant mixing raw material, dries in 60 DEG C of baking ovens;
(2) mixed powder after drying to be placed in alumina crucible in air atmosphere at 900 DEG C pre-burning 4 hours;
(3) preburning powdered material after grinding is calcined 4 hours in air atmosphere at 1400 DEG C;
(4) cooled product is pulverized namely obtain chemical constitution for (Ca
0.97sr
0.03)
0.99nb
2o
6: (Pr
0.8mn
0.2)
0.01elastic stress luminescent material.
Embodiment 12
Preparation has the niobate luminescent material (Ca of elastic stress luminescent properties
0.94sr
0.03ba
0.03)
0.993nb
2o
6: (Pr
0.5gd
0.5)
0.007:
(1) take raw material according to table 1, above raw material is analytical pure, after abundant mixing raw material, dries in 60 DEG C of baking ovens;
(2) mixed powder after drying to be placed in alumina crucible in air atmosphere at 1000 DEG C pre-burning 4 hours;
(3) preburning powdered material after grinding is calcined 5 hours in air atmosphere at 1500 DEG C;
(4) cooled product is pulverized namely obtain chemical constitution for (Ca
0.94sr
0.03ba
0.03)
0.993nb
2o
6: (Pr
0.5gd
0.5)
0.007elastic stress luminescent material.
By the niobate luminescent material powder with elastic stress luminescent properties obtained by embodiment 2-12 respectively with optically transparent organic elastomeric polymer materials A BS resin, polyacetal (PA), polycarbonate (PC), polyethylene (PE), polystyrene (PS), polypropylene (PP), polymethylmethacrylate (PMMA), urethane resin, polyester, epoxy resin, silicon rubber is mixed and made into thin slice with the mass ratio of 1: 10-5: 10, cylinder shape resinite, be coated on UUT surface, for the elastic stress luminescent properties of measure sample.
The niobate elastic stress luminescent material outward appearance that above-described embodiment 2-12 prepares is in white, and X-ray powder diffraction (XRD) test result is identical with embodiment 1 sample, the diffraction peak data of products obtained therefrom and CaNb
2o
6the diffraction data of powdery diffractometry standard card (00-039-1392) is consistent, and without dephasign, illustrates that gained luminescent material is the CaNb of pure phase
2o
6structure.Peak type and the peak position of the excitation spectrum of embodiment 2-12 sample and emmission spectrum and embodiment 1 sample are consistent, are only that peak exists difference by force.The elastic stress luminescent spectrum of embodiment 2-12 sample is consistent with the peak type of embodiment 1 sample and peak position, is only that peak exists difference by force.The elastic stress luminous intensity of each sample all can naked-eye observation under dark surrounds, and the most obvious in the elastic stress luminescence of the most strength of pressure load.The elastic stress luminous intensity of each sample strengthens with the increase applying pressure load, and in the pressure range of 0-1000N, the increase of elastic properties of materials stress irradiance intensity pressure intensity presents linear functional relation accurately.In the dispose procedure of pressure load, the luminescence of material decays rapidly.All there is strong thermal glow peak in each sample, show that material belongs to trap control type luminescent material, its elastic stress luminous intensity can be recovered after ultraviolet light irradiation, belongs to nondestructive stress light emitting material within the scope of 25-225 DEG C.
Embodiment in the present invention, only for the present invention will be described, does not form the restriction to right, other equivalent in fact substituting, all in scope that those skilled in that art can expect.
Claims (5)
1. there is a niobate luminescent material for elastic stress luminescent properties, it is characterized in that, with CaNb
2o
6material is matrix, with trivalent rare earth ions Pr
3+for activator, its chemical expression is [(Ca
1-xm
x)
1-z] Nb
2o
6: (Pr
1-yr
y)
z(0≤x≤0.2,0≤y≤0.5,0 < z≤0.1), wherein M represents Ca position substitute element, is selected from one or more in Mg, Sr, Ba; R represents rare earth or the transition metal of codoped, is selected from one or more in La, Nd, Sm, Eu, Gd, Yb, Lu, Cr, Mn, Ag, Cd; X, y, z represents molar content.
2. have a niobate luminescent material for elastic stress luminescent properties, it is characterized in that, the elastic stress glow peak of this material is the wire peak be positioned near 610nm, and monochromaticity is good; Material has strong elastic stress luminous intensity, can with the naked eye observe under dark surrounds; In elastic limit, the elastic stress luminous intensity of material is directly proportional to load intensity; Material belongs to trap control type luminescent material, and its elastic stress luminous intensity can be recovered after ultraviolet light irradiation, belongs to nondestructive stress light emitting material.
3. the preparation as described in claim 1,2 has the niobate luminescent material method of elastic stress luminescent properties, it is characterized in that, Ca, Mg, Sr and Ba adopt its oxide compound or carbonate to be raw material, Nb adopts its oxide compound to be raw material, the rare earth of Pr and codoped and transition metal adopt its oxide compound, nitrate or carbonate to be raw material, adopt the niobate luminescent material with elastic stress luminescent properties described in the preparation of high temperature process heat method, preparation process comprises the following steps:
A) get raw material by element chemistry metering score another name, add appropriate amount of deionized water or dehydrated alcohol, fully grinding post-drying obtains mixed powder;
B) by the powder pre-burning at 800 ~ 1000 DEG C in atmosphere of step a) gained, pre-burning soaking time is 3 ~ 6 hours;
C), after being ground by cooled pre-burning product, calcine at 1200 ~ 1500 DEG C in atmosphere, the sintering soak time is 3 ~ 8 hours;
D) by step c) namely pulverize after the cooling of the calcinate that obtains obtains having the niobate luminescent material of elastic stress luminescent properties.
4. the niobate luminescent material with elastic stress luminescent properties as described in claim 1-3, it is characterized in that, after obtained elastic stress luminescent material powder and optically transparent organic elastomeric polymer material mixing, laminate or cylinder shape resinite or be coated on UUT surface, mechanical stress suffered by these parts can be converted to luminous energy, realize stress distribution and detect.
5. the niobate luminescent material with elastic stress luminescent properties as described in claim 1-4, can be widely used in that pressure transmitter, mechanical stress are visual, artificial skin, smart skins, self-diagnosable system, ultraprecise device fabrication, organism, buildings and machine stress distribution detects, City Building is taken precautions against natural calamities and disaster reduction system, prediction earthquake produce, detect the infringement, researching human body disease etc. of aircraft and automobile.
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