CN106010533A - Energy-storage red luminescent stone and preparation method thereof - Google Patents

Energy-storage red luminescent stone and preparation method thereof Download PDF

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Publication number
CN106010533A
CN106010533A CN201610385540.5A CN201610385540A CN106010533A CN 106010533 A CN106010533 A CN 106010533A CN 201610385540 A CN201610385540 A CN 201610385540A CN 106010533 A CN106010533 A CN 106010533A
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stone
red light
accumulating type
long afterglow
type emitting
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CN201610385540.5A
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CN106010533B (en
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郑子山
林秋惠
陈国良
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Minnan Normal University
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Minnan Normal University
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • C09K11/7766—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
    • C09K11/7777—Phosphates

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Luminescent Compositions (AREA)

Abstract

The invention discloses an energy-storage red luminescent stone and a preparation method thereof. The energy-storage red luminescent stone is prepared by evenly mixing a red long afterglow luminescent material as the main material with Al2O3 or ZrO2 in the weight ratio of 80-99:1-20, molding, and then calcining at high temperature. The red long afterglow luminescent material has a chemical formula of (Zn1-alpha-beta-gamma-lambda Mn alpha Sm beta A gamma B lambda)3(PO4)2, wherein A represents Dy<3+> or Pr<3+>, B represents Na<+> or K<+>, and alpha, beta, gamma and lambda represent the molar coefficient of each various element. The luminescent stone has scientific prescription, uses environment-friendly materials rich in resources and low in price; and the preparation process is simple. After 15 minutes of ultraviolet lamp irradiation, the stone can be observed with bright red light in the dark, and visual afterglow time is up to 8 hours, and the stone does not contain radioactive substances, and has low cost, and crystal clear appearance better than the natural pearl after polishing.

Description

A kind of accumulating type emitting red light stone and preparation method thereof
Technical field
The invention belongs to field of material technology, be specifically related to a kind of accumulating type emitting red light stone and preparation method thereof.
Background technology
Legendary luminous pearl, also known as fluorescence stone or luminous stone, at night it can be seen that its self-luminescence, is a kind of gem naturally-produced in the Nature, the most precious.Some legendary luminous pearls are due to containing radiosiotope, it is not necessary to excite by any outside energy, and the activator contained by self is luminous with regard to energy oneself excitation.Owing to the most rare price of natural legendary luminous pearl is the highest, ordinary people cannot have at all, and the legendary luminous pearl of permanent shining contains harmful radiosiotope.Make luminous stone, imitated natural legendary luminous pearl with long persistence light storage material, many people can be fulfilled and have the dream of legendary luminous pearl, there is good commercial promise.
Patent of invention " a kind of energy-accumulating luminous stone and preparation method thereof " (CN101403475A) discloses prepares green of turning blue, yellow green, purple and sapphire luminous stone with long after glow luminous material and silicon dioxide.But this patent fails to provide the specific chemical composition of luminescent material used, it is that aluminosilicate may determine that it should be strontium aluminate or calcium aluminate long after glow luminous material from product disclosed in it.And the invention provides a kind of novel phosphoric acid zinc-base red long afterglow luminous material, and prepare a kind of novel accumulating type emitting red light stone with it.
Summary of the invention
It is an object of the invention to provide a kind of accumulating type emitting red light stone and preparation method thereof, its proportioning raw materials is scientific and reasonable, and processing technology is simple, and cost of manufacture is low, and without radioactive substance, the outward appearance of gained luminous stone, quality can exceed natural legendary luminous pearl.
For achieving the above object, the present invention adopts the following technical scheme that
A kind of accumulating type emitting red light stone, it is with red long afterglow luminous material and Al2O3Or ZrO2It is prepared from for raw material；Red long afterglow luminous material used and Al2O3Or ZrO2The ratio of percetage by weight be 80-99:1-20.
The chemical formula of described red long afterglow luminous material is: (Zn1- α - β - γ - λMnαSmβAγBλ)3(PO4)2；Wherein, A is Dy3+Or Pr3+, B is Na+Or K+, α, β, γ, λ represent the mole coefficient of each element, and its value is respectively α=0.001-0.05, β=0.001-0.06, γ=0.001-0.06, λ=0.001-0.06.
The preparation method of described red long afterglow luminous material is: weigh ZnO, MnCO the most respectively3、NH4H2PO4、Sm2O3、Pr2O3Or Dy2O3、Na2CO3Or K2CO3, weigh the boric acid of prepared luminescent material molal weight 1-10% simultaneously；It is mixed and is placed in ball grinder, by the rotating speed ball milling 2-3h of 200-600 r/min, be subsequently placed in and be filled with volumetric concentration 5%H2With 95%N2Reducing atmosphere stove in, in 900-1000 DEG C calcine 2-5h.
Wherein, Sm used2O3、Pr2O3、Dy2O3Purity be 99.99%, ZnO, MnCO used3、NH4H2PO4, boric acid, Na2CO3、K2CO3It is analytical pure.
Al used2O3、ZrO2For analytical pure.
The preparation method of described accumulating type emitting red light stone is to weigh red long afterglow luminous material and Al respectively by proportioning2O3Or ZrO2, mixing is placed in ball grinder, by the rotating speed ball milling 0.5h of 100-200 r/min, it is thus achieved that the mixture of mix homogeneously, then under 2-20 atmospheric pressure, mixture is used tabletting machine molding or employing isostatic pressing, then is placed in and is filled with volumetric concentration 5%H2With 95%N2Reducing atmosphere stove in, in 1050-1280 DEG C calcine 2-5h, to obtain final product.
The remarkable advantage of the present invention is: the invention provides a kind of accumulating type emitting red light stone, it is with Mn2+Ion is the phosphoric acid zinc-base red illuminating material (Zn of the centre of luminescence1- α - β - γ - λMnαSmβAγBλ)3(PO4)2As material of main part, and by being suitably introduced into aluminium sesquioxide or zirconium oxide to improve the hardness of luminous stone.
Accumulating type emitting red light stone prepared by the present invention is after UV illumination penetrates 15 minutes, it is observed that its bright red sent in darkroom；The initial strength of luminous stone reaches 2865 mcd/m2, range estimation can reach 8 hours persistence.
Accompanying drawing explanation
Fig. 1 is the XRD figure comparison diagram with standard spectrogram of accumulating type emitting red light stone prepared by the present invention.
Fig. 2 is the excitation-emission spectrogram of accumulating type emitting red light stone prepared by the present invention.
Detailed description of the invention
In order to make content of the present invention easily facilitate understanding, below in conjunction with detailed description of the invention, technical solutions according to the invention are described further, but the present invention is not limited only to this.
Sm used2O3、Pr2O3、Dy2O3Purity be 99.99%, ZnO, MnCO used3、NH4H2PO4、Na2CO3Or K2CO3, boric acid, Al2O3、ZrO2It is analytical pure.
Embodiment 1
By chemical formula (Zn0.996Mn0.001Sm0.001Dy0.001Na0.001)3(PO4)2Stoichiometric proportion weigh ZnO, MnCO respectively3、NH4H2PO4、Sm2O3、Dy2O3、Na2CO3, weigh the boric acid of prepared luminescent material molal weight 1% simultaneously；It is mixed and is placed in ball grinder, by the rotating speed ball milling 3h of 200 r/min, be subsequently placed in and be filled with volumetric concentration 5%H2With 95%N2Reducing atmosphere stove in, in 900 DEG C calcine 3h, obtain red long afterglow luminous material (Zn0.996Mn0.001Sm0.001Dy0.001Na0.001)3(PO4)2。
The ratio of weight percent is 80:20, weighs prepared red long afterglow luminous material and Al respectively2O3, mixing is placed in ball grinder, by the rotating speed ball milling 0.5h of 100 r/min, it is thus achieved that the mixture of mix homogeneously, then uses tablet machine mixture compression molding under 2 atmospheric pressures, then is placed in and is filled with volumetric concentration 5%H2With 95%N2Reducing atmosphere stove in, in 1050 DEG C calcine 5h, obtain accumulating type emitting red light stone.Prepared luminous stone, after ultraviolet light irradiates, can glow at dark certainly, 6 hours persistences.
Embodiment 2
By chemical formula (Zn0.975Mn0.01Sm0.005Dy0.005K0.005)3(PO4)2Stoichiometric proportion weigh ZnO, MnCO respectively3、NH4H2PO4、Sm2O3、Dy2O3、K2CO3, weigh the boric acid of prepared luminescent material molal weight 5% simultaneously；It is mixed and is placed in ball grinder, by the rotating speed ball milling 2h of 400 r/min, be subsequently placed in and be filled with volumetric concentration 5%H2With 95%N2Reducing atmosphere stove in, in 950 DEG C calcine 5h, obtain red long afterglow luminous material (Zn0.975Mn0.01Sm0.005Dy0.005K0.005)3(PO4)2。
The ratio of weight percent is 85:15, weighs prepared red long afterglow luminous material and ZrO respectively2, mixing is placed in ball grinder, by the rotating speed ball milling 0.5h of 150 r/min, it is thus achieved that the mixture of mix homogeneously, then uses tablet machine mixture compression molding under 10 atmospheric pressures, then is placed in and is filled with volumetric concentration 5%H2With 95%N2Reducing atmosphere stove in, in 1100 DEG C calcine 3h, obtain accumulating type emitting red light stone.Prepared luminous stone, after ultraviolet light irradiates, can glow at dark certainly, 7 hours persistences.
Embodiment 3
By chemical formula (Zn0.95Mn0.02Sm0.01Pr0.01Na0.01)3(PO4)2Stoichiometric proportion weigh ZnO, MnCO respectively3、NH4H2PO4、Sm2O3、Pr2O3、Na2CO3, weigh the boric acid of prepared luminescent material molal weight 10% simultaneously；It is mixed and is placed in ball grinder, by the rotating speed ball milling 2h of 600 r/min, be subsequently placed in and be filled with volumetric concentration 5%H2With 95%N2Reducing atmosphere stove in, in 1000 DEG C calcine 2h, obtain red long afterglow luminous material (Zn0.95Mn0.02Sm0.01Pr0.01Na0.01)3(PO4)2。
The ratio of weight percent is 90:10, weighs prepared red long afterglow luminous material and Al respectively2O3, mixing is placed in ball grinder, by the rotating speed ball milling 0.5h of 180 r/min, it is thus achieved that the mixture of mix homogeneously, then uses isostatic pressed mixture isostatic pressing under 5 atmospheric pressures, then is placed in and is filled with volumetric concentration 5%H2With 95%N2Reducing atmosphere stove in, in 1200 DEG C calcine 2h, obtain accumulating type emitting red light stone.Prepared luminous stone, after ultraviolet light irradiates, can glow at dark certainly, 8 hours persistences.
Embodiment 4
By chemical formula (Zn0.95Mn0.02Sm0.01Pr0.01Na0.01)3(PO4)2Stoichiometric proportion weigh ZnO, MnCO respectively3、NH4H2PO4、Sm2O3、Pr2O3、K2CO3, weigh the boric acid of prepared luminescent material molal weight 8% simultaneously；It is mixed and is placed in ball grinder, by the rotating speed ball milling 3h of 500 r/min, be subsequently placed in and be filled with volumetric concentration 5%H2With 95%N2Reducing atmosphere stove in, in 920 DEG C calcine 3h, obtain red long afterglow luminous material (Zn0.77Mn0.05Sm0.06Pr0.06K0.06)3(PO4)2。
The ratio of weight percent is 99:1, weighs prepared red long afterglow luminous material and ZrO respectively2, mixing is placed in ball grinder, by the rotating speed ball milling 0.5h of 200 r/min, it is thus achieved that the mixture of mix homogeneously, then uses isostatic pressed mixture isostatic pressing under 20 atmospheric pressures, then is placed in and is filled with volumetric concentration 5%H2With 95%N2Reducing atmosphere stove in, in 1280 DEG C calcine 2h, obtain accumulating type emitting red light stone.Prepared luminous stone, after ultraviolet light irradiates, can glow at dark certainly, 5 hours persistences.
Fig. 1 is the XRD figure comparison diagram with standard spectrogram of the accumulating type emitting red light stone of embodiment 1 preparation.As can be seen from Figure, gained XRD spectra is with the β-Zn of numbered 30-1489 in standard spectrogram3(PO4)2It is consistent.
Fig. 2 is the excitation-emission spectrogram of the accumulating type emitting red light stone of embodiment 1 preparation.As can be seen from Figure, it has individual emission peak at 616nm.
The foregoing is only presently preferred embodiments of the present invention, all impartial changes done according to scope of the present invention patent and modification, all should belong to the covering scope of the present invention.

Claims (7)

1. an accumulating type emitting red light stone, it is characterised in that: with red long afterglow luminous material and Al2O3Or ZrO2It is prepared from for raw material；Red long afterglow luminous material used and Al2O3Or ZrO2The ratio of percetage by weight be 80-99:1-20.
Accumulating type emitting red light stone the most according to claim 1, it is characterised in that: Al used2O3、ZrO2For analytical pure.
Accumulating type emitting red light stone the most according to claim 1, it is characterised in that: the chemical formula of described red long afterglow luminous material is: (Zn1- α - β - γ - λMnαSmβAγBλ)3(PO4)2；
Wherein, A is Dy3+Or Pr3+, B is Na+Or K+, α, β, γ, λ represent the mole coefficient of each element, and its value is respectively α=0.001-0.05, β=0.001-0.06, γ=0.001-0.06, λ=0.001-0.06.
Accumulating type emitting red light stone the most according to claim 3, it is characterised in that: the preparation method of described red long afterglow luminous material is: weigh ZnO, MnCO the most respectively3、NH4H2PO4、Sm2O3、Pr2O3Or Dy2O3、Na2CO3Or K2CO3, weigh the boric acid of prepared luminescent material molal weight 1-10% simultaneously；It is mixed and is placed in ball grinder, by the rotating speed ball milling 2-3h of 200-600 r/min, be subsequently placed in and be filled with volumetric concentration 5%H2With 95%N2Reducing atmosphere stove in, in 900-1000 DEG C calcine 2-5h.
Accumulating type emitting red light stone the most according to claim 4, it is characterised in that: Sm used2O3、Pr2O3、Dy2O3Purity be 99.99%, ZnO, MnCO used3、NH4H2PO4, boric acid, Na2CO3、K2CO3It is analytical pure.
6. the preparation method of an accumulating type emitting red light stone as claimed in claim 1, it is characterised in that: red long afterglow luminous material and Al is weighed respectively by proportioning2O3Or ZrO2, mixing is placed in ball grinder, by the rotating speed ball milling 0.5h of 100-200 r/min, it is thus achieved that the mixture of mix homogeneously, then that mixture is compressing, is placed in and is filled with volumetric concentration 5%H2With 95%N2Reducing atmosphere stove in, in 1050-1280 DEG C calcine 2-5h, to obtain final product.
The preparation method of accumulating type emitting red light stone the most according to claim 6, it is characterised in that: described compressing be under 2-20 atmospheric pressure use tabletting machine molding or use isostatic pressing.
CN201610385540.5A 2016-06-03 2016-06-03 A kind of accumulating type emitting red light stone and preparation method thereof Expired - Fee Related CN106010533B (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101403475A (en) * 2008-11-13 2009-04-08 北京航空航天大学 Energy accumulation luminous stone and its production method
CN101591533A (en) * 2009-06-25 2009-12-02 郑子山 A kind of red long afterglow luminous material and preparation method thereof
CN104804736A (en) * 2015-04-30 2015-07-29 闽南师范大学 Long-lasting phosphor material using defects as luminescence centers and preparation method of long-lasting phosphor material

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101403475A (en) * 2008-11-13 2009-04-08 北京航空航天大学 Energy accumulation luminous stone and its production method
CN101591533A (en) * 2009-06-25 2009-12-02 郑子山 A kind of red long afterglow luminous material and preparation method thereof
CN104804736A (en) * 2015-04-30 2015-07-29 闽南师范大学 Long-lasting phosphor material using defects as luminescence centers and preparation method of long-lasting phosphor material

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
J. WANG ET AL.，: ""A novel red long lasting phosphorescent (LLP) material β-Zn3(PO4)2:Mn2+, Sm3+"", 《MATERIALS RESEARCH BULLETIN》 *

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