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CN101058726A - Silicate long lag luminescent materials - Google Patents

Silicate long lag luminescent materials Download PDF

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Publication number
CN101058726A
CN101058726A CN 200710022778 CN200710022778A CN101058726A CN 101058726 A CN101058726 A CN 101058726A CN 200710022778 CN200710022778 CN 200710022778 CN 200710022778 A CN200710022778 A CN 200710022778A CN 101058726 A CN101058726 A CN 101058726A
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China
Prior art keywords
long
luminous
visible light
silicate material
long persistence
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CN 200710022778
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Chinese (zh)
Inventor
许忠
陈中军
王加相
蔡磊杰
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DONGHAI BRIGHT Co Ltd
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DONGHAI BRIGHT Co Ltd
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Priority to CN 200710022778 priority Critical patent/CN101058726A/en
Publication of CN101058726A publication Critical patent/CN101058726A/en
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Abstract

The invention relates to a silicate long afterglow luminous material, which is characterized by the following: regarding the A(Sr1-aMa1)O.B(Mg1-bM2b)O.C(Si1-cM3c)O2. DR.EN:Eux.Biy.Lnz(A, B, C, D, E, a, b, c, x, y and z are mole coefficients) as a chemical composition expression; clearing 420-650nm emission spectrum and showing the blue, blue-green, green, moss green, yellow, red long after glow luminous under 500nm. The invention shining various colors, which shapes an electron trap of producing the fettering action for the electron; improves the luminous intensity of luminous materials; increasing the afterglow duration.

Description

A kind of long persistence luminescent silicate material
Technical field
The present invention relates to a kind of luminescent material, particularly a kind of long persistence luminescent silicate material.
Background technology
Accumulating type luminescent material of the prior art is made through high temperature sintering as main parent with the ZnS:Cu sulfides.Because the sulphide phosphor fluorescent lifetime is short, brightness is not good; Poor chemical stability.In order to change these shortcomings, also there is the people once in sulfide, to add radioactive substance and compensates its shortcoming, not only harmful when still adding the radioactive substance operation, and can pollute environment.A lot of people have dropped into a large amount of experiments since nineteen nineties, having invented strontium aluminate salt is the long after glow luminous material of matrix, the bigger raising of luminosity, but also there is poor water resistance in this class material, too high to purity of raw materials and form requirement, thus its production cost improved; And, because its illuminant colour is single, on bigger degree, limited its application.
Summary of the invention
Technical problem to be solved by this invention is at the deficiencies in the prior art, provide a kind of new, illuminant colour is rich and varied, long persistence luminescent silicate material with excellent water tolerance and stability.
Technical problem to be solved by this invention is to realize by following technical scheme.The present invention is a kind of long persistence luminescent silicate material, is characterized in, its chemical constitution expression formula is:
A (Sr 1-aM a 1) OB (Mg 1-bM 2 b) OC (Si 1-cM 3 c) O 2DREN:Eu xBi yLn zWherein:
A, B, C, D, E, a, b, c, x, y, z are mole coefficient;
M 1Be selected from one or more compositions among Ca, Ba, the Zn;
M 2Be selected from a kind of or two kinds of compositions among Cd, the Be;
M 3Be selected from a kind of or two kinds of compositions among Ge, the Hf;
R is selected from P 2O 5, B 2O 3In a kind of or two kinds of compositions;
N is selected from one or more compositions among F, Cl, Br, the I;
Ln is selected from one or more compositions among Nd, Dy, Tm, La, Pr, Ho, Tb, Ce, Mn, Sn, Sb, Er, Yb, Sm, Tl, Cr, Mo, the W;
0≤A≤2.5； 0.2≤B≤2.5；
0.8≤C≤2.5； 0.001≤D≤0.5；
0.001≤E≤0.1； 0.00001≤x≤0.05；
0.00001≤y≤0.2； 0.00001≤z≤0.1；
0≤a≤1； 0≤b≤0.5； 0≤c≤0.5；
This luminescent material excites the emmission spectrum that can send down 420～650nm in visible light, can present indigo plant, bluish-green, green, yellowish green, yellow, red color is long-persistence luminous.
Technical problem to be solved by this invention can also further realize by following technical scheme.Above-described a kind of long persistence luminescent silicate material is characterized in, wherein: 0.88≤a≤1; 0.1≤b＜0.4 or 1.5＜B≤2.5.
Technical problem to be solved by this invention can also further realize by following technical scheme.Above-described a kind of long persistence luminescent silicate material is characterized in, its chemical constitution expression formula is:
A(Sr 1-aCa a)O·B(Mg 1-b)O·C(Si 1-c)O 2·DR·EN:Eu x·Bi y·Ln z
Technical problem to be solved by this invention can also further realize by following technical scheme.Above-described a kind of long persistence luminescent silicate material is characterized in, its main compound chemical structure expression formula is: A (Sr 2-dCa d) MgSi 2O 7, wherein: 0≤d≤2,0.8≤A≤1.2.
Technical problem to be solved by this invention can also further realize by following technical scheme.Above-described a kind of long persistence luminescent silicate material is characterized in, its main compound chemical structure expression formula is: Sr 1-aCa aMgSi 2O 7, wherein: 0.7≤a≤1.
Technical problem to be solved by this invention can also further realize by following technical scheme.Above-described a kind of long persistence luminescent silicate material is characterized in, this material main compound is Sr 2MgSi 2O 7, it can present indigo plant (sky blue) look under visible light excites long-persistence luminous.
Technical problem to be solved by this invention can also further realize by following technical scheme.Above-described a kind of long persistence luminescent silicate material is characterized in, this material main compound is Sr 1.5Ca 0.5MgSi 2O 7, it can present blue-green long persistence under visible light excites luminous.
Technical problem to be solved by this invention can also further realize by following technical scheme.Above-described a kind of long persistence luminescent silicate material is characterized in, this material main compound is SrCaMgSi 2O 7This material can present green long afterglow under visible light excites luminous.
Technical problem to be solved by this invention can also further realize by following technical scheme.Above-described a kind of long persistence luminescent silicate material is characterized in, this material main compound is Ca 2MgSi 2O 7This material can present yellow longpersistent under visible light excites luminous.
Technical problem to be solved by this invention can also further realize by following technical scheme.Above-described a kind of long persistence luminescent silicate material is characterized in, this material main compound is MgSiO 3This material can present red long-afterglow under visible light excites luminous.
Long persistence luminescent silicate material of the present invention can adopt that any method applicatory is prepared in the prior art, also can prepare by the following method: after raw material is put into the mortar mixing, put into the diamond spar crucible, in 1100 ℃-1350 ℃ reducing atmosphere sintering 1-4 hour, cooling back porphyrize promptly.
Compared with prior art, the technical solution of the present invention of the present invention and further design has the following advantages:
1, the glow color of long persistence luminescent silicate material of the present invention is along with the minimizing gradually and the M of Sr mole number 1Increasing gradually of (Ca etc.) mole number is from blue, bluish-green, green, yellowish green, yellow, variation continuously gradually; Sr mole number and M 1(Ca etc.) mole number becomes redness after zero, its glow color is rich and varied.
2, in long persistence luminescent silicate material of the present invention, because the adding of haloid element replaced the case of partial oxygen atom in lattice, thereby produce the coordination defective in matrix, and this generation of defects is owing to negative ion O in the halogen family ion substitution matrix 2-The later coordination defective that forms, this matrix defective forms the electron trap to electron production constraint effect.
3, in long persistence luminescent silicate material of the present invention, Bi 3+Adding two kinds of effects are arranged, the one, as active ions, form new activation system with rare earth ion such as europium, this system only has higher activation efficiency to silicate luminescent material; The 2nd, part replaces the cationic case in the matrix, forms cavitation damage, forms the suitable electron trap of the degree of depth.
4, in long persistence luminescent silicate material of the present invention, the new activation system formed of bismuth, europium, dysprosium particularly, making silicate is that the luminous intensity of luminescent material has obtained bigger raising, time of persistence is longer than existing silicate luminescent material, and the present invention has more superior chemical stability and resistance to elevated temperatures, even original intensity can surmount aluminate luminescent material.
Embodiment
Embodiment 1.A kind of long persistence luminescent silicate material, its chemical constitution expression formula is:
2.5SrO·2.5MgO·2.5SiO 2·0.5P 2O 5·0.1F:Eu 0.05·Bi 0.2·Dy 0.1
This luminescent material can present blue long afterflow under visible light excites luminous.
In this embodiment, Dy can be replaced or existence simultaneously by Nd or Tm.
Embodiment 2.A kind of long persistence luminescent silicate material, its chemical constitution expression formula is:
1.5(Ca 0.8Ba 0.5)O·2.0Mg 0.5Cd 0.5)O·2.2(Si 0.5Ge 0.5)O 2·0.4B 2O 3·0.05Cl:Eu 0.03·Bi 0.15·Dy 0.05
This luminescent material can present yellow longpersistent under visible light excites luminous.
In this embodiment, Dy can by La or Pr or Ho replaces or existence simultaneously.
Embodiment 3.A kind of long persistence luminescent silicate material, its chemical constitution expression formula is:
(Sr 1.6Ba 0.4)O·Mg 0.7Be 0.3O·(Si 1.5Hf 0.5)O 2·0.3B 2O 3·0.01Br:Eu 0.01·Bi 0.10·Dy 0.01
This luminescent material can present blue long-persistence luminous under visible light excites.
In this embodiment, Dy can be replaced or existence simultaneously by Tb or Ce.
Embodiment 4.A kind of long persistence luminescent silicate material, its chemical constitution expression formula is:
0.5(Sr 0.9Zn 0.1)O·0.25(Mg 0.8Be 0.2)O·0.5(Si 0.7Hf 0.3)O 2·0.2P 2O 5·0.001I:Eu 0.005·Bi 0.05·Dy 0.001
This luminescent material can present blue long afterflow under visible light excites luminous.
In this embodiment, Dy can by Sn or Sb or Er replaces or existence simultaneously.
Embodiment 5.A kind of long persistence luminescent silicate material, its chemical constitution expression formula is:
2(Sr 0.7Ca 0.2Ba 0.1)O·1.2(Mg 0.6Be 0.2)O·1.2(Si 1.5Ge 0.25)O 2·0.1P 2O 5·0.005I:Eu 0.0005·Bi 0.01·Dy 0.005
This luminescent material can present blue-green long persistence under visible light excites luminous.
In this embodiment, Dy can be replaced or existence simultaneously by Yb or Sm.
Embodiment 6.A kind of long persistence luminescent silicate material, its chemical constitution expression formula is:
1.8(Sr 0.6Ca 0.2Zn 0.2)O·1.1(Mg 0.5Cd 0.3Be 0.2)O·2(Si 0.6Ge 0.2Hf 0.2)O 2·0.05P 2O 5·0.015F:Eu 0.00005·Bi 0.001·Dy 0.0005
This luminescent material can present green long afterglow under visible light excites luminous.
In this embodiment, Dy can be replaced or existence simultaneously by Tl.
Embodiment 7.A kind of long persistence luminescent silicate material, its chemical constitution expression formula is:
1.8SrO·0.9MgO·1.8SiO 2·0.001P 2O 5·0.025F:Eu 0.00001·Bi 0.0001·Dy 0.00001
This luminescent material can present sky blue long-persistence luminous under visible light excites.
In this embodiment, Dy can by Cr or Mo or W replaces or existence simultaneously.
Embodiment 8.A kind of long persistence luminescent silicate material, its chemical constitution expression formula is:
2CaO·MgO·SiO 2·0.4P 2O 5·0.035Cl:Eu 0.04·Bi 0.00001·Dy 0.00005
This luminescent material can present yellow longpersistent under visible light excites luminous.
In this embodiment, Dy can be replaced or existence simultaneously by Nd and Tm.
Embodiment 9.A kind of long persistence luminescent silicate material, its chemical constitution expression formula is:
1.9(Ca 0.9·Ba 0.1)O·MgO·2SiO 2·0.5P 2O 5·0.045Br:Eu 0.014·Bi 0.00005·Dy 0.00055
This luminescent material can present yellow longpersistent under visible light excites luminous.
In this embodiment, Dy can be replaced or existence simultaneously by Nd, La and Pr mixture.
Embodiment 10.A kind of long persistence luminescent silicate material, its chemical constitution expression formula is:
1.5(Mg 0.9Cd 0.1)·1.5SiO 2·0.4P 2O 5·0.065Cl:Eu 0.034·Bi 0.0055·Dy 0.0055·Mn 0.025
This luminescent material can present red long-afterglow under visible light excites luminous.
In this embodiment, Dy can be replaced by any mixture of forming more than two kinds or two kinds among Tm, La, Pr, Ho, Tb, Ce, Sn, Sb, Er, Yb, Sm, Tl, Cr, Mo, the W or exist simultaneously.
Embodiment 11.A kind of long persistence luminescent silicate material, its chemical constitution expression formula is:
2.0MgO·2.0SiO 2·0.1B 2O 3·0.085I:Eu 0.085·Bi 0.035·Dy 0.085·Mn 0.025
This luminescent material can present red long-afterglow under visible light excites luminous.
In this embodiment, Dy can be replaced by the mixture of Dy, Nd and La or exist simultaneously.
Embodiment 12.A kind of long persistence luminescent silicate material, its chemical constitution expression formula is:
1.1(Mg 0.8Cd 0.2)O·1.2SiO 2·0.025B 2O 3·0.065I:Eu 0.0085·Bi 0.0035·Dy 0.0085·Mn 0.025
This luminescent material can present red long-afterglow under visible light excites luminous.
In this embodiment, Dy can be replaced by any mixture of forming more than two kinds or two kinds among Nd, Tm, La, Pr, Ho, Tb, Ce, Sn, Sb, Er, Yb, Sm, Tl, Cr, Mo, the W or exist simultaneously.
Embodiment 13.A kind of long persistence luminescent silicate material, its chemical constitution expression formula is:
1.2(Mg 0.9Be 0.3)O·1.8(Si 0.7Ge 0.1)O 2·0.035B 2O 3·0.025Br:Eu 0.00085·Bi 0.00035·Dy 0.00085·Mn 0.025
This luminescent material can present red long-afterglow under visible light excites luminous.
In this embodiment, Dy can be replaced by any mixture of forming more than two kinds or two kinds among Tm, La, Pr, Ho, Tb, Ce, Sn, Sb, Er, Yb, Sm, Tl, Cr, Mo, the W or exist simultaneously.
Embodiment 14.A kind of long persistence luminescent silicate material, its chemical constitution expression formula is:
0.2(Mg 1.8Be 0.1)O·0.8(Si 0.6Hf 0.1)O 2·0.15B 2O 3·0.015Br:Eu 0.015·Bi 0.015·Dy 0.015·Mn 0.025
This luminescent material can present red long-afterglow under visible light excites luminous.
In this embodiment, Dy can be replaced by any mixture of forming more than two kinds or two kinds among Dy, Tm, La, Pr, Ho, Tb, Ce, Sn, Sb, Er, Yb, Sm, Tl, Cr, Mo, the W or exist simultaneously.
Embodiment 15.A kind of long persistence luminescent silicate material, its chemical constitution expression formula is:
0.5(Mg 1.5Be 0.5)O·(Si 0.6Hf 0.4)O 2·0.25B 2O 3·0.025Br:Eu 0.025·Bi 0.025·Dy 0.025·Mn 0.025
This luminescent material can present red long-afterglow under visible light excites luminous.
In this embodiment, Dy can be replaced by any mixture of forming among Dy and Tm, La, Pr, Ho, Tb, Ce, Sn, Sb, Er, Yb, Sm, Tl, Cr, Mo, the W or exist simultaneously.
Embodiment 16.A kind of long persistence luminescent silicate material, its chemical constitution expression formula is:
0.8(Mg 1.6Cd 0.4)O·1.5SiO 2·0.35B 2O 3·0.035Br:Eu 0.035·Bi 0.035·Dy 0.035·Mn 0.025
This luminescent material can present red long-afterglow under visible light excites luminous.
In this embodiment, Dy can be replaced by any two kinds of mixtures formed among Dy and Tm, La, Pr, Ho, Tb, Ce, Sn, Sb, Er, Yb, Sm, Tl, Cr, Mo, the W or exist simultaneously.
Embodiment 17.A kind of long persistence luminescent silicate material, its main chemical constitution expression formula is:
Sr 2MgSi 2O 7:Eu·Bi·Dy
Its proportioning raw materials is:
SrCO 3 295.24g； MgO 40g；
SiO 2 120g； Eu 2O 3 8g；
Dy 2O 3 17.85g； Bi 2O 3 13.5g；
H 3BO 3 13.25g； NH 4H 2PO 4 6g；
NH 4F 7.8g。
Its method for making is, above-mentioned raw materials is put into the mortar mixing after, put into the diamond spar crucible, sintering is 3 hours in 1230 ℃ reducing atmosphere, cooling back porphyrize is promptly.This material is behind excited by visible light, and in the dark visible sky blue long-persistence luminous, time of persistence was greater than 12 hours.
Embodiment 18.A kind of long persistence luminescent silicate material, its main chemical constitution expression formula is:
Sr 1.5Ca 0.5MgSi 2O 7:Eu·Bi·Dy
Its proportioning raw materials is:
SrCO 3 221.43g； CaCO 3 50g；
MgO 40g； SiO 2 120g；
Eu 2O 3 5g； Dy 2O 3 12.25g；
Bi 2O 3 6.5g； H 3BO 3 5g；
NH 4H 2PO 4 10g； NH 4F 4.6g。
Its method for making is, above-mentioned raw materials is put into the mortar mixing after, put into the diamond spar crucible, sintering is 4 hours in 1200 ℃ reducing atmosphere, cooling back porphyrize is promptly.This material is behind excited by visible light, and in the dark visible blue-green long persistence is luminous, and time of persistence was greater than 12 hours.
Embodiment 19.A kind of long persistence luminescent silicate material, its main chemical constitution expression formula is:
SrCaMgSi 2O 7:Eu·Bi·Dy
Its proportioning raw materials is:
SrCO 3 147.62g； CaCO 3 100g；
MgO 40g； SiO 2 120g；
Eu 2O 3 2g； Dy 2O 3 5g；
Bi 2O 3 3g； H 3BO 3 12g；
NH 4H 2PO 4 3.8g； NH 4F 3.48g。
Its method for making is, above-mentioned raw materials is put into the mortar mixing after, put into the diamond spar crucible, sintering is 2.5 hours in 1130 ℃ reducing atmosphere, cooling back porphyrize is promptly.This material is behind excited by visible light, and in the dark visible green is long-persistence luminous, and time of persistence was greater than 8 hours.
Embodiment 20.A kind of long persistence luminescent silicate material, its main chemical constitution expression formula is:
Ca 2MgSi 2O 7:Eu·Bi·Dy
Its proportioning raw materials is:
CaCO 3 200g；
MgO 40g； SiO 2 120g；
Eu 2O 3 3.8g； Dy 2O 3 18.95g；
Bi 2O 3 15.35g； H 3BO 3 12.85g；
NH 4H 2PO 4?2.95g； NH 4F 1.58g。
Its method for making is, above-mentioned raw materials is put into the mortar mixing after, put into the diamond spar crucible, sintering is 3.5 hours in 1200 ℃ reducing atmosphere, cooling back porphyrize is promptly.This material is behind excited by visible light, and in the dark visible yellow color is long-persistence luminous, and time of persistence was greater than 6 hours.
Embodiment 21.A kind of long persistence luminescent silicate material, its main chemical constitution expression formula is:
MgSiO 3:Eu·Bi·Dy·Mn
Its proportioning raw materials is:
MgO 40g； SiO 2 60g；
Eu 2O 3 1.25g； Dy 2O 3 1.95g；
Bi 2O 3 3.35g； H 3BO 3 2.65g；
NH 4H 2PO 4?14.75g； NH 4F 2.25g；
MnO 2 2.25g
Its method for making is, above-mentioned raw materials is put into the mortar mixing after, put into the diamond spar crucible, sintering is 4 hours in 1250 ℃ reducing atmosphere, cooling back porphyrize is promptly.This material is behind excited by visible light, and in the dark red color visible is long-persistence luminous, and time of persistence was greater than 4 hours.
Embodiment 22.A kind of long persistence luminescent silicate material, its main chemical constitution expression formula is:
Sr 1.32Mg 2.45Si 2O 7:Eu·Bi·Dy
Its proportioning raw materials is:
SrCO 3 195g； MgO 98g；
SiO 2 120g； Eu 2O 3 3.45g；
Dy 2O 3 7.85g； Bi 2O 3 3.5g；
H 3BO 3 11.25g； NH 4H 2PO 4?2g；
NH 4F 1.2g。
Its method for making is, above-mentioned raw materials is put into the mortar mixing after, put into the diamond spar crucible, sintering is 4 hours in 1230 ℃ reducing atmosphere, cooling back porphyrize is promptly.This material is behind excited by visible light, and in the dark visible sky blue long-persistence luminous, time of persistence was greater than 16 hours.
Embodiment 23.A kind of long persistence luminescent silicate material, its main chemical constitution expression formula is:
Sr 1.287Mg 2.625Si 1.917O 7:Eu·Bi·Dy
Its proportioning raw materials is:
SrCO 3 190g； MgO 105g；
SiO 2 115g； Eu 2O 3 3.45g；
Dy 2O 3 7.85g； Bi 2O 3 3.5g；
NH 4H 2PO 4?2g； NH 4F 1.2g。
Its method for making is, above-mentioned raw materials is put into the mortar mixing after, put into the diamond spar crucible, sintering is 4 hours in 1230 ℃ reducing atmosphere, cooling back porphyrize is promptly.This material is behind excited by visible light, and in the dark visible sky blue long-persistence luminous, time of persistence was greater than 14 hours.
Embodiment 24.A kind of long persistence luminescent silicate material, its main chemical constitution expression formula is:
Sr 1.558Ca 0.306MgSi 2.097O 7:Eu·Bi·Dy
Its proportioning raw materials is:
SrCO 3 230g； MgO 40g；
CaCO 3 30.6g； SiO 2 125.8g；
Eu 2O 3 3.45g； Dy 2O 3 7.85g；
Bi 2O 3 2.8g； H 3BO 3 10.25g；
NH 4Cl 4.5g。
Its method for making is, above-mentioned raw materials is put into the mortar mixing after, put into the diamond spar crucible, sintering is 3 hours in 1150 ℃ reducing atmosphere, cooling back porphyrize is promptly.This material is behind excited by visible light, and in the dark visible blue is long-persistence luminous, and time of persistence was greater than 12 hours.
Embodiment 25.A kind of long persistence luminescent silicate material, its main chemical constitution expression formula is:
Sr 1.542Ca 0.306MgSi 2.097O 7:Eu·Bi·Dy
Its proportioning raw materials is:
SrCO 3 227.6g； MgO 40g；
CaCO 3 30.6g； SiO 2 125.8g；
Eu 2O 3 3.45g； Dy 2O 3 7.85g；
Bi 2O 3 2.5g； H 3BO 3 10.25g；
NH 4Br 2.45g。
Its method for making is, above-mentioned raw materials is put into the mortar mixing after, put into the diamond spar crucible, sintering is 3 hours in 1150 ℃ reducing atmosphere, cooling back porphyrize is promptly.This material is behind excited by visible light, and in the dark visible blue is long-persistence luminous, and time of persistence was greater than 16 hours.
Embodiment 26.A kind of long persistence luminescent silicate material, its main chemical constitution expression formula is:
SrCaMgSi 2O 7:Eu·Bi·Dy
Its proportioning raw materials is:
SrCO 3 147.62g； MgO 40g；
CaCO 3 100g； SiO 2 120g；
Eu 2O 3 0.88g； Dy 2O 3 14.95g；
Bi 2O 3 10g； NH 4H 2PO 4 15g；
NH 4Cl 3.6g。
Its method for making is, above-mentioned raw materials is put into the mortar mixing after, put into the diamond spar crucible, sintering is 4 hours in 1250 ℃ reducing atmosphere, cooling back porphyrize is promptly.This material is behind excited by visible light, and in the dark visible green is long-persistence luminous, and time of persistence was greater than 10 hours.
Embodiment 27.A kind of long persistence luminescent silicate material, its main chemical constitution expression formula is:
Sr 0.967CaMgSi 2O 7:Eu·Bi·Dy
Its proportioning raw materials is:
SrCO 3 142.8g； MgO 40g；
CaCO 3 100g； SiO 2 120g；
Eu 2O 3 0.88g； Dy 2O 3 14.95g；
Bi 2O 3 13g； H 3BO 3 13g；
NH 4F 2.1g。
Its method for making is, above-mentioned raw materials is put into the mortar mixing after, put into the diamond spar crucible, sintering is 4 hours in 1210 ℃ reducing atmosphere, cooling back porphyrize is promptly.This material is behind excited by visible light, and in the dark visible green is long-persistence luminous, and time of persistence was greater than 10 hours.
Embodiment 28.A kind of long persistence luminescent silicate material, its main chemical constitution expression formula is:
Ca 1.95MgSi 2O 7:Eu·Bi·Dy
Its proportioning raw materials is:
CaCO 3 195g； MgO 40g；
SiO 2 120g； Eu 2O 3 3.5g；
Dy 2O 3 14.7g； Bi 2O 3 2.6g；
H 3BO 3?9.82g； NH 4H 2PO 4 3.1g；
NH 4I 2.7g。
Its method for making is, above-mentioned raw materials is put into the mortar mixing after, put into the diamond spar crucible, sintering is 3 hours in 1100 ℃ reducing atmosphere, cooling back porphyrize is promptly.This material is behind excited by visible light, and in the dark visible yellow color is long-persistence luminous, and time of persistence was greater than 8 hours.
Embodiment 29.A kind of long persistence luminescent silicate material, its main chemical constitution expression formula is:
Ca 1.90MgSi 2O 7:Eu·Bi·Dy
Its proportioning raw materials is:
CaCO 3 190g； MgO 40g；
SiO 2 120g； Eu 2O 3 3.5g；
Dy 2O 3 14.7g； Bi 2O 3 4.88g；
H 3BO 3 10.82g； NH 4Cl 1.62g。
Its method for making is, above-mentioned raw materials is put into the mortar mixing after, put into the diamond spar crucible, sintering is 3 hours in 1100 ℃ reducing atmosphere, cooling back porphyrize is promptly.This material is behind excited by visible light, and in the dark visible yellow color is long-persistence luminous, and time of persistence was greater than 8 hours.
Embodiment 30.A kind of long persistence luminescent silicate material, its main chemical constitution expression formula is:
MgSi 0.97O 7:Eu·Bi·Dy·Mn
Its proportioning raw materials is:
MgO 40g； SiO 2 58g；
Eu 2O 3 1.12g； Dy 2O 3 6.76g；
Bi 2O 3 1.41g； H 3BO 3 4g；
NH 4H 2PO 4 5.83g； NH 4Cl 2.3g；
Sb 2O 3 0.62g； MnO 2 2.7g。
Its method for making is, above-mentioned raw materials is put into the mortar mixing after, put into the diamond spar crucible, sintering is 4 hours in 1150 ℃ reducing atmosphere, cooling back porphyrize is promptly.This material is behind excited by visible light, and in the dark red color visible is long-persistence luminous, and time of persistence was greater than 5 hours.
Embodiment 31.A kind of long persistence luminescent silicate material, its main chemical constitution expression formula is:
MgSiO 3:Eu·Bi·Dy·Mn
Its proportioning raw materials is:
MgO 40g； SiO 2 60g；
Eu 2O 3 1.12g； Dy 2O 3 6.76g；
Bi 2O 3 1.46g； H 3BO 3 6.2g；
NH 4H 2PO 4 4.82g； NH 4F 1.6g；
Sb 2O 3 0.62g； MnO 2 2.7g。
Its method for making is, above-mentioned raw materials is put into the mortar mixing after, put into the diamond spar crucible, sintering is 4 hours in 1150 ℃ reducing atmosphere, cooling back porphyrize is promptly.This material is behind excited by visible light, and in the dark red color visible is long-persistence luminous, and time of persistence was greater than 4.5 hours.

Claims (10)

1, a kind of long persistence luminescent silicate material is characterized in that, its chemical constitution expression formula is:
A(Sr 1-aM a 1)O·B(Mg 1-bM 2 b)O·C(Si 1-cM 3 c)O 2.DR·EN:Eu x·Bi y·Ln z
Wherein:
A, B, C, D, E, a, b, c, x, y, z are mole coefficient;
M 1Be selected from one or more compositions among Ca, Ba, the Zn;
M 2Be selected from a kind of or two kinds of compositions among Cd, the Be;
M 3Be selected from a kind of or two kinds of compositions among Ge, the Hf;
R is selected from P 2O 5, B 2O 3In a kind of or two kinds of compositions;
N is selected from one or more compositions among F, Cl, Br, the I;
Ln is selected from one or more compositions among Nd, Dy, Tm, La, Pr, Ho, Tb, Ce, Mn, Sn, Sb, Er, Yb, Sm, Tl, Cr, Mo, the W;
0≤A≤2.5；0.2≤B≤2.5；
0.8≤C≤2.5；0.001≤D≤0.5；
0.001≤E≤0.1；0.00001≤x≤0.05；
0.00001≤y≤0.2；0.00001≤z≤0.1；
0≤a≤1；0≤b≤0.5；0≤c≤0.5；
This luminescent material excites the emmission spectrum that can send down 420～650nm in visible light, can present indigo plant, bluish-green, green, yellowish green, yellow, red color is long-persistence luminous.
2, a kind of long persistence luminescent silicate material according to claim 1 is characterized in that, wherein: 0.88≤a≤1; 0.1≤b＜0.4 or 1.5＜B≤2.5.
3, a kind of long persistence luminescent silicate material according to claim 1 is characterized in that, its chemical constitution expression formula is:
A(Sr 1-aCa a)O·B(Mg 1-b)O·C(Si 1-c)O 2.DR·EN:Eu x·Bi y·Ln z。
4, a kind of long persistence luminescent silicate material according to claim 1 is characterized in that, its main compound chemical structure expression formula is: A (Sr 2-dCa d) MgSi 2O 7, wherein: 0≤d≤2,0.8≤A≤1.2.
5, a kind of long persistence luminescent silicate material according to claim 1 is characterized in that, its main compound chemical structure expression formula is: Sr 1-aCa aMgSi 2O 7, wherein: 0.7≤a≤1.
6, a kind of long persistence luminescent silicate material according to claim 1 is characterized in that, this material main compound is Sr 2MgSi 2O 7, it can present blue long afterflow under visible light excites luminous.
7, a kind of long persistence luminescent silicate material according to claim 1 is characterized in that, this material main compound is Sr 1.5Ca 0.5MgSi 2O 7, this material can present blue-green long persistence under visible light excites luminous.
8, a kind of long persistence luminescent silicate material according to claim 1 is characterized in that, this material main compound is SrCaMgSi 2O 7, this material can present green long afterglow under visible light excites luminous.
9, a kind of long persistence luminescent silicate material according to claim 1 is characterized in that, this material main compound is Ca 2MgSi 2O 7, this material can present yellow longpersistent under visible light excites luminous.
10, a kind of long persistence luminescent silicate material according to claim 1 is characterized in that, this material main compound is MgSiO 3This material can present red long-afterglow under visible light excites luminous.
CN 200710022778 2007-05-29 2007-05-29 Silicate long lag luminescent materials Pending CN101058726A (en)

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101575510B (en) * 2009-06-17 2012-08-01 湘潭大学 Silicate green long afterglow material and preparation method thereof
CN104987865A (en) * 2015-07-24 2015-10-21 广西远大玻璃节能科技股份有限公司 Cerium and erbium-doped silicate long-afterglow light-emitting material and preparation method thereof
CN107722978A (en) * 2017-10-30 2018-02-23 闽南师范大学 A kind of multi-component oxide long after glow luminous material and preparation method thereof
CN107722972A (en) * 2017-10-30 2018-02-23 闽南师范大学 A kind of green long afterglow luminescent material and preparation method thereof
CN107964162A (en) * 2017-12-23 2018-04-27 安徽金源家居工艺品有限公司 A kind of preparation method of luminescent plastic rattan
CN108253316A (en) * 2017-12-31 2018-07-06 安徽普发照明有限公司 A kind of semiconductor light emitting component of high-cooling property, low attenuation
CN108300454A (en) * 2017-12-31 2018-07-20 安徽普发照明有限公司 High-cooling property semiconductor lighting phosphor material powder
TWI743662B (en) * 2020-01-21 2021-10-21 國立臺灣大學 Long afterglow material and preparation method thereof
CN117304922A (en) * 2023-11-29 2023-12-29 西安建筑科技大学 Ultra-long afterglow material capable of regulating and controlling trap, and preparation method and application thereof

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101575510B (en) * 2009-06-17 2012-08-01 湘潭大学 Silicate green long afterglow material and preparation method thereof
CN104987865A (en) * 2015-07-24 2015-10-21 广西远大玻璃节能科技股份有限公司 Cerium and erbium-doped silicate long-afterglow light-emitting material and preparation method thereof
CN107722978A (en) * 2017-10-30 2018-02-23 闽南师范大学 A kind of multi-component oxide long after glow luminous material and preparation method thereof
CN107722972A (en) * 2017-10-30 2018-02-23 闽南师范大学 A kind of green long afterglow luminescent material and preparation method thereof
CN107722972B (en) * 2017-10-30 2020-11-06 闽南师范大学 Green long-afterglow luminescent material and preparation method thereof
CN107722978B (en) * 2017-10-30 2020-11-06 闽南师范大学 Multi-component oxide long-afterglow luminescent material and preparation method thereof
CN107964162A (en) * 2017-12-23 2018-04-27 安徽金源家居工艺品有限公司 A kind of preparation method of luminescent plastic rattan
CN108253316A (en) * 2017-12-31 2018-07-06 安徽普发照明有限公司 A kind of semiconductor light emitting component of high-cooling property, low attenuation
CN108300454A (en) * 2017-12-31 2018-07-20 安徽普发照明有限公司 High-cooling property semiconductor lighting phosphor material powder
TWI743662B (en) * 2020-01-21 2021-10-21 國立臺灣大學 Long afterglow material and preparation method thereof
CN117304922A (en) * 2023-11-29 2023-12-29 西安建筑科技大学 Ultra-long afterglow material capable of regulating and controlling trap, and preparation method and application thereof
CN117304922B (en) * 2023-11-29 2024-03-08 西安建筑科技大学 Ultra-long afterglow material capable of regulating and controlling trap, and preparation method and application thereof

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