CN1203208A - Ceramic luminescent material and producing technique thereof - Google Patents
Ceramic luminescent material and producing technique thereof Download PDFInfo
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- CN1203208A CN1203208A CN 97111836 CN97111836A CN1203208A CN 1203208 A CN1203208 A CN 1203208A CN 97111836 CN97111836 CN 97111836 CN 97111836 A CN97111836 A CN 97111836A CN 1203208 A CN1203208 A CN 1203208A
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Abstract
A luminous ceramic material used to coating it on surface of object for showing and decoration in darkness contains matrix including alkali-earth metal compound and alumina or aluminium hydroxide, boron compound, Eu as activating agent, Dy or Ho as coactivating agent, and the X compound or fluoride of alkali-earth metal element M. Said luminous material prepared by heating at 1420-1560 deg.C for 1-4 hr contains MFX crystal, where M is one or more of Ca, Mg, Sr and Ba, X is chosen from Cl, Br and I, and F is fluorine. It has strong light storage and emitting power.
Description
The present invention relates to a kind of stupalith, particularly ceramic luminescent material and manufacturing process thereof.
Its component of existing ceramic luminescent material is by alkaline earth metal compound, and being added with aluminate is matrix, is activator with the rare earth element, carries out the sosoloid sintering through heating and forms.Existing ceramic luminescent material is the firing temperature that prolongs with traditional phosphor; promptly below 1300 ℃; the Phosphorscent phosphor of record among the Chinese invention patent prospectus CN1095748A (on November 30th, 1994) for example; it is the mixture of Strontium carbonate powder, aluminum oxide, europium sesquioxide, boric acid formation; under the protection of nitrogen hydrogen stream, fired 1 hour at 1300 ℃.Obtain this compound powder after the cooling, cross screen sizing, obtain this luminescent material, obtain light-accumulated luminous preferably effect.But this luminescent material solid state reaction when 1300 ℃ of heating is insufficient, can not form sosoloid preferably.
The applicant was matrix with reference to above-mentioned prescription with alkaline-earth metal Sr compound and aluminate once, and rare earth element Eu compound is activator and is equipped with rare-earth compound Dy, Ho for the agent of living altogether, is added with H
3BO
3Test, this test recipe is as follows:
Al
2O
338 gram Dy
2O
31.2 gram
SrCO
352 gram Ho
2O
31.2 gram
Eu
2O
31.2 gram H
3BO
33.8 gram
Test heating in nitrogen hydrogen under the different heating temperature, 1. keep 4 hours postcooling to 1420 ℃, obtain luminescent material, its initial luminous intensity is 180mcd/m
2, fluorescent lifetime 1 hour.2. keep cold after 3 hours during to 1480 ℃, obtain this luminescent material, its initial luminous intensity is 880mcd/m
2, fluorescent lifetime 6 hours.3. keep 3 hours postcooling during to 1510 ℃, the initial luminous intensity of the luminescent material that obtains is 900mcd/m
2, fluorescent lifetime is 8 hours.4. during to 1560 ℃, material occurs and dissolve phenomenon, initial luminous intensity drops to 300mcd/m
2, fluorescent lifetime 2 hours.On light-accumulated luminous ability, still need further to improve.
The object of the invention provides a kind of light-accumulated luminous ability height, ceramic luminescent material that luminous stabilising decay is slower and manufacturing process thereof.
The present invention seeks to realize by following technical scheme.The prescription of this ceramic luminescent material is by alkaline earth metal compound, and being added with aluminum oxide or aluminium hydroxide is matrix, is that the compound of activator, other rare earth element is the agent of living altogether with Eu thulium compound, also contains the compound such as the H of boron
3BO
3Particularly in prescription, be added with the X compound of (1) alkali earth metal M, M is Ca, Mg, Sr, Ba, X is Cl, Br, I, also be added with the fluorine cpd of (2) this alkaline-earth metal M, i.e. the compound of the fluorine of Ca, Mg, Sr, Ba is after heating is fired, make the crystal that contains the chemical molecular formula of MFX in this luminescent material, wherein:
M represents any one or more among Ca, Mg, Sr, the Ba,
X represents any among Cl, Br, the I,
F is a fluorine element.
Said components is mixed, fire through the oxygen barrier heating and form this ceramic luminescent material, once in an embodiment with SrCO
3And Al
2O
3Be matrix, the Xization thing that is added with (1) alkali earth metal M is BaCl
2, the fluorochemical of (2) alkaline-earth metal M is BaF
2, test, after the oxygen barrier heating is fired, contain the BaFCl crystal in this luminescent material.This crystal can significantly be strengthened the light-accumulated luminous ability of this luminescent material, make this material become very strong optical stimulated luminescence material, promptly in the Eu of its crystallo-luminescence center, after mixing the BaFCl crystal, replace positively charged ion Ba to cause the distortion of local lattice, through near luminescence center, forming the stable Cl heart after the illumination, can efficiently the property amount of these light be put aside, in the time of in the dark, can emit institute's accumulative amount once more with the form of light, and for different types of light such as daylight, light, natural light, its accumulating capability is all fine.Adopt the muriate of alkali earth metal barium in the prescription, effect is very good, adopts bromide such as BaBr
2, iodide such as BaI
2Also can reach similar effect.
Make luminescent material reach very high luminous efficiency and hold luminous energy power, also must select appropriate manufacturing process for use, the manufacture technology of ceramic luminescent material of the present invention is when heating, adopt nitrogen or hydrogen or nitrogen hydrogen mixeding gas to be full of process furnace, carry out the oxygen barrier heating, kept 1-4 hour, the oxygen barrier cooling.After Heating temperature was to burn till more than 1420 ℃, this luminescent material just had tangible luminous intensity and holds luminous energy power, reaches practical function, when temperature when burning till for 1480 ℃, solid solution reaction is better, its luminous luminous energy power of holding increases, in the time of 1500 ℃, significantly improve.Performance is best when temperature increases to 1510 to 1520 ℃, and when temperature increased successively, performance progressively descended, and when increasing to 1560 ℃, then the luminous energy power of holding of this luminescent material and luminous power all reduce greatly.
The present invention compares with above-mentioned test recipe, owing to adopted chlorine, the fluorine cpd that added alkali earth metal in existing prescription, makes the distortion that causes the local lattice in this luminescent material, holds light and luminous power thereby significantly improved it.
Do with embodiment below and specify.
Embodiment 1.Prescription is: (adding composition (1) is BaCl
2, (2) are BaF
2)
Al
2O
338 gram Dy
2O
31.2 gram
SrCO
352 gram Ho
2O
31.2 gram
H
3BO
33.8 gram BaCl
22.1 gram
Eu
2O
31.2 gram BaF
22.4 gram
In this prescription, SrCO
3And Al
2O
3Be matrix, Eu
2O
3Be activator, Dy
2O
3, Ho
2O
3Be the agent of living altogether, promptly impel the mobilizing function of this activator to strengthen BaCl
2, BaF
2Cause the distored component of local in this luminescent material for making, these components are mixed, be heated to 1420 ℃ in nitrogen hydrogen, keep being cooled to 800 ℃ and obtaining luminescent material after 4 hours, the initial luminous intensity of this luminescent material is 1000mcd/m
2, fluorescent lifetime 3 hours.
Embodiment 2, get the compound of embodiment 1, with its mixing, keep 3 hours be heated to 1480 ℃ in nitrogen hydrogen mixeding gas after, and cold promptly to obtain the initial luminous intensity of luminescent material after 800 ℃ be 2800mcd/m
2, fluorescent lifetime is 8 hours.
Embodiment 3, get the compound of embodiment 1 after, kept 3 hours after in nitrogen hydrogen mixeding gas, being heated to 1500 ℃, cold promptly to 800 ℃, the initial luminous intensity that obtains this luminescent material is 3320mcd/m
2, fluorescent lifetime is more than 18 hours.
Embodiment 4, get the compound of embodiment 1 after, in nitrogen and hydrogen mixture, be heated to 1510 ℃, kept 3 hours, cold promptly to 800 ℃, the initial luminous intensity that obtains this luminescent material is 4000mcd/m
2, fluorescent lifetime is more than 20 hours.
Embodiment 5, get the compound of embodiment 1 after, in nitrogen and hydrogen mixture, be heated to 1520 ℃ and kept 3 hours, cold promptly to 800 ℃, the initial luminous intensity that obtains this luminescent material is 3360mcd/m
2, fluorescent lifetime is more than 20 hours.
Embodiment 6, get the compound of embodiment 1 after, in nitrogen and hydrogen mixture, be heated to 1530 ℃, kept 3 hours, cold promptly to 800 ℃, the initial luminous intensity that obtains this luminescent material is 3000mcd/m
2, fluorescent lifetime is 15 hours.
Embodiment 7, get the compound of embodiment 1 after, in nitrogen hydrogen mixeding gas, be heated to 1560 ℃, kept 2 hours, cold phenomenon appears dissolving in this luminescent material promptly to 800 ℃, initial luminous intensity 1000mcd/m
2, fluorescent lifetime 2 hours.
Embodiment 8, press compound and the heating means of embodiment 1, only with BaF
2Change Weight To 1.86 grams, BaCl
2Change 1 gram into, under 1510 ℃ of temperature, kept 3 hours, be cooled to below 800 ℃ after, obtaining the initial luminous intensity of luminescent material is 4000mcd/m
2, fluorescent lifetime is more than 16 hours.
Embodiment 9, press compound and the heating means of embodiment 1, only with BaF
2Change Weight To 3 grams, BaCl
2Change Weight To 2.2 gram kept 3 hours under 1510 ℃ of temperature, be cooled to below 800 ℃ after, obtaining the initial luminous intensity of luminescent material is 3300mcd/m
2, fluorescent lifetime is more than 16 hours.
Embodiment 10, fill a prescription to (added ingredients (1) is BaCl
2, (2) are MgF
2)
Al
2O
336 gram BaCl
22 grams
SrCO
350 gram Eu
2O
31.2 gram
MgF
26 gram Dy
2O
31.2 gram
H
3BO
33.8 gram
Heating 3 hours in nitrogen hydrogen is come out of the stove after being cooled to 800 ℃ under 1510 ℃ of temperature, and initial luminous intensity is 2900mcd/m
2, fluorescent lifetime is more than 14 hours.
Embodiment 11, fill a prescription to be: (adding composition (1) is BaCl
2(2) be CaF
2)
Al
2O
336 gram Eu
2O
31.2 gram
SrCO
350 gram Dy
3O
31.2 gram
CaF
26 gram H
3BO
33.8 gram
BaCl
22 grams
Heating is 3 hours in 1510 ℃ of nitrogen hydrogen, comes out of the stove after being cooled to 800 ℃, and initial luminous intensity is 3000mcd/m
2, fluorescent lifetime is more than 10 hours.
Embodiment 12, fill a prescription to (added ingredients (1) is BaBr
2, (2) are BaF
2):
Al
2O
336 gram H
3BO
35 grams
SrCO
350 gram Eu
2O
31.2 gram
BaF
25 gram Dy
2O
31.2 gram
BaBr
21 gram
Come out of the stove initial luminous intensity 2900mcd/m for 800 ℃ in 1510 ℃ of heating cooling in 3 hours
2, fluorescent lifetime is more than 10 hours.
Embodiment 13.Prescription is for (adding composition (1) is BaI
2, (2) are BaF
2):
Al
2O
336 gram H
3BO
35 grams
SrCO
350 gram Eu
2O
31.2 gram
BaF
25 gram Dy
2O
31.2 gram
BaI
21 gram
Heating is 3 hours in 1510 ℃ of nitrogen hydrogen, is cooled to 800 ℃ and comes out of the stove, initial luminous intensity 2800mcd/m
2, fluorescent lifetime is more than 10 hours.
Embodiment 14, fill a prescription to be (increase has P):
SrCO
351 gram BaCl
22 grams
Al
2O
336 gram BaF
23 grams
H
3BO
35 gram (NH4) HPO4,2 grams
Eu
2O
31.2 gram Ho
2O
31.2 gram
Heating is 3 hours in 1510 ℃ of nitrogen hydrogen, is cooled to 800 ℃ and comes out of the stove, initial luminous intensity 3200mcd/m
2, fluorescent lifetime is more than 12 hours.Illustrate that adding P can improve its luminous intensity and fluorescent lifetime.
Table 1 is the consolidated statement of above embodiment 1 to 14, and embodiment of the invention contrast as shown in table 1 is as follows, as can be seen:
1. equal effective than aforesaid test recipe of the result of each embodiment.The light application time of the embodiment of the invention is 3-5 minute, and its light-accumulated luminous ability is stronger, and the light application time of afore-mentioned test prescription is more than 10 minutes, but light-accumulated luminous ability is relatively poor.
2. in the present invention to add (1) BaCl
2(2) BaF
2Effect best, the BaCl among the embodiment 8,9
2And BaF
2Different among content and the embodiment 1-7, but effect is still better.Initial luminous intensity as embodiment 4,8 is 4000mcd/m
2Embodiment 5,9 takes second place, all at 3300mcd/m
2More than, fluorescent lifetime is more than 16 hours, and the Heating temperature point is 1510 and 1520 ℃.Embodiment 3,6 takes second place again, but initial luminous intensity is still at 3000mcd/m
2More than, fluorescent lifetime is more than 15 hours, and Heating temperature is outside 1510-1520 ℃ of scope.
3. embodiment 12,13, and wherein adding composition (1) is BaBr
2, BaI
2, (2) are BaF
2, it is BaCl that its effect adopts (1)
2Embodiment 4,8 poor.
4. among the embodiment 10,11, adding composition (1) is BaCl
2, (2) adopt MgF
2, CaF
2, but effect is BaF with (2)
2Embodiment 4 for poor.
5. among the embodiment 1,2,, can not make material composition form solid appearance body fully, and embodiment 7 because crossing up to 1560 ℃ material is dissolved, temperature reduce its luminescent properties greatly because Heating temperature is not enough.
6. embodiment 14 is for adding phosphoric in the prescription, and this also can increase to the luminescent material performance.
7. comprehensive the foregoing description is BaCl to add (1) in prescription
2, (2) are BaF
2The effect of making ceramic luminescent material is best, Heating temperature with between 1480-1520 ℃ for well.
Ceramic luminescent material of the present invention has and holds luminous energy power and stable luminous power fast, and decay of luminescence is slow, be applicable to be coated in the implements surface as decorate and dark in show and use.Table 1
| Embodiment | Add composition | Heating temperature ℃ | Effect | ||
| (1) the X compound of alkaline-earth metal M | (2) fluorochemical of alkaline-earth metal M | Initial luminous intensity mcd/m 2 | Fluorescent lifetime hour | ||
| ?1 ?2 ?3 ?4 ?5 ?6 ?7 ? ?8 ?9 ?10 ?11 ?12 ?13 ?14 | ???BaCl 22.1 gram ＂ ＂ ＂ ＂ ＂ ＂ ＂ ＂ ＂ ＂ ＂ ＂ ＂ 1 gram ＂ 2.2 gram ＂ 2 gram ＂ 2 gram BaBr21 gram BaI 21 gram BaCl 22 grams (adding P) | ??BaF 22.4 gram ＂ ＂ ＂ ＂ ＂ ＂ ＂ ＂ ＂ ＂ ＂ ＂ ＂ 1.86 gram ＂ 3 gram MgF26 gram CaF 26 gram BaF 25 gram BaF 25 gram BaF 23 grams | 1,420 1,480 1,500 1,510 1,520 1,530 1560 materials dissolve 1510 ＂ ＂ ＂ ＂ ＂ ＂ | ????1000 ????2800 ????3320 ????4000 ????3360 ????3000 ????1000 ? ????4000 ????3300 ????2900 ????3000 ????2900 ????2800 ????3200 | ????3 ????8 ????18 ????20 ????20 ????15 ????2 ? ????16 ????16 ????14 ????10 ????10 ????10 ????12 |
Claims (7)
1. ceramic luminescent material and manufacturing process thereof, contain in the prescription with alkaline earth metal compounds, being added with aluminum oxide or aluminium hydroxide is matrix, compound with thulium Eu is an activator, the compound that also contains boron, make through oxygen barrier heating and oxygen barrier cooling, it is characterized in that: the X compound that also contains (1) alkali earth metal M, (2) compound of the fluorine of this alkali earth metal, after temperature 1420-1560 ℃ was fired in following 1-4 hour, make the crystal that contains the chemical molecular formula of representing with MFX in this luminescent material, wherein:
M is any one or more among Ca, Mg, Sr, the Ba,
X is any among Cl, Br, the I,
F is a fluorine element.
2. ceramic luminescent material according to claim 1 and manufacturing process thereof is characterized in that: also contain the P element in the described prescription.
3. ceramic luminescent material according to claim 1 and 2 and manufacturing process thereof is characterized in that: be added with among thulium Dy, the Ho one or more as the agent of living altogether in prescription.
4. ceramic luminescent material according to claim 3 and manufacturing process thereof is characterized in that: the X compound of described (1) alkali earth metal M is BaCL
2, the compound of the fluorine of (2) this alkali earth metal M is BaF
2
5. ceramic luminescent material according to claim 4 and manufacturing process thereof is characterized in that: described oxygen barrier Heating temperature is best to be 1480-1520 ℃, and the oxygen barrier cooling temperature is 800 ℃.
6. ceramic luminescent material according to claim 3 and manufacturing process thereof is characterized in that: described oxygen barrier heating and oxygen barrier are cooled to heating in nitrogen or hydrogen or nitrogen and hydrogen mixture, cooling.
7. ceramic luminescent material according to claim 4 and manufacturing process thereof is characterized in that: described oxygen barrier heating and oxygen barrier are cooled to heating in nitrogen or hydrogen or nitrogen and hydrogen mixture, cooling.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 97111836 CN1203208A (en) | 1997-06-24 | 1997-06-24 | Ceramic luminescent material and producing technique thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 97111836 CN1203208A (en) | 1997-06-24 | 1997-06-24 | Ceramic luminescent material and producing technique thereof |
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|---|---|
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012155811A1 (en) * | 2011-05-13 | 2012-11-22 | Byd Company Limited | Method for selectively metallizing surface of ceramic substrate, ceramic product and use of ceramic product |
| CN103205811A (en) * | 2012-01-16 | 2013-07-17 | 中国科学院新疆理化技术研究所 | Large size BaClBF4 nonlinear optical crystal, and preparation method and application thereof |
| CN106278188A (en) * | 2016-06-30 | 2017-01-04 | 李文红 | A kind of high temperature luminescent ceramic and preparation method thereof |
| CN109266335A (en) * | 2018-11-02 | 2019-01-25 | 岭南师范学院 | A kind of yellow longpersistent luminescent material and preparation method thereof |
-
1997
- 1997-06-24 CN CN 97111836 patent/CN1203208A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012155811A1 (en) * | 2011-05-13 | 2012-11-22 | Byd Company Limited | Method for selectively metallizing surface of ceramic substrate, ceramic product and use of ceramic product |
| US11382216B2 (en) | 2011-05-13 | 2022-07-05 | Byd Company Limited | Method for selectively metallizing surface of ceramic substrate, ceramic product and use of ceramic product |
| CN103205811A (en) * | 2012-01-16 | 2013-07-17 | 中国科学院新疆理化技术研究所 | Large size BaClBF4 nonlinear optical crystal, and preparation method and application thereof |
| CN103205811B (en) * | 2012-01-16 | 2015-08-19 | 中国科学院新疆理化技术研究所 | Large size chlorine barium fluoborate non-linear optic crystal and its production and use |
| CN106278188A (en) * | 2016-06-30 | 2017-01-04 | 李文红 | A kind of high temperature luminescent ceramic and preparation method thereof |
| CN109266335A (en) * | 2018-11-02 | 2019-01-25 | 岭南师范学院 | A kind of yellow longpersistent luminescent material and preparation method thereof |
| CN109266335B (en) * | 2018-11-02 | 2021-09-17 | 岭南师范学院 | Yellow long-afterglow luminescent material and preparation method thereof |
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