CN101768434A - High-temperature-resistant long-decay characteristic light-emitting material and preparation method thereof - Google Patents
High-temperature-resistant long-decay characteristic light-emitting material and preparation method thereof Download PDFInfo
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- CN101768434A CN101768434A CN200810241177A CN200810241177A CN101768434A CN 101768434 A CN101768434 A CN 101768434A CN 200810241177 A CN200810241177 A CN 200810241177A CN 200810241177 A CN200810241177 A CN 200810241177A CN 101768434 A CN101768434 A CN 101768434A
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Abstract
The invention provides a high-temperature-resistant long-decay characteristic light-emitting material and a preparation method thereof. The method for preparing the high-temperature-resistant and long-decay characteristic light-emitting material consists of the following steps: mixing a primary phosphor with long decay characteristics and boron-containing compounds, and baking the mixed powder at the temperature of 800-1000 DEG C, thereby obtaining a granular high-temperature-resistant long-decay characteristic light-emitting material with the D phase (including D') coated on the A phase.
Description
Technical field
The present invention relates to a kind of high thermal resistance long after glow luminous material and preparation method thereof, relate in particular to a kind of long afterglow property that does not significantly reduce common long after glow luminous material, and the long after glow luminous material that high-temperature stability is good, further relate to a kind of long afterglow property that does not significantly reduce common long after glow luminous material, and high-temperature stability and all good long after glow luminous material of water-proofing performance.
Background technology
In the existing long after glow luminous material, modal luminous composition is with MAl
2O
4The compound of expression is as the parent crystallization, and wherein M is selected from calcium, strontium, barium etc.Hold the glimmering body of photosensitiveness such as strontium aluminate class more commonly, such fluor can reach the long after glow luminous material with excellent steady persistence performance by adding activator as Eu, Dy etc.Specifically, existing with SrAl
2O
4: the long after glow luminous material that Eu represents, it is with SrAl
2O
4Be parent, with Eu
2+As activator, after being excited, send the green glow that predominant wavelength is 520nm, further add a small amount of Dy when therein, form with SrAl
2O
4: during fluor that Eu, Dy represent, at Dy
3+Effect under, can prolong time of persistence of its light that sends greatly, become the long after glow luminous material of at present the most frequently used aluminium strontium phosphate-gallate series.
Another kind of long after glow luminous material is with MAl
14O
25The compound of expression is as the parent crystallization, and wherein M is selected from calcium, strontium, barium etc.Such as: with Sr
4Al
14O
25For parent crystalline fluor, with Eu
2+As activator, after being excited, send the blue light of 480nm.
In part strontium aluminate class long after glow luminous material, also may there be above two kinds of parent crystallizations simultaneously.
Existing long after glow luminous material is used excited by visible light usually, after stopping to excite, can reach in considerable time (as: dozens of minutes was by several hours) and also can with the naked eye see twilight sunset.
Summary of the invention
Based on prior art, the present inventor finds that through further investigation the high thermal resistance of existing long after glow luminous material is relatively poor, as: with Eu
2+As the strontium aluminate long after glow luminous material of activator, if be placed on higher temperature, for example 800～1000 ℃, in such high temperature oxidation stability environment, can lose the function of its activator, cause the fluorescent characteristic forfeiture.Without being limited by theory, the present inventor thinks that this may be owing to the Eu as activator
2+Eu can further be oxidized to
3+Thereby, make the high thermal resistance variation of this long after glow luminous material.
In addition, the water tolerance of existing long after glow luminous material is also relatively poor, if long-term exposure can be lost fluorescent characteristic and twilight sunset in air (moisture is arranged in the air) and other wet environment.Without being limited by theory, the present inventor thinks that this may be owing to have a large amount of textural defect such as cavity in the particle of fluor, can absorb airborne moisture etc. in air, causes the decomposition of the parent of fluor, thereby lose luminescence center, forfeiture fluorescent characteristic and twilight sunset.
Along with on the market for the continuous increase of the demand of strontium chlorate MClO 3 fluorescent substance with environment durability, the long after glow luminous material that further requirement has good high thermal resistance further requires with good high thermal resistance and water-proof long after glow luminous material.
The objective of the invention is to solve above-mentioned existing issue, a kind of high thermal resistance long after glow luminous material and preparation method thereof is provided, the long after glow luminous material that obtains also has good high-temperature stability when significantly not reducing its long afterglow property.
Further, provide a kind of high temperature resistant and water-proof long after glow luminous material and preparation method thereof, the long after glow luminous material that obtains also has good high-temperature stability and water-proofing performance when significantly not reducing long afterglow property
For addressing the above problem, according to the embodiment of the present invention, high thermal resistance long after glow luminous material of the present invention obtains by existing long after glow luminous material further being processed, being improved.Being about to existing long after glow luminous material (being referred to herein as primary fluor's body) pulverizes, carry out uniform mixing with the powder of boron-containing compound, the mixed powder that obtains is burnt till once again, thereby obtain comparing, also improved the long after glow luminous material of its high-temperature stability when significantly not reducing persistence characteristic with former elementary glimmering body; And then also improved the long after glow luminous material of its high-temperature stability and water-proofing performance when having obtained significantly not reducing persistence characteristic.
In this article, the long afterglow property of luminescent material is meant uses excited by visible light, after stopping it and exciting, can reach in considerable time and also can with the naked eye see twilight sunset, and this time is changeable according to the needs of using, and is preferably dozens of minutes by several hours.
In this article, be meant can anti-800～1000 ℃ high temperature for the high thermal resistance of luminescent material.
In this article, be meant can soaking-resistant for the water tolerance of luminescent material.
According to preferred implementation of the present invention, use conventional method to burn till by the raw material powder that will contain Sr, Al, O, B, Eu, Dy, obtain with Sr (Al, B)
2O
4: Eu, Dy and/or Sr
4(Al, B)
14O
25: primary fluor's body that Eu, Dy represent.Then, the primary fluor body is pulverized, carried out uniform mixing, the mixed powder that obtains is burnt till once again, thereby obtain when significantly not reducing long afterglow property, also having the long after glow luminous material of good high-temperature stability with the powder of boron-containing compound.
That is to say, the invention provides following long after glow luminous material and preparation method thereof:
(1) a kind of high thermal resistance long after glow luminous material is characterized in that it prepares by the following method:
Primary fluor's body that will have long afterglow property mixes with boron-containing compound, and the mixture that obtains is burnt till at 800～1100 ℃, obtains the high thermal resistance long after glow luminous material.
As (1) described high thermal resistance long after glow luminous material, it is characterized in that (2) described boron-containing compound is the mineral compound that can generate boron oxide in the temperature-rise period that burns till.
(3) as (1) or (2) described high thermal resistance long after glow luminous material, it is characterized in that,
That selects in the group that described boron-containing compound is made up of following material is at least a: inorganic borate, boric acid, boron oxide and their mixture.
(4) as (3) described high thermal resistance long after glow luminous material, it is characterized in that described inorganic borate is a borax.
As (1) to (4) each described high thermal resistance long after glow luminous material, it is characterized in that (5) the particulate structure of the luminescent material of formation is that the particle of primary fluor's body or cluster shape particle are at room temperature wrapped up by the material of vitreous state (D).
(6) as (1) to (5) each described high thermal resistance long after glow luminous material, it is characterized in that, before mixing, described primary fluor body is crushed to below 50 orders, boron-containing compound also is crushed to below 50 orders.
(7) as (1) to (6) each described high thermal resistance long after glow luminous material, it is characterized in that firing time is 2～8 hours.
(8) as (1) to (7) each described high thermal resistance long after glow luminous material, it is characterized in that firing temperature is 900～1050 ℃, firing time is 3～7 hours.
(9) as (1) to (8) each described high thermal resistance long after glow luminous material, it is characterized in that described primary fluor body is the aluminate series long afterglow luminescent material.
(10) as (9) described high thermal resistance long after glow luminous material, it is characterized in that,
This aluminate series long afterglow luminescent material is an alkaline-earth metal class aluminate-series long after glow luminous material.
(11) as (9) described high thermal resistance long after glow luminous material, it is characterized in that,
This aluminate series long afterglow luminescent material is a strontium aluminate series long afterglow luminescent material.
(12) as (1) to (11) each described high thermal resistance long after glow luminous material, it is characterized in that,
Described primary fluor body is by the preparation of the method that may further comprise the steps, wherein, by burning till the raw material powder that contains Sr, Al, O, B, Eu, Dy, obtain containing with Sr (Al, B)
2O
4: Eu, Dy and/or Sr
4(Al, B)
14O
25: primary fluor's body of the compound that Eu, Dy represent, the temperature that this primary fluor's body burns till is 1100～1500 ℃, firing time is 3～8 hours, is reducing atmosphere burning till the later stage firing atmosphere at least.
(13) arrive (12) each described high thermal resistance long after glow luminous material as (1), it is characterized in that with respect to 100 weight part primary fluor bodies, the addition that this boron-containing compound is converted into boron oxide is 20～50 weight parts above-mentioned.
(14) a kind of preparation method of high thermal resistance long after glow luminous material, it comprises at least:
Primary fluor's body that will have long afterglow property mixes with boron-containing compound, and the mixed powder that obtains is burnt till at 800～1100 ℃, obtains the high thermal resistance long after glow luminous material.
As (14) described preparation method, it is characterized in that (15) described boron-containing compound is the mineral compound that can generate boron oxide in the temperature-rise period that burns till.
(16) as (14) or (15) described preparation method, it is characterized in that,
That selects in the group that described boron-containing compound is made up of following material is at least a: inorganic borate, boric acid, boron oxide or their mixture.
As (16) described preparation method, it is characterized in that (17) described inorganic borate is a borax.
As (14) to (17) each described preparation method, it is characterized in that (18) the particulate structure of the luminescent material of formation is that the particle of primary fluor's body or cluster shape particle are at room temperature wrapped up by the material of vitreous state (D).
(19) as (14) to (18) each described preparation method, it is characterized in that, before mixing, described primary fluor body is crushed to below 50 orders, boron-containing compound also is crushed to below 50 orders.
As (14) to (19) each described preparation method, it is characterized in that (20) firing time is 2～8 hours.
As (14) to (20) each described preparation method, it is characterized in that (21) firing temperature is 900～1050 ℃, firing time is 3～7 hours.
(22) as (14) to (21) each described preparation method, it is characterized in that,
Described primary fluor body is the aluminate series long afterglow luminescent material.
(23) as (22) described preparation method, it is characterized in that,
This aluminate series long afterglow luminescent material is an alkaline-earth metal class aluminate-series long after glow luminous material.
(24) as (23) described preparation method, it is characterized in that,
This aluminate series long afterglow luminescent material is a strontium aluminate series long afterglow luminescent material.
(25) as (14) to (24) each described preparation method, it is characterized in that,
Described primary fluor body is by the preparation of the method that may further comprise the steps, wherein, by burning till the raw material powder that contains Sr, Al, O, B, Eu, Dy, obtain containing with Sr (Al, B)
2O
4: Eu, Dy and/or Sr
4(Al, B)
14O
25: primary fluor's body of the compound that Eu, Dy represent, the firing temperature of primary fluor's body are 1100～1500 ℃, and firing time is 3～8 hours, are reducing atmosphere burning till the later stage firing atmosphere at least.
(26) arrive (25) each described preparation method as (14), it is characterized in that with respect to 100 weight part primary fluor bodies, the addition that this boron-containing compound is converted into boron oxide is 20～50 weight parts above-mentioned.
(27) arrive (26) each described preparation method as (14), it is characterized in that described firing atmosphere is N
2+ H
2
Description of drawings
Fig. 1 is the photo of primary fluor's body grain pattern of obtaining of embodiment 7;
Fig. 2 is the photo of the long after glow luminous material grain pattern that obtains of embodiment 7;
Fig. 3 is a part particulate enlarged view among Fig. 2.
Embodiment
Preferred implementation of the present invention below is described.
A kind of embodiment according to high thermal resistance long after glow luminous material of the present invention, primary fluor's body that will have long afterglow property mixes with boron-containing compound, and the mixture that obtains burnt till at 800～1100 ℃, obtain the high thermal resistance long after glow luminous material.Wherein the long afterglow property of this primary fluor's body is meant and uses excited by visible light, after stopping it and exciting, can reach in considerable time and also can with the naked eye see twilight sunset, and this time is changeable according to the needs of using, and is preferably dozens of minutes by several hours.A kind of embodiment according to high thermal resistance long after glow luminous material of the present invention, can be that primary fluor's body is pulverized with existing long after glow luminous material, carry out uniform mixing with the powder of boron-containing compound, the mixed powder that obtains is burnt till, formed the high thermal resistance long after glow luminous material of the present invention after the modification.
Wherein this primary fluor's body can be existing any long after glow luminous material, comprise long after glow luminous material, noctilucence fluor or the twilight sunset fluor put down in writing in disclosed each patent application now, be preferably the aluminate series long afterglow luminescent material, more preferably alkaline-earth metal class aluminate-series long after glow luminous material, more preferably strontium aluminate series long afterglow long after glow luminous material.Such primary fluor's body as an example, can enumerate luminescent material as the patent of invention ZL99100285.7 of Beijing Hua Long Ya Yang Technology Development Co., Ltd etc., the luminescent material of the patent of invention ZL97100694.6 of Beijing Hua Long Ya Yang Technology Development Co., Ltd etc., disclosed long-afterglow fluorescent body among the Japanese kokai publication hei 8-73845, disclosed twilight sunset fluor among the Japanese kokai publication hei 8-170076, it also can be disclosed fluor among the Chinese CN1154710 with twilight sunset, disclosed long after glow luminous material etc. also can be any long after glow luminous material product that is available commercially among the TOHKEMY 2000-154382.No matter adopt which kind of primary fluor's body, as long as the present inventor recognizes this primary fluor's body powder and boron-containing compound powder uniform mixing, the mixed powder that obtains is burnt till once again, obtain the long after glow luminous material of the present invention after the modification, can not change or significantly not reduce former other characteristics of luminescences of elementary fluor substantially, under the prerequisite such as persistence characteristic, light characteristic etc., further improved its high thermal resistance, more preferably can improve its water tolerance simultaneously, thereby obtain brand-new long after glow luminous material.This product has not only kept good practicality, also has the better adaptability to environment, longer service life.
Without being limited by theory, the present inventor thinks, by increasing with primary fluor's body and the process of burning till after boron-containing compound mixes, improve the grain pattern of primary fluor's body, make boron-containing compound outside the particle of former elementary fluor, form the embracing layer of vitreous state, the characteristic of the former elementary fluor of not remarkably influenced of one side, the existence of this embracing layer on the other hand, if make when luminescent material is heated once again, the embracing layer of vitreous state may form molten state in being subjected to thermal process, thereby can stop airborne oxygen to be diffused into primary fluor's body, suppress the further oxidation of activator, thereby kept the luminescent properties of luminescent material, thereby can greatly improve its high thermal resistance.
Simultaneously, owing to around the particle of fluor, there is more complete embracing layer, stopped the decomposition for primary fluor's body such as the aqueous vapor of long after glow luminous material in environment for use, thereby improved water tolerance.Therefore, can greatly improve its high thermal resistance and water tolerance according to preferred long after glow luminous material of the present invention.
Above-mentioned boron-containing compound is meant the mineral compound that can resolve into boron oxide in the temperature-rise period that burns till, for example inorganic borate, boric acid, boron oxide or their mixture etc., and inorganic borate is such as borax (Na
2B
4O
710H
2O, sodium tetraborate).This boron-containing compound is preferably borax or boron oxide, and more preferably if borax owing to using borax, can obtain the excellent especially long after glow luminous material of high warm nature and water tolerance.
In the method, for primary fluor's body and boron-containing compound are mixed, and primary fluor's body can be surrounded preferably at the embracing layer that is formed by boron-containing compound, preferably need pulverize this primary fluor's body, the size of the primary fluor's body powder that obtains is below 50 orders, more preferably below 100 orders, excessive as fruit granule, in the burning till of back, be difficult to obtain the fluor of even structure, too small as fruit granule, the tendency that increases cost is arranged during pulverizing.Be not particularly limited for the mode of pulverizing, can adopt general breaking method.
The primary fluor's body powder that obtains and the powder of boron-containing compound are carried out uniform mixing.There is no particular limitation for the blended mode.
The usage quantity of above-mentioned boron-containing compound, with respect to 100 weight part primary fluor bodies, the addition that this boron-containing compound is converted into boron oxide is 20～50 weight parts, is preferably 20～45 weight parts, more preferably 25～40 weight parts.Boron-containing compound uses in this scope, can form embracing layer preferably after burning till with primary fluor body powder, thereby improve high thermal resistance and water tolerance that the present invention raises the photosensitiveness fluor.If too much, then the thickness of the embracing layer of Xing Chenging is excessive, and the fragility increase of long after glow luminous material in the pulverizing of the processing of long after glow luminous material and use, is easy to make this embracing layer and primary fluor's body particle separation, thereby loses the effect of protection.If very few, then be difficult to form the complete embracing layer that wraps up primary fluor's body.
Above-mentioned boron-containing compound preferably passes through milled processed with before the primary fluor body mixes, such as, preferably be ground to below 50 orders, more preferably be ground to below 100 orders.Do not accept the qualification of opinion, through milled processed, it is more even that this boron-containing compound is mixed with the primary fluor body, makes embracing layer can intactly wrap up primary fluor's body, and the high thermal resistance and the water tolerance of the long after glow luminous material that obtains are better.
With primary fluor's body powder mixes evenly after, this mixed powder was burnt till 2～8 hours at 800～1100 ℃, treat the furnace temperature cooling after, obtain long after glow luminous material of the present invention.This firing temperature is preferably 900～1050 ℃, and firing time is preferably 3～7 hours, more preferably 4～6 hours.The atmosphere of preferably burning till is preferably reducing atmosphere, and more preferably this reducing atmosphere is CO or N
2+ H
2For different boron-containing compounds, firing temperature can suitably be adjusted, and when for example using preferred borax, preferably burns till in 3～7 hours down at 900～1050 ℃.
Preferred embodiment prepare employed primary fluor body in the high thermal resistance long after glow luminous material of the present invention according to one of the present invention, preferably the raw material powder that contains Sr, Al, O, B, Eu, Dy burnt till, obtain with Sr (Al, B)
2O
4: Eu, Dy and/or Sr
4(Al, B)
14O
25: primary fluor's body that Eu, Dy represent.
Can be about 1: 1.3～1: 4 by the atomic ratio of the Al/Sr of control in the raw material, thus the luminescent material that forms contain be expressed as Sr (Al, B)
2O
4: Eu, Dy and/or Sr
4(Al, B)
14O
25: Eu, the compound of Dy, its with Sr (Al, B)
2O
4And/or Sr
4(Al, B)
14O
25Be parent, with Eu
2+, Dy
3+As activator, after being excited, Sr (Al, B)
2O
4: Eu, Dy send the green glow that predominant wavelength is 520nm, and Sr4 (Al, B)
14O
25: Eu, Dy send the blue light that predominant wavelength is 480nm.Such primary fluor's body has and reaches tens hours visual twilight sunset.
Also can further contain elements such as Ca, Ba in the above-mentioned raw materials.
In the raw material of primary fluor of the present invention body, the addition of B be mol ratio B/Sr with Sr than 0.02～0.12, preferred 0.03～0.10.The raw material that contains B in raw material powder is generally selected in boric acid, borax or the boron oxide one or more.In the prior art, add small amount of boron in the raw material powder and it is generally acknowledged two effects of playing, the effect of first fusing assistant can reduce the temperature when burning till; Its two, the adding of boron can enter crystalline network, improves original intensity, prolongs time of persistence.Can select SrCO as the raw material that contains Sr
3, Sr (NO
3)
2, Sr (OH)
2In at least a, these raw materials can decompose in the temperature-rise period that burns till, formation SrO.
In the raw material of primary fluor's body, can select at least a in its oxysalt as the raw material that contains Al, these raw materials can decompose in the temperature-rise period that burns till, and form Al
2O
3Also can directly use aluminum oxide, preferably use aluminum oxide for containing the Al raw material.
With Sr (Al, B)
2O
4: in primary fluor's body that Eu, Dy represent, Eu adds as activator (promoting agent), and in raw material powder, the addition of Eu is that the mol ratio of Eu/Sr is 0.001～0.20, and preferred 0.05～0.15.Generally the form with oxide compound joins in the raw material powder.
With Sr (Al, B)
2O
4: in primary fluor's body that Eu, Dy represent, Dy adds as activator (promoting agent), and in raw material powder, the addition of Dy is that the mol ratio of Dy/Sr is 0.001～0.20, and preferred 0.05～0.15.Generally the form with oxide compound joins in the raw material powder.
Preferred primary fluor body is to contain the powder of the raw material of Sr, Al, B, Eu, Dy, to mix according to the ratio of desirable Al, Sr, B, Eu, Dy, to burn till under 1100～1500 ℃ temperature then, to prepare primary fluor's body.In sintering process, can in burning till, all adopt reducing atmosphere, but preferably adopt oxidizing atmosphere (for example air) in the early stage of burning till, in the later stage of burning till atmosphere is replaced by reducing atmosphere, for example CO or H
2+ N
2, the more preferably latter.The firing time of accumulative total is 3～8 hours.Then, be cooled to room temperature.
The primary fluor's body that obtains is pulverized, obtained the following particle of 50 orders, be preferably 100 orders～200 orders.Excessive as fruit granule, be difficult to obtain the fluor of even structure in the burning till afterwards, too small as fruit granule, the tendency that increases cost is arranged during pulverizing.Be not particularly limited for the mode of pulverizing, can adopt general breaking method.
Pass through the further processing to primary fluor's body as described in the present invention, the long after glow luminous material of the present invention that obtains is compared high thermal resistance with former elementary fluor and is further improved.
Below in conjunction with specific embodiment long after glow luminous material of the present invention and preparation method thereof is further specified, but this specific embodiment does not play the qualification effect to the present invention.
Embodiment 1
(1) preparation of primary fluor's body:
According to the mol ratio of the element shown in the table 1, prepare the raw material powder that contains Sr, Al, O, B, Eu, Dy of respective amount, wherein, the mol ratio of Al/Sr is 1.3.Each raw material thorough mixing is even, burns till under 1300 ℃ 4 hours, adopts air atmosphere at preceding 2 hours that burn till, and at back 2 hours that burn till atmosphere is replaced by H
2+ N
2Reducing atmosphere obtains primary fluor's body.
(2) preparation of long after glow luminous material:
It is below 50 orders that top (1) step resulting primary fluor body is ground, add borax powder, the addition of borax powder is the primary fluor's body with respect to 100 weight parts, borax is 30 weight parts after being converted into boron oxide, they are carried out thorough mixing, mixture was carried out burning till the second time under 1000 ℃ 3 hours, and the atmosphere in the sintering process is H
2+ N
2Reducing atmosphere then, is cooled to room temperature and obtains long after glow luminous material.
Resulting long after glow luminous material is carried out fluorescence, twilight sunset, glow color, high thermal resistance, water tolerance detect, obtain that the results are shown in Table 2.
Embodiment 2
(1) preparation of primary fluor's body:
Prepare primary fluor's body according to embodiment 1 described method.
(2) preparation of long after glow luminous material:
It is below 50 orders that top (1) step resulting primary fluor body is ground, add borax powder, the addition of borax powder is the primary fluor's body with respect to 100 weight parts, borax is 50 weight parts after being converted into boron oxide, carry out thorough mixing, mixture was carried out burning till the second time under 1000 ℃ 3 hours, and the atmosphere in the sintering process is H
2+ N
2Reducing atmosphere then, is cooled to room temperature and obtains long after glow luminous material.
Embodiment 3
(1) preparation of primary fluor's body:
Prepare primary fluor's body according to embodiment 1 described method.
(2) preparation of long after glow luminous material:
It is below 50 orders that top (1) step resulting primary fluor body is ground, add boric acid powder, the addition of boric acid powder is the primary fluor's body with respect to 100 weight parts, boric acid is 30 weight parts after being converted into boron oxide, carry out thorough mixing, mixture was carried out burning till the second time under 900 ℃ 3 hours, and the atmosphere in the sintering process is H
2+ N
2Reducing atmosphere then, is cooled to room temperature and obtains long after glow luminous material.
Embodiment 4
(1) preparation of primary fluor's body:
Prepare primary fluor's body according to embodiment 1 described method.
(2) preparation of long after glow luminous material:
It is below 50 orders that top (1) step resulting primary fluor body is ground, add boric acid powder, the addition of boric acid powder is the primary fluor's body with respect to 100 weight parts, boric acid is 50 weight parts after being converted into boron oxide, carry out thorough mixing, mixture was carried out burning till the second time under 900 ℃ 3 hours, and the atmosphere in the sintering process is H
2+ N
2Reducing atmosphere then, is cooled to room temperature and obtains long after glow luminous material.
Embodiment 5
(1) preparation of primary fluor's body:
Prepare primary fluor's body according to embodiment 1 described method.
(2) preparation of long after glow luminous material:
It is below 50 orders that top (1) step resulting primary fluor body is ground, add the boron oxide powder, the addition of boron oxide powder is the primary fluor's body with respect to 100 weight parts, boron oxide is 30 weight parts, carry out thorough mixing, mixture was carried out burning till the second time under 1000 ℃ 3 hours, and the atmosphere in the sintering process is H
2+ N
2Reducing atmosphere then, is cooled to room temperature and obtains long after glow luminous material.
Embodiment 6
(1) preparation of primary fluor's body:
Prepare primary fluor's body according to embodiment 1 described method.
(2) preparation of long after glow luminous material:
It is below 50 orders that top (1) step resulting primary fluor body is ground, add the boron oxide powder, the addition of boron oxide powder is the primary fluor's body with respect to 100 weight parts, boron oxide is 50 weight parts, carry out thorough mixing, mixture was carried out burning till the second time under 1000 ℃ 3 hours, and the atmosphere in the sintering process is H
2+ N
2Reducing atmosphere then, is cooled to room temperature and obtains long after glow luminous material.
Embodiment 7
(1) preparation of primary fluor's body:
According to the mol ratio of the element shown in the table 1, prepare the raw material powder that contains Sr, Al, O, B, Eu, Dy of respective amount, wherein, the mol ratio of Al/Sr is 2.0.And each raw material thorough mixing is even, burns till under 1300 ℃ 3 hours, adopts air atmosphere at preceding 1 hour that burns till, and at back 2 hours that burn till atmosphere is replaced by H
2+ N
2Reducing atmosphere obtains primary fluor's body.
(2) preparation of long after glow luminous material:
It is below 50 orders that top (1) step resulting primary fluor body is ground, add borax powder, the addition of borax powder is the primary fluor's body with respect to 100 weight parts, borax is 40 weight parts after being converted into boron oxide, they are carried out thorough mixing, mixture was burnt till under 1000 ℃ 3 hours, and the atmosphere in the sintering process is H
2+ N
2Reducing atmosphere then, is cooled to room temperature and obtains long after glow luminous material.
Resulting long after glow luminous material is carried out fluorescence, twilight sunset, glow color, high thermal resistance, water tolerance detect, obtain that the results are shown in Table 2.
Embodiment 8
(1) preparation of primary fluor's body:
According to the mol ratio of the element shown in the table 1, prepare the raw material powder that contains Sr, Al, O, B, Eu, Dy of respective amount, wherein, the mol ratio of Al/Sr is 2.0.And each raw material thorough mixing is even, burns till under 1300 ℃ 4 hours, adopts air atmosphere at preceding 2 hours that burn till, and at back 2 hours that burn till atmosphere is replaced by H
2+ N
2Reducing atmosphere obtains primary fluor's body.
(2) preparation of long after glow luminous material:
It is below 50 orders that top (1) step resulting primary fluor body is ground, add borax powder, the addition of borax powder is the primary fluor's body with respect to 100 weight parts, borax is 30 weight parts after being converted into boron oxide, they are carried out thorough mixing, mixture was burnt till under 1050 ℃ 3 hours, and the atmosphere in the sintering process is H
2+ N
2Reducing atmosphere then, is cooled to room temperature and obtains long after glow luminous material.
Resulting long after glow luminous material is carried out fluorescence, twilight sunset, glow color, high thermal resistance, water tolerance detect, obtain that the results are shown in Table 2.
Embodiment 9
(1) preparation of primary fluor's body:
According to the mol ratio of the element shown in the table 1, prepare the raw material powder that contains Sr, Al, O, B, Eu, Dy of respective amount, wherein, the mol ratio of Al/Sr is 2.5.And each raw material thorough mixing is even, burns till under 1300 ℃ 3 hours, adopts air atmosphere at preceding 1 hour that burns till, and at back 2 hours that burn till atmosphere is replaced by H
2+ N
2Reducing atmosphere obtains primary fluor's body.
(2) preparation of long after glow luminous material:
It is below 100 orders that top (1) step resulting primary fluor body is ground, add borax powder, the addition of borax powder is the primary fluor's body with respect to 100 weight parts, borax is 20 weight parts after being converted into boron oxide, they are carried out thorough mixing, mixture was burnt till under 1050 ℃ 3 hours, and the atmosphere in the sintering process is H
2+ N
2Reducing atmosphere then, is cooled to room temperature and obtains long after glow luminous material.
Resulting long after glow luminous material is carried out fluorescence, twilight sunset, glow color, high thermal resistance, water tolerance detect, obtain that the results are shown in Table 2.
Embodiment 10
(1) preparation of primary fluor's body:
According to the mol ratio of the element shown in the table 1, prepare the raw material powder that contains Sr, Al, O, B, Eu, Dy of respective amount, wherein, the mol ratio of Al/Sr is 3.0.And each raw material thorough mixing is even, burns till under 1300 ℃ 3 hours, adopts air atmosphere at preceding 1 hour that burns till, and at back 2 hours that burn till atmosphere is replaced by H
2+ N
2Reducing atmosphere obtains primary fluor's body.
(2) preparation of long after glow luminous material:
It is below 100 orders that top (1) step resulting primary fluor body is ground, add borax powder, the addition of borax powder is the primary fluor's body with respect to 100 weight parts, borax is 40 weight parts after being converted into boron oxide, they are carried out thorough mixing, mixture was burnt till under 1000 ℃ 4 hours, and the atmosphere in the sintering process is H
2+ N
2Reducing atmosphere then, is cooled to room temperature and obtains long after glow luminous material.
Resulting long after glow luminous material is carried out fluorescence, twilight sunset, glow color, high thermal resistance, water tolerance detect, obtain that the results are shown in Table 2.
Embodiment 11
(1) preparation of primary fluor's body:
According to the mol ratio of the element shown in the table 1, prepare the raw material powder that contains Sr, Al, O, B, Eu, Dy of respective amount, wherein, the mol ratio of Al/Sr is 3.5.And each raw material thorough mixing is even, burns till under 1300 ℃ 3 hours, adopts air atmosphere at preceding 1 hour that burns till, and at back 2 hours that burn till atmosphere is replaced by H
2+ N
2Reducing atmosphere obtains primary fluor's body.
(2) preparation of long after glow luminous material:
It is below 100 orders that top (1) step resulting primary fluor body is ground, add borax powder, the addition of borax powder is the primary fluor's body with respect to 100 weight parts, borax is 30 weight parts after being converted into boron oxide, they are carried out thorough mixing, mixture was burnt till under 1000 ℃ 4 hours, adopted air atmosphere, atmosphere is replaced by H at back 2 hours that burn till at preceding 2 hours that burn till
2+ N
2Reducing atmosphere then, is cooled to room temperature and obtains long after glow luminous material.
Resulting long after glow luminous material is carried out fluorescence, twilight sunset, glow color, high thermal resistance, water tolerance detect, obtain that the results are shown in Table 2.
Embodiment 12
(1) preparation of primary fluor's body:
According to the mol ratio of the element shown in the table 1, prepare the raw material powder that contains Sr, Al, O, B, Eu, Dy of respective amount, wherein, the mol ratio of Al/Sr is 4.0.And each raw material thorough mixing is even, burns till under 1300 ℃ 3 hours, adopts air atmosphere at preceding 1 hour that burns till, and at back 2 hours that burn till atmosphere is replaced by H
2+ N
2Reducing atmosphere obtains primary fluor's body.
(2) preparation of long after glow luminous material:
It is below 100 orders that top (1) step resulting primary fluor body is ground, add borax powder, the addition of borax powder is the primary fluor's body with respect to 100 weight parts, borax is 30 weight parts after being converted into boron oxide, they are carried out thorough mixing, mixture was burnt till under 1000 ℃ 4 hours, and the atmosphere in the sintering process is H
2+ N
2Reducing atmosphere then, is cooled to room temperature and obtains long after glow luminous material.
Resulting long after glow luminous material is carried out fluorescence, twilight sunset, glow color, high thermal resistance, water tolerance detect, obtain that the results are shown in Table 2.
Comparative example 1
According to the mol ratio of the element shown in the table 1, prepare the raw material powder that contains Sr, Al, O, B, Eu, Dy of respective amount, wherein, the mol ratio of Al/Sr is 2.0.And each raw material thorough mixing is even, burns till under 1300 ℃ 3 hours, adopts air atmosphere at preceding 1 hour that burns till, and at back 2 hours that burn till atmosphere is replaced by H
2+ N
2Reducing atmosphere obtains long after glow luminous material.
Resulting long after glow luminous material is carried out fluorescence, twilight sunset, glow color, high thermal resistance, water tolerance detect, obtain that the results are shown in Table 2.
Comparative example 2
According to the mol ratio of the element shown in the table 1, prepare the raw material powder that contains Sr, Al, O, Eu, Dy of respective amount, wherein, the mol ratio of Al/Sr is 2.0.And each raw material thorough mixing is even, burns till under 1500 ℃ 3 hours, adopts air atmosphere at preceding 1 hour that burns till, and at back 2 hours that burn till atmosphere is replaced by H
2+ N
2Reducing atmosphere obtains long after glow luminous material.
Resulting long after glow luminous material is carried out fluorescence, twilight sunset, glow color, high thermal resistance, water tolerance detect, obtain that the results are shown in Table 2.
Each embodiment and comparative example method for testing performance and result
(1) electron probe microanalysis (Electron probe microanalysis:EPMA)
After the long after glow luminous material that the foregoing description 7 is obtained carries out milled processed, utilize the EPMA-1600 of Shimadzu Seisakusho Ltd.'s system that morphology analysis and composition scanner uni mensuration that this long after glow luminous material carries out EPMA are ground by the ceramic grinding machine each phosphor particle that obtains, lapped face to test sprays the carbon processing, use EPMA-1600 (Shimadzu Seisakusho Ltd.'s preparation) that the section of each fluor is observed then, and analyze the distribution and the relative proportion of each element.Wherein, acceleration voltage is 15kV.
Obtain the photo shown in Fig. 1,2,3.
Fig. 1 is the particulate photo of primary fluor's body of embodiment 7.
As shown in Figure 1, primary fluor's body is particulate state after pulverizing, be subjected to the influence of crushing process, the particulate size and the shape that form are inconsistent, composition analysis to particulate center (for example a place among Fig. 1) shows, the atomic ratio of Sr, Al, O is about 1: 2: 4, the structure that shows its parent be Sr (Al, B)
2O
4, and contain a spot of Eu and Dy, and some particulate color is omited dark (for example b place among Fig. 1) in photo in addition, and the result of composition analysis shows that the atomic ratio of Sr, Al, O is in close proximity to Sr
4Al
14O
25Ratio, the structure that its parent is described is Sr
4(Al, B)
14O
25: Eu, Dy contains a spot of Eu and micro-Dy.
Fig. 2 is the long after glow luminous material grain pattern photo that embodiment 7 obtains, wherein the ratio of the Al/Sr in primary fluor's body is 2.0, the amount of burning till the borax that adds in the step in (2) step is the primary fluor's body with respect to 100 weight parts, and borax is 40 weight parts after being converted into boron oxide.Fig. 2 has reflected the macroscopic particles structure of the high thermal resistance long-afterglow material that obtains, and Fig. 3 is a part particulate enlarged view among Fig. 2.
As can be seen from Figure 2, after primary fluor's body particle being mixed with borax and burns till once again, obtain the phosphor particle of cluster shape, the particulate size of each cluster is more even.Independent cluster shape particle after amplifying is further observed, as shown in Figure 3, as can be seen, at cluster shape particle center for arrange closely, particle shape and the more regular particle of size, particle (position A among the figure) is carried out composition analysis revealed Sr, Al, O than for being 1: 2: 4 substantially, and contain a spot of Eu and Dy, this shows, these particles be Sr (Al, B)
2O
4: Eu, Dy.This illustrates that these particles are that the particle of primary fluor's body forms through burning till the back, mixed basic structure and the composition that does not change primary fluor's body that burn till once again of the particle of primary fluor's body and boron-containing compound just makes the particulate size and dimension improve in burning till.
Primary fluor body particle through with the cluster shape particle of the fluor that is fired into once again of borax, be in configuration aspects and primary fluor's the most significant difference of body particulate, the Sr of cluster shape (Al, B)
2O
4: form one deck embracing layer (position D among the figure) around the Eu, Dy particulate.As can be seen from Figure 3, and grayish Sr (Al, B)
2O
4: Eu, Dy particle (hereinafter will be called the A phase by the cluster particle that primary fluor's body forms) is wrapped up by the glass state material D of black (D phase hereinafter referred to as), D is present in around the cluster shape particulate mutually, closely wrap cluster shape particle, make the particle close proximity of A phase form the cluster shape on the one hand, be wrapped to form the A phase particle of cluster shape on the other hand from peripheral integral body.
For D from composition analysis as can be known, it mainly is made of B, O, wherein also contains the Dy of higher proportion simultaneously.Except with A mutually particle outside thin layer, also can form granular particle (D` among Fig. 3) closely the thin layer of contact and parcel A phase.Wherein, without being limited by theory, the contriver thinks that tight contact A mutually and wrap up the thin layer of A phase, it may be the structure of non-crystalline state, the existence that this D that is made up of thin layer and particulate state (comprises D`) mutually is important in very for long after glow luminous material of the present invention, can when significantly not reducing the persistence characteristic of primary fluor's body, significantly improve the water tolerance and the high thermal resistance of fluor.Without being limited by theory, the contriver thinks, owing to primary fluor's body being mixed with boron-containing compound and burning till once again, obtained the structure that D in the luminescent material of the present invention is wrapped in the A phase mutually, the existence of D phase has stopped the decomposition for the A phase such as the aqueous vapor in the fluor environment for use, thereby improves water tolerance.Simultaneously, if when luminescent material is heated once again, D phase (also may form molten state in being subjected to thermal process) can stop airborne oxygen to be diffused into the A phase, suppresses the further oxidation as the Eu of activator, thereby has kept the luminescent properties of luminescent material.
In addition, without being limited by theory, the contriver thinks, the part in the B atom in the boron-containing compound that is added in (2) step with primary fluor's body generation solid state reaction, further occupies the site of the Al atom in the precursor structure in burning till.Such solid state reaction is not destroyed parent crystalline structure, and the homogeneity that helps primary fluor body particulate to form, and helps to make uniform particlesization.
In addition, other each embodiment and Comparative Examples are also carried out similar EPMA analysis, and, identify each phase that forms carrying out XRD analysis.
(2) mensuration of persistence characteristicRespectively the fluor that obtains was placed in the darkroom 24 hours, after the twilight sunset cancellation, excited 10 minutes with the brightness of 200 luxs, measure its persistence characteristic by the aura determinator then with the light source of 360nm.
(3) mensuration of water resistanceEach the fluor 2g that obtains is put into the ion exchanged water (about 25 ℃ of water temperature) of 48g respectively, observes the variation of its solution, and measure solution the pH value.Each fluor is soaked 7 days in water after, each sample is put into the darkroom immediately and carried out visual inspection after 20 minutes in irradiation under the sunlight, the situation (initial luminescent properties) of record observed light this moment.Putting into the darkroom after 2 hours, its luminous situation that detects by an unaided eye once again (afterglow performance).
(3) mensuration of resistance to elevated temperaturesEach fluor that obtains is heated to 1000 ℃ in air, be incubated 30 fens in after, be cooled to room temperature.Each sample is put into the darkroom immediately and carried out visual inspection after 20 minutes in irradiation under the sunlight, the situation (initial luminescent properties) of record observed light this moment.Putting into the darkroom after 2 hours, its luminous situation that detects by an unaided eye once again (afterglow performance).
Judging criterion
◎ is visual, and is bright
Zero is visual, dark
△ mays be seen indistinctly
* no visible light
The result of the various mensuration of embodiment 1～12 and comparative example 1～2 is as shown in table 2.
Comparative example 1 is that the Al/Sr ratio is 2.0 o'clock, in preparation primary fluor body process, added the primary fluor body of boracic raw material as fusing assistant, comparative example 2 is the primary fluor's bodies that do not add the boracic raw material in preparation primary fluor body process, and comparative example 1 and 2 is a typical steady persistence long after glow luminous material in the prior art.The particulate composition analysis of primary fluor's body of the comparative example 1,2 that is undertaken by EPMA shows, the mol ratio of Sr, Al, O is essentially 1: 2: 4 in the particle, and containing a small amount of Eu and Dy, EPMA observes the particle of these fluor, is grain pattern as shown in Figure 1 basically.Simultaneously the analytical results of XRD also shows, formed Sr (Al, B)
2O
4The crystal of structure, this show obtained Sr (Al, B)
2O
4: Eu, primary fluor's body of Dy has very faint Sr simultaneously
4Al
14O
25The peak, show to have formed a spot of Sr
4(Al, B)
14O
25: Eu, Dy crystal.Because the Sr that forms
4(Al, B)
14O
25: Eu, Dy measures seldom, and the light that primary fluor's body the sent range estimation of formation is for green.
With the mol ratio of Al/Sr is that the raw material powder of 1.3～2.0 (embodiment 1～8) carries out burning till of (1) step, obtain primary fluor's body of embodiment 1～8, after these primary fluor's bodies are added boron-containing compound in the ratio shown in the table 1, burn till once again, obtain the fluor of embodiment 1～8.The particulate composition and the structure of the fluor of the embodiment 1～8 that is undertaken by EPMA are analyzed, the result shows, when the Al/Sr ratio is 1.3～2.0, the grain pattern of the final fluor that forms and Fig. 2, grain pattern shown in Figure 3 are basic identical, all show the structure of being wrapped up uniform A phase by the D of amorphous mutually.The mol ratio of Sr, Al, O is essentially 1: 2: 4 in the particle, and contains a small amount of Eu and Dy, and the composition analysis of A phase shows and is mainly SrAl
2O
4The analytical results of XRD also shows simultaneously, has formed SrAl
2O
4The crystal of structure.At Al/Sr is 2.0 o'clock, and the XRD spectrum can have very faint Sr in the peak
4Al
14O
25The peak, show to have formed a spot of Sr
4Al
14O
25Crystal.Because the Sr that forms in the fluor of embodiment 1～8
4Al
14O
25Measure seldom, the light range estimation that primary fluor's body of formation and final fluor are sent is for green.
With the mol ratio of Al/Sr is that the raw material powder of 2.5～4.0 (embodiment 9～12) carries out burning till of (2) step, obtain primary fluor's body of embodiment 9～12, after these primary fluor's bodies are added boron-containing compound in the ratio shown in the table 1, burn till once again, obtain the fluor of embodiment 9～12.The particulate composition and the structure of the fluor of the embodiment 9～12 that is undertaken by EPMA are analyzed, the result shows, when the Al/Sr ratio is 2.5～4.0, the grain pattern of the final fluor that forms also very approaches Fig. 2, grain pattern shown in Figure 3, all shows the structure of being wrapped up uniform A phase by the D of amorphous mutually.From particle, can conclude on the mol ratio of Sr, Al, O, along with the increase of Al/Sr mol ratio, Sr (Al, B)
2O
4The particulate amount reduce Sr gradually
4(Al, B)
14O
25Amount increase gradually, when Al/Sr is 4.0, form whole Sr basically
4(Al, B)
14O
25Along with Sr
4(Al, B)
14O
25The increase of amount, the glow color of the primary fluor's body of embodiment 9～12 and final fluor also changes to some extent, from being mainly to change green into and add blueness with the green, final be blueness substantially.Simultaneously the analytical results of XRD also shows, along with the increase of the mol ratio of Al/Sr, Sr
4(Al, B)
14O
25: Eu, the spectrum peak of Dy strengthens gradually, Sr (Al, B)
2O
4The spectrum peak weaken gradually.
Luminous and the afterglow property of the final fluor of embodiment 1～12 is compared (being 100 o'clock comparative figure with the initial luminosity of comparative example 1) with comparative example 1, though initial luminous brightness and persistence characteristic has to a certain degree the decline of (about 10%), but still show luminous preferably and persistence characteristic, suitable substantially with the luminous and afterglow property of comparative example 1,2.
The luminescent material with comparative example and embodiment in air, be heated to 1000 ℃ and be incubated 30 minutes after, the luminescent material of comparative example has been lost the characteristics of luminescence and persistence characteristic substantially, and the luminescent material of embodiment 1～12 has still kept luminous preferably and fluorescent characteristic, and this is considered to the activator Eu in the fluorescent material of comparative example
2+Further be oxidized to Eu at high temperature
3+Thereby, destroyed the center of giving out light of fluor, lost luminous power, and the fluorescent material of embodiment pines for adding, the twinkler particle is subjected to the parcel of D phase, thereby has stoped the further oxidation of Eu, has kept luminescence center.
In addition, after the luminescent material of comparative example 1,2 soaked in through 7 days water, it had lost luminous and persistence characteristic substantially, occurred the outstanding turbid state of white in the solution after the immersion, and the pH value of solution also sharply rises, and is roughly about 13.Serious hydrolysis takes place in the luminescent material that shows comparative example in water, completely destroy the structure of parent.
Compare with comparative example 1,2, the luminescent material of embodiment 1～12 all shows good luminescent characteristic and persistence characteristic.The contriver thinks, is wrapped in luminescent material (A phase) amorphous phase material D on every side and has protected phosphor matrix to avoid the hydrolysis of moisture content effectively, thereby kept luminous preferably and fluorescent characteristic.Though soaked the white suspension liquid that also has in the water of embodiment 1～12 to a certain degree, it is many that its amount will be lacked, pH value of aqueous solution is roughly 11～11.5, shows that the hydrolysis rate of luminescent material is compared remarkable reduction with comparative example.
Claims (27)
1. high thermal resistance long after glow luminous material is characterized in that it prepares by the following method:
Primary fluor's body that will have long afterglow property mixes mutually with boron-containing compound, and the mixture that obtains is burnt till at 800～1100 ℃.
2. high thermal resistance long after glow luminous material as claimed in claim 1 is characterized in that, described boron-containing compound is the mineral compound that can generate boron oxide in the temperature-rise period that burns till.
3. high thermal resistance long after glow luminous material as claimed in claim 1 or 2 is characterized in that,
That selects in the group that described boron-containing compound is made up of following material is at least a: inorganic borate, boric acid, boron oxide and their mixture.
4. high thermal resistance long after glow luminous material as claimed in claim 3 is characterized in that described inorganic borate is a borax.
5. as each described high thermal resistance long after glow luminous material of claim 1 to 4, it is characterized in that the particulate structure of the luminescent material of formation is that the particle of primary fluor's body or cluster shape particle are at room temperature wrapped up by the material of vitreous state (D phase).
6. as each described high thermal resistance long after glow luminous material of claim 1 to 5, it is characterized in that, before mixing, described primary fluor body is crushed to below 50 orders, boron-containing compound also is crushed to below 50 orders.
7. as each described high thermal resistance long after glow luminous material of claim 1 to 6, it is characterized in that firing time is 2～8 hours.
8. as each described high thermal resistance long after glow luminous material of claim 1 to 7, it is characterized in that firing temperature is 900～1050 ℃, firing time is 3～7 hours.
9. as each described high thermal resistance long after glow luminous material of claim 1 to 8, it is characterized in that described primary fluor body is the aluminate series long afterglow luminescent material.
10. high thermal resistance long after glow luminous material as claimed in claim 9 is characterized in that,
This aluminate series long afterglow luminescent material is an alkaline-earth metal class aluminate-series long after glow luminous material.
11. high thermal resistance long after glow luminous material as claimed in claim 9 is characterized in that,
This aluminate series long afterglow luminescent material is a strontium aluminate series long afterglow luminescent material.
12., it is characterized in that described primary fluor body is by the preparation of the method that may further comprise the steps as each described high thermal resistance long after glow luminous material of claim 1 to 11, wherein, by burning till the raw material powder that contains Sr, Al, O, B, Eu, Dy, obtain containing with Sr (Al, B)
2O
4: Eu, Dy and/or Sr
4(Al, B)
14O
25: primary fluor's body of the compound that Eu, Dy represent, the temperature that this primary fluor's body burns till is 1100～1500 ℃, firing time is 3～8 hours, is reducing atmosphere burning till the later stage firing atmosphere at least.
13., it is characterized in that with respect to 100 weight part primary fluor bodies, the addition that this boron-containing compound is converted into boron oxide is 20～50 weight parts above-mentioned as each described high thermal resistance long after glow luminous material of claim 1 to 12.
14. the preparation method of a high thermal resistance long after glow luminous material, it comprises at least:
Primary fluor's body that will have long afterglow property mixes mutually with boron-containing compound, and the mixed powder that obtains is burnt till at 800～1100 ℃.
15. preparation method as claimed in claim 14 is characterized in that, described boron-containing compound is the mineral compound that can generate boron oxide in the temperature-rise period that burns till.
16. as claim 14 or 15 described preparation methods, it is characterized in that,
That selects in the group that described boron-containing compound is made up of following material is at least a: inorganic borate, boric acid, boron oxide or their mixture.
17. preparation method as claimed in claim 16 is characterized in that, described inorganic borate is a borax.
18., it is characterized in that the particulate structure of the luminescent material of formation is that the particle of primary fluor's body or cluster shape particle are at room temperature wrapped up by the material of vitreous state (D phase) as each described preparation method of claim 14 to 17.
19., it is characterized in that as each described preparation method of claim 14 to 18, before mixing, described primary fluor body is crushed to below 50 orders, boron-containing compound also is crushed to below 50 orders.
20., it is characterized in that firing time is 2～8 hours as each described preparation method of claim 14 to 19.
21., it is characterized in that firing temperature is 900～1050 ℃ as each described preparation method of claim 14 to 20, firing time is 3～7 hours.
22. as each described preparation method of claim 14 to 21, it is characterized in that,
Described primary fluor body is the aluminate series long afterglow luminescent material.
23. preparation method as claimed in claim 22 is characterized in that,
This aluminate series long afterglow luminescent material is an alkaline-earth metal class aluminate-series long after glow luminous material.
24. preparation method as claimed in claim 23 is characterized in that,
This aluminate series long afterglow luminescent material is a strontium aluminate series long afterglow luminescent material.
25. as each described preparation method of claim 14 to 24, it is characterized in that,
Described primary fluor body is by the preparation of the method that may further comprise the steps, wherein, by burning till the raw material powder that contains Sr, Al, O, B, Eu, Dy, obtain containing with Sr (Al, B)
2O
4: Eu, Dy and/or Sr
4(Al, B)
14O
25: primary fluor's body of the compound that Eu, Dy represent, the firing temperature of primary fluor's body are 1100～1500 ℃, and firing time is 3～8 hours, are reducing atmosphere burning till the later stage firing atmosphere at least.
26., it is characterized in that with respect to 100 weight part primary fluor bodies, the addition that this boron-containing compound is converted into boron oxide is 20～50 weight parts above-mentioned as each described preparation method of claim 14 to 25.
27., it is characterized in that described firing atmosphere is N as each described preparation method of claim 14 to 26
2+ H
2
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102250612A (en) * | 2011-05-24 | 2011-11-23 | 暨南大学 | Surface finishing method for aluminate long afterglow luminescent material |
| CN104300077A (en) * | 2010-11-09 | 2015-01-21 | 四川新力光源股份有限公司 | Light-emitting material with light-decay characteristic |
| WO2020199413A1 (en) * | 2019-04-04 | 2020-10-08 | 中建材创新科技研究院有限公司 | Mineral wool board and preparation method thereof |
| CN115895650A (en) * | 2022-12-30 | 2023-04-04 | 山东理工大学 | Water-resistant high-temperature-resistant long-afterglow rare earth luminescent material and preparation method thereof |
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2008
- 2008-12-26 CN CN200810241177A patent/CN101768434A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104300077A (en) * | 2010-11-09 | 2015-01-21 | 四川新力光源股份有限公司 | Light-emitting material with light-decay characteristic |
| CN104300077B (en) * | 2010-11-09 | 2017-12-01 | 四川新力光源股份有限公司 | A kind of luminescent material with light-decay characteristic |
| CN102250612A (en) * | 2011-05-24 | 2011-11-23 | 暨南大学 | Surface finishing method for aluminate long afterglow luminescent material |
| WO2020199413A1 (en) * | 2019-04-04 | 2020-10-08 | 中建材创新科技研究院有限公司 | Mineral wool board and preparation method thereof |
| CN115895650A (en) * | 2022-12-30 | 2023-04-04 | 山东理工大学 | Water-resistant high-temperature-resistant long-afterglow rare earth luminescent material and preparation method thereof |
| CN115895650B (en) * | 2022-12-30 | 2024-01-26 | 山东理工大学 | Waterproof high-temperature-resistant long-afterglow rare earth luminescent material and preparation method thereof |
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