CN105969350B - A kind of blue-green long persistence luminescent material and preparation method thereof - Google Patents
A kind of blue-green long persistence luminescent material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of blue-green long persistence luminescent material and preparation method thereof, its chemical expression is MnxZr1‑0.5xP2O7, wherein x=0.005 ~ 0.12, the raw material of the luminescent material is ZrOCl2·8H2O、(NH4)2HPO4And MnCO3、H3BO3, citric acid and Macrogol 4000.The centre of luminescence of obtained luminescent material is Zr4+And Mn2+, wherein blue-light-emitting part comes from Zr4+And green emitting comes from Mn2+, after the min of light-illuminating 15, light source is removed, material can be observed in the dark can persistently turn blue more than the h of green glow 10, and materials synthesis cost is low, chemical stability is high.
Description
Technical field
The invention belongs to field of light emitting materials, and in particular to a kind of blue-green long persistence luminescent material and preparation method thereof.
Background technology
Long-afterglow material is embedded photoluminescent material, can store ambient light irradiation energy, under the disturbance of temperature, slowly
Institute's storage energy is discharged in the form of visible ray, in road safety marker, the lighting installation of urgent accident, aviation and automobile
Instrument show, the various fields such as anti-counterfeiting technology, building decoration, industrial art coating have extensive purposes.It is long-persistence luminous
Material is mainly made up of matrix, activator (centre of luminescence) and auxiliary activator.Existing patented technology and document report are equal
Using rare earth ion or some transition metal ions as the centre of luminescence, such as Eu2+、Eu3+、Tb3+、Nd3+、Mn2+、Cu+Deng.Such as invent specially
Sharp " a kind of red long afterglow luminous material and preparation method thereof "（ZL200910112064.X）Disclose material (Zn1-α-βMnα
Lnβ)3（P1-0.8γSiγO4）2Technology of preparing；Patent of invention " a kind of overlength afterglow long persistence luminescent silicate material and its preparation
Method "（CN201010516567）Disclose material Ba3.992-xSi6O16:Eu0.008,RxTechnology of preparing；Patent of invention is " a kind of
The method of quickly synthesizing long-persistence luminescent material "（CN101899298A）Disclose material C a(0.8-2x) Zn0.2TiO3:xPr3+,
xNa+Technology of preparing；Patent of invention " a kind of manganese ion-activated red long-afterglow luminescent material and preparation method thereof "
（CN102719243A ）Disclose materials A lN:Mn2+Technology of preparing；Patent of invention " a kind of red long afterglow luminous material and
Its preparation method " (CN103160278A) discloses material ZnGa2O4：aCr3+,bDy3+, its luminescent center ion is respectively Eu2 +, Eu3+, Pr3+, Mn2+And Cr3+.In addition some documents（Referring to Mater. Chem. Phys. 99 (2006) 494, J.
Lumin. 156 (2014) 25 and (2011) H697 of J. Electrochem. Soc. 158）Also report with Ag+,
Cu+, Ce3+Transition metal ions is as centre of luminescence etc..Document J. Rare Earths 22 (1) (2004) 83 report β-
Zn3(PO4)2:Zr4+Blue-green long persistence luminescent material, Zr4+As the centre of luminescence.Existing technology is using expensive rare earth member
Element also tends to introduce some expensive rare earth elements as the centre of luminescence of luminescent material or in order to improve the luminescent properties of material
As sensitizer, such as patent of invention patent of invention（CN201010516567）Disclosed luminescent material Ba3.992-xSi6O16:
Eu0.008,RxAnd patent of invention（CN101899298A）Disclosed luminescent material Ca(0.8-2x) Zn0.2TiO3:xPr3+, xNa+,
Invention disclosed technology and the document reported use transition metal ions or Zr4+Twilight sunset as the luminescent material of the centre of luminescence
Performance is all bad, and document J. Rare Earths 22 (1) (2004) 83 report β-Zn3(PO4)2:Zr4+Blue-green long persistence
The persistence of luminescent material only has half an hour, and when making the long after glow luminous material twilight sunset of the centre of luminescence with transition metal ions
Between it is all very short, such as document（Zhangzhou Normal College's journal（Natural science edition）, 4（2006）P93）The Cu of report+As the centre of luminescence
Sr2ZnSi2O7：Cu+Persistence only has 2 hours.Therefore, preparing one kind has persistence length, stable performance, need not mix
The miscellaneous other expensive rare earth elements and luminescent material that the cost of material is low is significantly.
The content of the invention
It is an object of the invention in view of the shortcomings of the prior art, providing a kind of blue-green long persistence luminescent material and its preparation
Method.The centre of luminescence of obtained luminescent material is Zr4+And Mn2+, wherein blue-light-emitting part comes from Zr4+And green hair
Light comes from Mn2+, after the min of light-illuminating 15, light source is removed, material can be observed in the dark can persistently turn blue green glow 10
More than h, and materials synthesis cost is low, chemical stability is high.
To achieve the above object, the present invention adopts the following technical scheme that：
A kind of blue-green long persistence luminescent material, with Zr4+And Mn2+The centre of luminescence, its chemical expression are MnxZr1- 0.5xP2O7, wherein x=0.005 ~ 0.12.
A kind of preparation method of blue-green long persistence luminescent material as described above, specifically includes following steps：
（1）Stoichiometrically accurately weigh raw material ZrOCl respectively first2·8H2O、(NH4)2HPO4And MnCO3；
（2）Then H is weighed3BO3And citric acid；
（3）ZrOCl2·8H2O、(NH4)2HPO4、H3BO3With citric acid plus water be configured to mass percent concentration for 15 ~
30wt% mixture solution A；In MnCO3Middle addition 3mol/L nitric acid is simultaneously completely dissolved it, then adds distilled water to be configured to matter
Measure the settled solution B that percent concentration is 15 ~ 30wt%；
（4）By step（3）The solution A and solution B prepared are well mixed, molten with 25wt% ammoniacal liquor or the regulation of 65wt% nitric acid
The pH value of liquid is to 2 ~ 5；Macrogol 4000 then is added in A and B mixed solution, is persistently stirred under 65 ~ 85 DEG C of water-bath
Mix untill gel is formed；
（5）By step（4）The gel of formation is put in an oven in 110 DEG C of dry 12 h, after dried gel abrasive
It is fitted into the crucible of jacketed, interior crucible setting-out product outer crucible is put activated carbon and covered, and is placed in Muffle furnace, 950 ~ 1100
The h of calcination 2 ~ 5, naturally cools to room temperature at DEG C, produces blue-green long persistence luminescent material.
Step（2）Middle H3BO3Mol ratio with luminescent material is 0.2 ~ 1.2:1, the mol ratio of citric acid and luminescent material is
0.8~3.5:1。
Step（4）Middle A and B mixed solution and the weight ratio of Macrogol 4000 are 1000:0.5~5.
The beneficial effects of the present invention are：
The centre of luminescence of luminescent material obtained by the present invention is Zr4+And Mn2+, wherein blue-light-emitting part comes from Zr4+
And green emitting comes from Mn2+, after the min of light-illuminating 15, light source is removed, material can be observed in the dark can continue to send out
More than the h of blue green light 10, and materials synthesis cost is low, chemically ten stabilization of material of main part.Mn2+For the centre of luminescence, material hair
The significant contributor of optical property, and Zr4+The centre of luminescence be can be used as but also as sensitized ions, had very to the luminescent properties of material
Good improvement result.
Brief description of the drawings
Fig. 1 is Mn made from embodiment 10.1Zr0.95P2O7XRD and its standard spectrogram PDF49-1079；
Fig. 2 is Mn made from embodiment 10.1Zr0.95P2O7Excitation and emission spectra figure；
Fig. 3 is Mn made from embodiment 10.1Zr0.95P2O7Thermoluminescence；
Fig. 4 is Mn0.1Zr0.95P2O7Decay of afterglow curve of the material under different synthesis temperatures.
Embodiment
Below in conjunction with specific embodiment, the present invention will be further described, but the present invention is not limited only to these embodiments.
Embodiment 1
A kind of blue-green long persistence luminescent material, its chemical expression are Mn0.1Zr0.95P2O7, preparation method includes following
Step：
（1）Stoichiometrically accurately weigh raw material ZrOCl respectively first2·8H2O、(NH4)2HPO4And MnCO3；
（2）Then H is weighed3BO3And citric acid, H3BO3Mol ratio with luminescent material is 0.6:1, citric acid and luminous material
The mol ratio of material is 2.5:1；
（3）ZrOCl2·8H2O、(NH4)2HPO4、H3BO3Being configured to mass percent concentration with citric acid plus water is
22wt% mixture solution A；In MnCO3Middle addition 3mol/L nitric acid is simultaneously completely dissolved it, then adds distilled water to be configured to matter
Measure the settled solution B that percent concentration is 22wt%；
（4）By step（3）The solution A and solution B prepared are well mixed, with the pH value of 65wt% nitre acid-conditioning solutions extremely
2；Macrogol 4000, the weight ratio of A and B mixed solution and Macrogol 4000 are then added in A and B mixed solution
For 1000:2.5, continued stirring until under 75 DEG C of water-bath untill forming gel；
（5）By step（4）The gel of formation is put in an oven in 110 DEG C of dry 12 h, after dried gel abrasive
It is fitted into the crucible of jacketed, interior crucible setting-out product outer crucible is put activated carbon and covered, and is placed in Muffle furnace, at 1000 DEG C
Lower calcination 4h, naturally cools to room temperature, produces blue-green long persistence luminescent material.
By obtained luminescent material after the min of light-illuminating 15, light source is removed, material can be observed in the dark to be held
More than supervention blue green light 10h.
Embodiment 2
A kind of blue-green long persistence luminescent material, its chemical expression are Mn0.005Zr0.9975P2O7, preparation method include with
Lower step：
（1）Stoichiometrically accurately weigh raw material ZrOCl respectively first2·8H2O、(NH4)2HPO4And MnCO3；
（2）Then H is weighed3BO3And citric acid, H3BO3Mol ratio with luminescent material is 0.2:1, citric acid and luminous material
The mol ratio of material is 0.8:1；
（3）ZrOCl2·8H2O、(NH4)2HPO4、H3BO3Being configured to mass percent concentration with citric acid plus water is
15wt% mixture solution A；In MnCO3Middle addition 3mol/L nitric acid is simultaneously completely dissolved it, then adds distilled water to be configured to matter
Measure the settled solution B that percent concentration is 15wt%；
（4）By step（3）The solution A and solution B prepared are well mixed, with the pH value of 65wt% nitre acid-conditioning solutions extremely
3；Macrogol 4000, the weight ratio of A and B mixed solution and Macrogol 4000 are then added in A and B mixed solution
For 1000:0.5, continued stirring until under 65 DEG C of water-bath untill forming gel；
（5）By step（4）The gel of formation is put in an oven in 110 DEG C of dry 12 h, after dried gel abrasive
It is fitted into the crucible of jacketed, interior crucible setting-out product outer crucible is put activated carbon and covered, and is placed in Muffle furnace, at 950 DEG C
The h of calcination 5, naturally cools to room temperature, produces blue-green long persistence luminescent material.
By obtained luminescent material after the min of light-illuminating 15, light source is removed, material can be observed in the dark to be held
More than supervention blue green light 8.5h.
Embodiment 3
A kind of blue-green long persistence luminescent material, its chemical expression are Mn0.12Zr0.94P2O7, preparation method includes following
Step：
（1）Stoichiometrically accurately weigh raw material ZrOCl respectively first2·8H2O、(NH4)2HPO4And MnCO3；
（2）Then H is weighed3BO3And citric acid, H3BO3Mol ratio with luminescent material is 1.2:1, citric acid and luminous material
The mol ratio of material is 3.5:1；
（3）ZrOCl2·8H2O、(NH4)2HPO4、H3BO3Being configured to mass percent concentration with citric acid plus water is
30wt% mixture solution A；In MnCO3Middle addition 3mol/L nitric acid is simultaneously completely dissolved it, then adds distilled water to be configured to matter
Measure the settled solution B that percent concentration is 30wt%；
（4）By step（3）The solution A and solution B prepared are well mixed, with the pH value of 65wt% nitre acid-conditioning solutions extremely
2；Macrogol 4000, the weight ratio of A and B mixed solution and Macrogol 4000 are then added in A and B mixed solution
For 1000:5, continued stirring until under 85 DEG C of water-bath untill forming gel；
（5）By step（4）The gel of formation is put in an oven in 110 DEG C of dry 12 h, after dried gel abrasive
It is fitted into the crucible of jacketed, interior crucible setting-out product outer crucible is put activated carbon and covered, and is placed in Muffle furnace, at 1100 DEG C
The lower h of calcination 3, naturally cools to room temperature, produces blue-green long persistence luminescent material.
By obtained luminescent material after the min of light-illuminating 15, light source is removed, material can be observed in the dark to be held
More than supervention blue green light 7h.
Mn synthesized by the present inventionxZr1-0.5xP2O7Long after glow luminous material, its X-ray diffraction data and PDF standard cards
In 49-1079 it is consistent（See Fig. 1）, emission peak is a very wide bands of a spectrum from 420 to 550, and main peak is located at 471nm（Fig. 2）, it is
Blue green light.The centre of luminescence of luminescent material is Zr4+And Mn2+, wherein blue-light-emitting part comes from Zr4+And green emitting comes from
In Mn2+.Oxygen defect can be produced in reducing atmosphere, from the thermoluminescence in Fig. 3, it can be clearly seen that have at 358K
Very strong heat releases peak, and this peak belongs to oxygen defect.
The foregoing is only presently preferred embodiments of the present invention, all equivalent changes done according to scope of the present invention patent with
Modification, it should all belong to the covering scope of the present invention.
Claims (4)
- A kind of 1. blue-green long persistence luminescent material, it is characterised in that：The centre of luminescence of the luminescent material is Zr4+And Mn2+, its Chemical expression is MnxZr1-0.5xP2O7, wherein x=0.005 ~ 0.12.
- A kind of 2. method for preparing blue-green long persistence luminescent material as claimed in claim 1, it is characterised in that：Specifically include Following steps：（1）Stoichiometrically accurately weigh raw material ZrOCl respectively first2·8H2O、(NH4)2HPO4And MnCO3；（2）Then H is weighed3BO3And citric acid；（3）ZrOCl2·8H2O、(NH4)2HPO4、H3BO3It is 15 ~ 30wt% to be configured to mass percent concentration with citric acid plus water Mixture solution A；In MnCO3Middle addition 3mol/L nitric acid is simultaneously completely dissolved it, then adds distilled water to be configured to quality hundred Divide the settled solution B that specific concentration is 15 ~ 30wt%；（4）By step（3）The solution A and solution B prepared are well mixed, with 25wt% ammoniacal liquor or 65wt% nitre acid-conditioning solutions PH value is to 2 ~ 5；Macrogol 4000 then is added in A and B mixed solution, is continued stirring until under 65 ~ 85 DEG C of water-bath Untill forming gel；（5）By step（4）The gel of formation is put in an oven in 110 DEG C of dry 12 h, will be loaded after dried gel abrasive In the interior crucible of the crucible of jacketed, outer crucible is put activated carbon and covered, and is placed in Muffle furnace, is burnt at 950 ~ 1100 DEG C 2 ~ 5 h are burnt, room temperature is naturally cooled to, produces blue-green long persistence luminescent material.
- 3. the preparation method of blue-green long persistence luminescent material according to claim 2, it is characterised in that：Step（2）In H3BO3Mol ratio with luminescent material is 0.2 ~ 1.2:1, the mol ratio of citric acid and luminescent material is 0.8 ~ 3.5:1.
- 4. the preparation method of blue-green long persistence luminescent material according to claim 2, it is characterised in that：Step（4）Middle A It is 1000 with B mixed solution and the weight ratio of Macrogol 4000:0.5~5.
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