CN1063211C - Long-persistence and high-brightness luminous material and its prepn - Google Patents
Long-persistence and high-brightness luminous material and its prepn Download PDFInfo
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- CN1063211C CN1063211C CN96100981A CN96100981A CN1063211C CN 1063211 C CN1063211 C CN 1063211C CN 96100981 A CN96100981 A CN 96100981A CN 96100981 A CN96100981 A CN 96100981A CN 1063211 C CN1063211 C CN 1063211C
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Abstract
The present invention relates to a luminescent material with long afterglow and high brightness. The present invention is characterized in that the material is prepared from monoclinic system crystals shown by a general formula of M. N. AL[2-x]BxO4, wherein M represents an alkaline earth metal; N represents a rare earth element; x meets a formula of 0.1<=x<=1; M is generally strontium; N is generally europium; a part of M can be replaced by at least one alkaline earth metal in Mg, Ca and Ba; except europium, N can use other rare earth elements as additional activating agents. The luminescent material has the characteristics of long afterglow and high brightness.
Description
The present invention relates to long after glow luminous material, particularly after 200nm～450nm is ultraviolet ray excited, have the invention of the phosphor material of steady persistence high brightness characteristic.
Phosphor material is meant and is being subjected to sunlight, luminescent lamp and other people worker's light source, and energy-absorbing when particularly ultraviolet ray excited changes the energy that absorbs into visible light, can continue luminous material after stopping exciting.Keep luminous material of long period after stopping and being referred to as long-decay phosphor material exciting.
In the past, the luminescent coating that uses on dial, the safe label was to mix in paint, the printing ink etc. as the phosphor material of representative as the activated material and make to add copper (ZnS:Cu) in zinc sulphide.When this class sulfide is subjected to certain wavelength ultraviolet ray excited, absorb its energy, the form with visible light gives off energy then, is the same with the luminescence mechanism of above-mentioned phosphor material.But this class sulfide is extremely short time of persistence, and the chemical structure instability is not had a photostabilization etc., so there are a lot of problems aspect practical application.When for example, being used for Luminous Timekeeper, human eye time of persistence of discerning has only 20～30 minutes; When being subjected to uviolizing the photolysis phenomenon takes place so that lose luminescent properties, so can not be used for open air or the like.
In order to prolong the time of persistence of sulfide, adopted the interpolation radioactive substance, Pm for example, give the way of its self-luminosity, but owing to used radioactive substance, strict in the processing of material, and make waste treatment need high costs such as used utensil and draining, use hardly now.
Different with this sulfide phosphor material, the sixties have proposed to add rare earth elements europium and have made fluorescent material in alkali earth metal aluminate.For example, disclosing in the United States Patent (USP) the 3rd, 294,699 is the strontium aluminate luminous material (SrAl of activator with the divalent europium
2O
4: Eu), the addition of this divalent europium is 2～8mol% of strontium aluminate, and its luminescence peak is 520nm to this fluorescent material when ultraviolet ray excited being subjected to.But this fluorescent material possesses twilight sunset hardly, and is different with phosphor material and long-decay phosphor material.
Also have and in strontium aluminate, add the example that other alkaline-earth metal is made fluorescent material.For example, English Patent the 1st, 190,520 disclose a kind of divalent europium activated fluorescent material, and it consists of BaxS-ryCazEnpAl
12O
19(wherein x+y+z+p=1, one or two can be 0,0.001≤p≤0.1 among x, y, the z).This fluorescent material is being subjected to when ultraviolet ray excited, and peak luminous wavelength is 380nm～440nm.These fluorescent materials all are to be subjected to the luminous at that time of ultraviolet ray or electron excitation, to be mainly used in cathode tube etc.
In recent years, having developed desired being subjected to can for a long time luminous luminescent material behind certain energy excitation.For example, Chinese invention patent application publication number CN1053807A discloses a kind of long after glow luminous material, and its general expression is m (Sr
1-xEu
x) OnAl
2O
3YB
2O
3(1≤m≤5,1≤n≤8,0.001≤y≤0.35).This long after glow luminous material is to be raw material with the oxide compound of aluminium, strontium, europium or the salt that can produce these oxide compounds after heating, behind 1200 ℃～1600 ℃ temperature sintering, uses N again
2And H
2Make 1000 ℃～1400 ℃ reductive methods.
But have only 4～5 hours the time of persistence of this long after glow luminous material reality, and original intensity is low, poor practicability.The present inventor is for solving above-mentioned variety of problems, luminescent material to alkali earth metal aluminate and rare earth metal activator composition improves, various structures and new xln are carried out various researchs, develop the luminescent material that has high initial brightness and steady persistence than the luminescent material of above-mentioned sulfide and alkali earth metal aluminate and rare earth activated dose of combination, finished the present invention.
So the purpose of this invention is to provide have steady persistence, the luminescent material of high initial brightness characteristic and preparation method thereof.
The present invention seeks to reach by following each invention:
1. a long Persistence and high brightness fluorescent materials is characterized in that by general expression MNAl
2-xB
xO
4The sintered body of expression constitutes, and in the formula, M represents alkaline-earth metal, and N represents rare earth element, 0.1≤x≤1.
2. the long Persistence and high brightness fluorescent materials put down in writing of preceding paragraph 1 is characterized in that M is a strontium, and N is an europium.
3. the long Persistence and high brightness fluorescent materials put down in writing of preceding paragraph 2 is characterized in that the part of the strontium of M representative can be by Mg, Ca, and at least a alkaline-earth metal is replaced among the Ba.
4. the long Persistence and high brightness fluorescent materials of being put down in writing in the preceding paragraph 2 or 3, it is characterized in that: the part of the europium of N representative can be by La, Ce, Pr, Nd, Sm, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, at least a metal is replaced among Mn or the Bi.
5. the long Persistence and high brightness fluorescent materials of being put down in writing in any one of preceding paragraph 1 to 4, the addition that it is characterized in that N are more than the 0.001mol% of metal of M representative, below the 10mol%.
6. the preparation method of preceding paragraph 1 described high-brightness long persistence luminescent material is characterized in that the preparation method comprises following operation:
(1) takes by weighing material by stoichiometric ratio;
(2) starting material that weigh up are even through ground and mixed;
(3) with the calcination 2～4 hours under 800～1200 ℃ of temperature of mixed material;
(4) with sintered compact reductase 12～4 hour under 800～1200 ℃ of temperature;
(5) sintered compact is cooled off;
(6) cooled sintered compact is pulverized;
(7) will pulverize the body sub-sieve.
7. the preparation method of aforementioned 6 described high-brightness long persistence luminescent materials is characterized in that operation (4) is directly to reduce with powdered carbon.
8. aforementioned 6 described high-brightness long persistences are sent out preparation methods, it is characterized in that operation (3) and (4) carry out simultaneously.
Below, the present invention is described in detail.
Long Persistence and high brightness fluorescent materials of the present invention, its general expression is:
M·N·Al
2-xB
xO
4，
In the formula, M is an alkaline-earth metal, and N is a rare earth element, 0.1≤X≤1.M can be strontium, calcium, barium, magnesium, and N can be La, Ce, Pr, Nd, Sm, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Mn, Bi.The principal constituent of this sintered body is a kind of monoclinic system crystal body.
The representational sintered body of long Persistence and high brightness fluorescent materials of the present invention is SrEuAl
2-xB
xO
4, this sintered body has the steady persistence high brightness characteristic.More particularly, with burning till after strontium oxide, aluminum oxide and boron oxide or boron compound and the mixing of europium sesquioxide activator, resulting sintered body is the monoclinic system crystal body.The content of boron is in this sintered body: it is 2: 4 that boron and aluminium add up to the ratio with oxygen, and the content X of boron is 0.1～1.
Among the present invention, strontium oxide, aluminum oxide and boron oxide or boron compound at high temperature burn till, and can generate SrAl
2-xB
xO
4The xln of structure, according to actual XRD determining result, this xln is the monoclinic system crystal body, not only has steady persistence after the activation by activator and additional activation agent, and briliancy (brightness) is also high especially, with prior art m (Sr
1-xEu
x) O.nAl
2O
3.yB
2O
3Compare and have more superior performance.Among the present invention, the part of strontium can be by Mg, Ca, and at least a element is replaced among the Ba, as total amount and the Al by Sr and Mg and/or Ca and/or Ba
2-xB
xO
4Ratio be 1: 1.Here said a part of strontium is meant the part of the total content of the strontium in the xln, just accounts for the Mg of the total content of strontium in the xln, Ca, the ratio of Ba.
The content of boron is less than at 0.1 o'clock among the present invention, can not produce what influence to the steady persistence performance of xln, and on the contrary more than 1 o'clock, it is that sintered body thereby performance will change that the sintered body of burning till just transfers boron oxide to.Be generally 0.3～0.8.In the prior art, for example European patent discloses and records SrAl in the 0094132nd
2O
4Can add boron oxide during manufacturing as fusing assistant, its addition is the 0.002mol to 0.1mol of aluminium, surpasses this scope and then can not bring into play desired effect.
In other publication, for example Japan's special permission discloses among the flat 7-11250 and records: making SrAl
2O
4Spinel structure the time, can add boron oxide as fusing assistant, the addition of its boron oxide is 1～10%.The reason that the amount of adding boron oxide is limited is: can not produce the effect of fluxing at 1% o'clock that is less than weight, surpassing 10% o'clock burned material will solidify, and pulverizing thereafter and gradation operation will be very difficult.Different with foregoing invention, long Persistence and high brightness fluorescent materials of the present invention, by add with the atomicity of aluminium than 0.1～1 amount, obtained the xln different (oblique crystal), thereby obtained and the SrAl that does not have steady persistence with spinel structure
2O
4: the luminescent material that Eu is different with steady persistence and high briliancy characteristic.Long Persistence and high brightness fluorescent materials hardness of the present invention is very high, and its hardness is 6.5～7.
Among the present invention, the part of the strontium of M representative, the Ca that can be up to 25mol% substitutes.The amount of Ca is during more than the 25mol% of strontium, and xln may collapse.Same reason, the addition of Ba can be at most below the 10mol% of strontium, and the addition of Mg can be at most below the 30mol% of strontium.By adding these alkali earths elements, can obtain the different luminescent material of emission wavelength.Above-mentioned alkaline-earth metal can be used alone, and is also available two or more.Use when two or more, its addition adds up to and Al
2-xB
xO
4Ratio be 1: 1.
The raw material of making long Persistence and high brightness fluorescent materials of the present invention is: the oxide compound of strontium, calcium, barium, magnesium or can generate the salt of these oxide compounds by heating.The activator of using among the present invention is an europium, raw material can be with europium sesquioxide or by heating the salt that can generate europium sesquioxide.And, among the present invention, except that europium, also can add additional activator, thereby improve briliancy.The raw material of additional activation agent, the oxide compound of available additional activation agent or after heating, can generate the salt of these oxide compounds.
Long Persistence and high brightness fluorescent materials of the present invention is MNAl
2-xB
xO
4Tectosome, N is a bivalent rare earth element europium activator, such tectosome have can be practical twilight sunset and briliancy.In order to improve MNAl
2-xB
xO
4Briliancy, also can add the additional activation agent, La for example, Ce, Pr, Nd, Sm, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Mn, one or more among the Bi.This tectosome is a kind of monoclinic system crystal body basically, can obtain brighter briliancy under the effect of the element of rare earth class.In these additional activation agent, with Dy, Nd, Ho, Ce are better.The usage quantity of activator and additional activation agent is MNAl
2-xB
xO
40.001～10mol% of M in the structure of expression.When the consumption of activator and additional activation agent is less than 0.001mol%, can not obtain good activation effect, but when surpassing 10mol%, the quencher phenomenon may take place." activator and additional activation agent activate " is meant strontium oxide, aluminum oxide, boron oxide or boron compound and europium sesquioxide as activator among the present invention, and the oxide compound of at least a rare earth element compound that maybe can generate this oxide compound mixes as the additional activation agent and burns till.
The method for preparing luminescent material of the present invention comprises seven steps.
Introduce a kind of manufacture method of high briliancy luminescent material of the present invention below.After various raw materials are fully pulverized, uniform mixing, with mixture 800 ℃～1200 ℃ sintering temperatures 2～4 hours.With the sintered compact that obtains reductase 12～4 hour under 800 ℃～1100 ℃ temperature, then sintered compact cooling, pulverizing, gradation (classification) promptly be can be made into luminescent material of the present invention.In the above-mentioned manufacture method, sintering circuit integrates once more, and promptly under 800 ℃～1200 ℃ temperature, directly sintering also could in 2～4 hours under reducing atmosphere.Reducing atmosphere is not had particular restriction, and general used reducing atmosphere and reduction means also can be used.Because long Persistence and high brightness fluorescent materials of the present invention does not use any radioactive substance, "dead" harm, safety, but hardness is high and life-time service.
Owing to added more boron in the luminescent material of the present invention, so not only changed the structure of sintered body but also made its firing temperature reduce.Sintering temperature is at 800～1200 ℃, and the carbon rod electric furnace just can reach the requirement of sintering temperature, is the electric furnace of calrod and do not need expensive molybdenum disilicide, has so just reduced facility investment and the production cost produced.
Long Persistence and high brightness fluorescent materials of the present invention can be sneaked in printing ink and the coating and be used as luminous paint, because luminescent material of the present invention has high briliancy characteristic, be used for identification at night and have good especially effect, for example as the road Identification sign, the Central Line of road, billboard etc. also can be used for the backboard of stationery, toy, sports goods, liquid crystal board etc., and are luminous owing to the energy that slowly discharges the absorption on daytime, not needing other any energy, is a kind of advanced luminescent material.
Long Persistence and high brightness fluorescent materials of the present invention, by at high temperature burning till with strontium oxide, aluminum oxide, boron oxide and platinum oxide or by the material that heat can generate these oxide compounds, form the monoclinic system crystal body, thereby have steady persistence and high briliancy, made novel long Persistence and high brightness fluorescent materials.Thereby its briliancy is further improved by the agent of further interpolation additional activation.
Below in conjunction with embodiment the present invention is advanced to describe in detail, but the present invention is not limit by these embodiment.
Embodiment 1:
Get: SrCO
3730.6g; Al
2O
3474.3g; H
3BO
343.3g
As the activator raw material, get: Eu
2O
34.4g;
After these raw material pulverizing, thorough mixing is put into crucible then.This crucible is placed electric furnace, in reducing atmosphere, kept 3 hours under 1100 ℃ of temperature, be cooled to 200 ℃ then, from electric furnace, take out.Further be cooled to ball mill pulverizing after the room temperature, cross 200 mesh sieves, make luminescent material of the present invention [1].
Embodiment 2:
Get: SrCO
3730.6g; Al
2O
3474.3g; H
3BO
343.3g
As the activator raw material, get: Eu
2O
34.4g;
Additional activation agent raw material is got: Dy
2O
34.6g;
After these raw material pulverizing, thorough mixing is put into crucible then.This crucible is placed electric furnace, in reducing atmosphere, kept 3 hours under 1100 ℃ of temperature, be cooled to 200 ℃ then, from electric furnace, take out.Further be cooled to ball mill pulverizing after the room temperature, cross 200 mesh sieves, make luminescent material of the present invention [2]
Embodiment 3:
Get: SrCO
31299g; AL
2O
3877.2g; H
3BO
3173g; CaCO
35g; BaCO
310g;
Activator and additional activation agent raw material are got: Eu
2O
38.8g; Dy
2O
39.3g; Nd
2O
38.4g;
After these raw material pulverizing, thorough mixing places crucible then.This crucible is placed electric furnace, under reductive condition, kept 2 hours in 1200 ℃ of temperature, keep 2～3 hours (following identical) at 800 ℃～1000 ℃ thereafter, make luminescent material of the present invention [3] with embodiment 2
Embodiment 4:
Get: SrCO
3649.5g; Al
2O
3438.6g; H
3BO
386.5g; CaO
10g;
Activator and additional activation agent raw material are got: Eu
2O
38.8g; Dy
2O
39.3g;
Make luminescent material of the present invention [4] with the manufacture method identical with embodiment 2
Embodiment 5:
Get: SrCO
31299g; Al
2O
3948.6g; H
3BO
386.5g; CaCO
3197g.
Activator and additional activation agent raw material are got: Eu
2O
317.6g; Dy
2O
316.8g;
With these raw material pulverizing, thorough mixing is placed in the crucible.This crucible is put in people's electric furnace, kept 2 hours, import CO gas when being cooled to 800 ℃～1000 ℃ then, kept 2 hours at 800 ℃～1200 ℃.From electric furnace, take out after being cooled to 200 ℃ then.Further be cooled to ball mill pulverizing after the room temperature, cross 200 mesh sieves, make luminescent material of the present invention [5].
Embodiment 6:
Get: SrCO
3129.4g; Al
2O
351g; H
3BO
361.81g; BaCO
319.73g;
Activator and additional activation agent raw material are got: Eu
2O
31.75g; Dy
2O
31.86g;
After these raw material pulverizing, thorough mixing is placed in the crucible then.This crucible is placed electric furnace, and 800 ℃～1200 ℃ kept 3 hours under reductive condition.From electric furnace, take out after being cooled to 200 ℃.Further be cooled to ball mill pulverizing after the room temperature, cross 200 mesh sieves, make luminescent material of the present invention [6].
Embodiment 7:
Get: SrCO
371.6g; Al
2O
350.5g; H
3BO
30.3g;
Activator and additional activation agent raw material are got: Eu
2O
30.88g; Nd
2O
30.84g; Dy
2O
30.93g;
After these raw material pulverizing, thorough mixing is placed in the crucible then.This crucible is placed electric furnace, and 800 ℃～1400 ℃ kept 3 hours under reductive condition, kept 2 hours at 1300 ℃ again, took out from electric furnace after being cooled to 200 ℃ thereafter.Pulverize after further being cooled to room temperature, cross 200 mesh sieves, make luminescent material of the present invention [7].
The vinyl disc that luminescent material of the present invention (1)～(7) that embodiment 1～7 is made and each 0.2g test portion of zinc sulphide phosphor material are put into the 10mm diameter, in room temperature, under the 25RH% humidity, 15W luminescent lamp vertical range 20cm irradiation is after 15 minutes, measure the briliancy of each test portion with brightness photometer (TOPCONBM-5, the TOPCON of Amada Co., Ltd. system) at each time point.Measurement result shows, but luminescent material of the present invention emission wavelength under luminescent lamp or sunlight and other ultraviolet irradiation is the greenish light of 500nm-520nm.Its initial luminance is more than 10 times of initial luminance of zinc sulphide phosphatization material in the past, and can reach 30～70 hours visual time of persistence, is a kind of novel steady persistence high brightness phosphor material with excellent properties.Test result is shown in table 1.
Can know from table 1 and to find out that traditional zinc sulphide phosphor material briliancy less than 3 hours the time is almost 0.But long Persistence and high brightness fluorescent materials of the present invention stops still to have considerable brightness in back 3 hours in irradiation, and the ratio that has added the additional activation agent has only the higher briliancy of having of europium activator.The original intensity of long Persistence and high brightness fluorescent materials of the present invention is more than 10 times of zinc sulphide phosphor material.
Long Persistence and high brightness fluorescent materials of the present invention is by activator activated boracic sintered body, principal constituent is the monoclinic system crystal body, so have steady persistence and high briliancy characteristic, and then having higher briliancy by the sintered body of activator and additional activation agent activated, boracic, steady persistence and high brightness are that luminescent material of the present invention has two outstanding effects.
Table 1 (seeing the literary composition back)
Table 1
| Elapsed time (minute) | Briliancy (mcd/m 2) | |||||||
| Luminescent material of the present invention | Tradition zinc sulphide fluorescent material | |||||||
| Embodiment [1] | Embodiment [2] | Embodiment [3] | Embodiment [4] | Embodiment [5] | Embodiment [6] | Embodiment [7] | ||
| 0.5 | 961 | 3560 | 3860 | 3430 | 3160 | 3210 | 3940 | 280 |
| 2 | 519 | 1362 | 1495 | 1260 | 1060 | 1010 | 1560 | 120 |
| 3 | 387 | 936 | 1053 | 878 | 684 | 664 | 1100 | 80.2 |
| 4 | 272 | 722 | 818 | 712 | 535 | 510 | 910 | 61.7 |
| 5 | 146 | 579 | 666 | 568 | 426 | 414 | 689 | 48.9 |
| 10 | 89 | 292 | 343 | 280 | 217 | 203 | 364 | 22.3 |
| 15 | 76.1 | 189 | 213 | 179 | 140.5 | 129 | 257 | 15.6 |
| 20 | 61.7 | 151.3 | 181 | 149.0 | 107.7 | 98.1 | 204 | 11.2 |
| 25 | 58.3 | 113.8 | 135.9 | 108.7 | 85.1 | 73.2 | 157 | 7.8 |
| 30 | 55.2 | 89.7 | 104.7 | 77.3 | 70.4 | 58.7 | 130 | 3.6 |
| 40 | 49.2 | 61 | 77.9 | 59.2 | 52.6 | 40.1 | 90.2 | 2.5 |
| 60 | 42.1 | 51.8 | 61.7 | 48.4 | 42.4 | 34.2 | 67.9 | 1.8 |
| 120 | 15.8 | 26 | 36.3 | 25.3 | 17.2 | 15.1 | 37.1 | 0.3 |
| 180 | 8.9 | 14.2 | 27.5 | 13.2 | 13.7 | 11.2 | 28.2 | 0 |
| 240 | 7.6 | 13.1 | 20.0 | 10.5 | 9.7 | 9.5 | 21.2 | 0 |
| 480 | 3.5 | 5.4 | 6.9 | 5.2 | 4.3 | 4.3 | 7.1 | |
| 600 | 2.3 | 3.5 | 4.5 | 3.1 | 2.4 | 2.3 | 4.5 | |
| 720 | 1.8 | 3.2 | 3.8 | 3.0 | 2.2 | 2.3 | 3.9 | |
| 1800 | 0.9 | 2.8 | 3.2 | 2.4 | 1.7 | 1.9 | 3.2 | |
Claims (4)
1. long Persistence and high brightness fluorescent materials is characterized in that by general expression:
MNAl
2-xB
xO
4The sintered compact of expression constitutes, and in the formula, M represents alkaline-earth metal, and N represents rare earth element europium, neodymium, dysprosium, 0.1≤X≤1, and the addition of N is more than the 0.001mol% of alkaline-earth metal of M representative, below the 10mol%.
2. the long Persistence and high brightness fluorescent materials of putting down in writing as claim 1, its characteristic is that M is a strontium, N is an europium.
3. the long Persistence and high brightness fluorescent materials of putting down in writing as claim 1 is characterized in that M is at least a alkaline-earth metal among strontium and magnesium, calcium, the barium.
4. the preparation method of the described long Persistence and high brightness fluorescent materials of claim 1, by
(1) takes by weighing material by stoichiometric ratio
(2) starting material that weigh up are even through ground and mixed
(3) with mixed material calcination
(4) sintered compact is reduced
(5) sintered compact is cooled off
(6) cooled sintered compact is pulverized
(7) will pulverize the body sub-sieve
Constitute, it is characterized in that the calcination reduction temperature is 800-1200 ℃, calcination time and recovery time were respectively 2-4 hour, and the reduction operation is that carbon dust directly reduces.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96100981A CN1063211C (en) | 1995-07-17 | 1996-03-28 | Long-persistence and high-brightness luminous material and its prepn |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95107496.2 | 1995-07-17 | ||
| CN95107496 | 1995-07-17 | ||
| CN96100981A CN1063211C (en) | 1995-07-17 | 1996-03-28 | Long-persistence and high-brightness luminous material and its prepn |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1152018A CN1152018A (en) | 1997-06-18 |
| CN1063211C true CN1063211C (en) | 2001-03-14 |
Family
ID=25743724
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN96100981A Expired - Fee Related CN1063211C (en) | 1995-07-17 | 1996-03-28 | Long-persistence and high-brightness luminous material and its prepn |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1086727C (en) * | 1998-01-14 | 2002-06-26 | 中日合资无锡帕克斯装饰制品有限公司 | Fine granule luminous storage fluorescence powder and its preparation method |
| CN1112420C (en) * | 1998-04-24 | 2003-06-25 | 中国科学院长春物理研究所 | Red phosphor powder for high pressure mercury lamp |
| CN103013507A (en) * | 2012-12-26 | 2013-04-03 | 广州有色金属研究院 | Ultrafine rare-earth aluminate long-persistence luminescent material and preparation method thereof |
| CN103333685B (en) * | 2013-06-27 | 2015-07-29 | 河北大学 | A kind of Yb 2+new type long-persistence luminescent material of doping and preparation method thereof |
| CN107867825A (en) * | 2017-11-02 | 2018-04-03 | 杭州显庆科技有限公司 | A kind of mechanoluminescence transparent ceramic material and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1095748A (en) * | 1993-04-28 | 1994-11-30 | 根本特殊化学株式会社 | Phosphorscent phosphor |
-
1996
- 1996-03-28 CN CN96100981A patent/CN1063211C/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1095748A (en) * | 1993-04-28 | 1994-11-30 | 根本特殊化学株式会社 | Phosphorscent phosphor |
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| Publication number | Publication date |
|---|---|
| CN1152018A (en) | 1997-06-18 |
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