CN1810921A - Red long afterglow luminescent material and its prepn - Google Patents
Red long afterglow luminescent material and its prepn Download PDFInfo
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- CN1810921A CN1810921A CN 200610033929 CN200610033929A CN1810921A CN 1810921 A CN1810921 A CN 1810921A CN 200610033929 CN200610033929 CN 200610033929 CN 200610033929 A CN200610033929 A CN 200610033929A CN 1810921 A CN1810921 A CN 1810921A
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Abstract
The present invention relates to one kind of red long afterglow luminescent material and its preparation. The material has the chemical composition of MgZn2(PO4)2:xMn2+, yM, where x=0.01-0.1 mole, y =0.01-0.05 mole, M is one of Tb3+, Pb3+, Ce3+, Dy3+, Pr3+ and Gd3+. It is prepared through a high temperature solid process including weighing and mixing the material, pre-baking at 200-600 deg.c for 3-5 hr, maintaining at 850-1200 deg.c in hot carbon reducing atmosphere for 4-12 hr, cooling, grinding and sieving. The material, after being irradiated under ultraviolet ray or sunlight for certain time, can glow with red light for 1-3 hr in dark condition. It has low synthesis temperature, high chemical stability, wide material selecting range and simple preparation process.
Description
Technical field
The present invention relates to field of light emitting materials, especially relate to a kind of novel red long after glow luminous material and preparation method thereof.
Background technology
Long after glow luminous material, can absorb ambient light according to energy and with energy storage, after closing excitaton source, slowly release in the form of room temperature with visible light, therefore it has pollution-free, energy-conservation, safety, economic dispatch advantage, can be used for various signs in the dark surrounds and indication, beautifying and decorating etc.Preparation technology green and blue long afterflow fluorescent material tends to ripe (" light-storing and emitting material and goods thereof " gradually, Xiao Zhiguo, Chemical Industry Press, 2002), in order to be made into the long after glow luminous material that emits white light with commercial green and blue long afterflow fluorescent material, people concentrate on sight the research and development of red long-afterglow phosphor powder now.Because human eye is responsive especially to ruddiness, so red long afterglow luminous material can be obtained application in more areas than blue, green long afterglow luminescent material.
Red long afterglow luminous material is just to find the nineties in last century, up to now, best red long afterglow luminous material is adulterated alkaline earth sulfide of divalent europium and trivalent europium-doped yttrium oxysulfide (pertinent literature such as J.Electrochem.Soc.2000,147 (1), 386-389; Jpn.Rare Earth, 1999,35,41-45).But these are that the red long afterglow luminous material of matrix exists fast light radiativity and the unsettled shortcoming of matrix with sulfide.Above-mentioned two kinds of red long afterglow luminous materials and business-like at present blueness and green long afterglow luminescent material all are as active ions with divalent europium or trivalent europium, divalent europium is luminous to be by producing the 5d-4f transition, because 5d attitude engery level cracking is influenced by crystal field seriously, make that divalent europium can be rubescent, yellow, blue, green, purple light, the trivalent europium is because luminous easily, be still the active ions of lamp phosphor and CRT fluorescent material ruddiness composition at present, a large amount of demands costs an arm and a leg raw material three europium sesquioxides, thereby the production cost height has restricted with europium and has used widely as the red long afterglow luminous material of activator.Therefore, still need now to seek matrix good stability, the steady persistence performance is good, production cost is low red long afterglow material.
Mn
2+Emission of ions spectrum is more similar to divalent europium, all is the broadband, and its emission wavelength is also closely related with matrix, doped with Mn
2+The ionic luminescent material can be launched the various light from the ultraviolet to the infrared wavelength.With Mn
2+The long-afterglow material that excites can reduce production costs greatly, improves the market competitiveness, enlarges the Application Areas of long-afterglow material.
At present, with Mn
2+Ion still is in the laboratory study stage as the long-afterglow material of activator.Wherein, Chinese invention patent application 03109879.7 disclose several pleochroic with zinc phosphate as matrix and with Mn
2+Ion is as the long-afterglow luminescent powder of activator, but this material still exists defective, after-glow brightness a little less than, time of persistence is shorter, the β-Zn that glows
3(PO
4)
2: Mn
2+Sintering temperature is more than 950 ℃.
Summary of the invention
The objective of the invention is to overcome the shortcoming of prior art, provide a kind of low for equipment requirements, step is simple; Low and the good stability of matrix Tc; Product hardness is moderate, easily pulverizes; Raw materials cost is low, and product produces red long-afterglow, and after-glow brightness is stronger, and the time is longer, does not contain the novel red long after glow luminous material of radioelement.
Another object of the present invention is to provide the preparation method of above-mentioned red long afterglow luminous material.
Red long afterglow luminous material of the present invention is with Mn
2+Ion is active ions, with the MgZn of monocline
2(PO
4)
2Be matrix, its chemical general formula is MgZn
2(PO
4)
2: xMn
2+, yM, Mn in the formula
2+Mole number x be 0.01～0.1, co-activation ion M is Tb
3+, Pb
3+, Ce
3+, Dy
3+, Pr
3+, Gd
3+In a kind of, the mole number y of M is 0.01～0.05; The material fluorescence that under ultra violet lamp, takes on a red color.The emission wavelength of this material is a broad band, and between 550～700nm, maximum emission peak is positioned at about 620nm; CIE chromatic graph degree calculate its radiative chromaticity coordinates for (x=0.622, y=0.366).
Matrix MgZn
2(PO
4)
2Make Mn than being easier to
2+The product of singly mixing is under ultra violet lamp, and time of persistence is very short.Behind selected coactivator among the present invention that mixed, in the thermoluminescence spectrogram, observe and be positioned at about 100 ℃, there is a heat-flash to release photopeak, illustrate that this material has the suitable trap of the degree of depth, after material was subjected to illumination, the trap of material stored energy, after removing excitaton source, slow release energy and pass to active ions Mn again
2+, make Mn
2+Ion continues luminous.
The preparation method of red long afterglow luminous material of the present invention is:
Adopt high temperature solid-state method, according to the following steps preparation: with MgO, ZnO, NH
4H
2PO
4For feedstock production matrix, in matrix, with MnCO
3For raw material mixes active ions, with Tb
3+, Pb
3+, Ce
3+, Dy
3+, Pr
3+, Gd
3+In the pairing oxide compound of a kind of ion be that raw material mixes coactivator, grind mixing, in hot carbon reduction atmosphere, pre-burning is 3～5 hours under 200～500 ℃ of conditions, take out the cooling back, grind and mix, be incubated 4～12 hours again under 850～1200 ℃ of conditions, the cooling back grinds to sieve and gets product;
MgO, ZnO, NH
4H
2PO
4And MnCO
3The mol ratio of add-on is 1: 1: 2: 0.01～0.1, and the add-on of coactivator is 0.01～0.05 (1～5%) of MgO add-on mole number.
Described hot carbon reduction atmosphere is meant, the mixture that grinds mixing is put into monkey, monkey is put into a big crucible that activated carbon granule is housed again.
For further realizing purpose of the present invention also comprising fusing assistant in above-mentioned preparation method's the matrix, described fusing assistant is boric acid or ammonium chloride, and its consumption is 0.1～3.0% of a raw material total mass.
The XRD figure of the long after glow luminous material of method for preparing as shown in Figure 1, among the figure all diffraction peak position and relative intensity all with standard card (JCPDS No.31-1468) on data in full accord, illustrate that the product that obtains is the MgZn of pure phase
2(PO
4)
2Fig. 2 is the excitation spectrum (a) and emmission spectrum (b) of product, from excitation spectrum, this product can effectively be excited by the visible light about UV-light and wavelength 413nm, and from its emmission spectrum, what product was launched is the ruddiness with wide wavelength region, and maximum emission wavelength is positioned at about 620nm.Fig. 3 is the thermoluminescence spectrogram of product, occurs a very strong peak about 100 ℃, and this illustrates that this product has the suitable trap of the degree of depth, and the energy storage power at ambient temperature, and can slowly be emitted energy, passes to active ions, realizes continuing luminous.
Advantage of the present invention is that preparation technology is low for equipment requirements, and step is simple; Low and the good stability of matrix Tc; Product hardness is moderate, easily pulverizes; Raw materials cost is low, and product produces red long-afterglow, and 2 meters external enwergys are with the naked eye clearly observed twilight sunset, do not contain radioelement.
Description of drawings
Fig. 1 is the XRD figure of red long afterglow luminous material of the present invention;
Fig. 2 is the exciting light spectrogram (a) and emmission spectrum figure (b) (illustration is the part enlarged view of excitation spectrum) of red long afterglow luminous material of the present invention;
Fig. 3 is the thermoluminescence spectrogram of red long afterglow luminous material of the present invention.
Embodiment
The present invention is further illustrated below in conjunction with embodiment, but the scope of protection of present invention is not limited to the scope that embodiment represents.
Example 1
Accurately take by weighing magnesium oxide (MgO) 0.2015g, zinc oxide (ZnO) 0.8139g, primary ammonium phosphate (NH
4H
2PO
4) 1.1502g, manganous carbonate (MnCO
3) 0.0574g, terbium sesquioxide (Tb
4O
7) 0.0934g, in agate mortar, ground about 30 minutes, make the raw material thorough mixing even.The raw material that mixes is transferred in the monkey, again monkey is put into a big crucible that activated carbon granule is housed, covered the lid of big crucible, put into box-type furnace, 500 ℃ of pre-burnings 3 hours, cooling is taken out, and regrinding is about 15 minutes, and the speed with 5 ℃ of per minutes is raised to 850 ℃ again, and be incubated 5 hours, take out behind the naturally cooling, grind gently, promptly get product.Through XRD analysis is the MgZn of pure phase
2(PO
4)
2, product shone 5 minutes under 254nm or 366nm ultraviolet lamp, produced red fluorescence.Close ultraviolet lamp, in dark situation, obvious red color visible twilight sunset, twilight sunset continues about 1.5 hours.
Example 2
Accurately take by weighing magnesium oxide (MgO) 0.2015g, zinc oxide (ZnO) 0.8139g, primary ammonium phosphate (NH
4H
2PO
4) 1.1502g, manganous carbonate (MnCO
3) 0.0574g, terbium sesquioxide (Tb
4O
7) 0.0934g, boric acid (H
3BO
3) 0.0694g, in agate mortar, ground about 30 minutes, make the raw material thorough mixing even.The raw material that mixes is transferred in the monkey, again monkey is put into a big crucible that activated carbon granule is housed, covered the lid of big crucible, put into box-type furnace, 500 ℃ of pre-burnings 3 hours, cooling is taken out, and regrinding is about 15 minutes, and the speed with 5 ℃ of per minutes is raised to 850 ℃ again, and be incubated 5 hours, take out behind the naturally cooling, grind gently, promptly get product.Through XRD analysis is the MgZn of pure phase
2(PO
4)
2, product shone 5 minutes under 254nm or 366nm ultraviolet lamp, produced red fluorescence.Close ultraviolet lamp, in dark situation, obvious red color visible twilight sunset, twilight sunset continues about 2.5 hours.
Example 3
Accurately take by weighing magnesium oxide (MgO) 0.2015g, zinc oxide (ZnO) 0.8139g, primary ammonium phosphate (NH
4H
2PO
4) 1.1502g, manganous carbonate (MnCO
3) 0.0574g, Praseodymium trioxide (Pr
6O
11) 0.0851g, boric acid (H
3BO
3) 0.0694g, in agate mortar, ground about 30 minutes, raw material is mixed.The raw material that mixes is transferred in the monkey, again monkey is put into a big crucible that activated carbon granule is housed, covered the lid of big crucible, put into box-type furnace, 500 ℃ of pre-burnings 5 hours, cooling is taken out, and regrinding is about 15 minutes, and the speed with 5 ℃ of per minutes is raised to 1200 ℃ again, and be incubated 5 hours, take out behind the naturally cooling, grind gently, promptly get product.Through XRD analysis is the MgZn of pure phase
2(PO
4)
2, product shone 5 minutes under 254nm or 366nm ultraviolet lamp, produced red fluorescence.Close ultraviolet lamp, in dark situation, obvious red color visible twilight sunset, twilight sunset continues about 3 hours.
Example 4
Accurately take by weighing magnesium oxide (MgO) 0.2015g, zinc oxide (ZnO) 0.8139g, primary ammonium phosphate (NH
4H
2PO
4) 1.1502g, manganous carbonate (MnCO
3) 0.0574g, Praseodymium trioxide (Pr
6O
11) 0.0851g, ammonium chloride (NH
4Cl) 0.0600g ground about 30 minutes in agate mortar, and raw material is mixed.The raw material that mixes is transferred in the monkey, again monkey is put into a big crucible that activated carbon granule is housed, covered the lid of big crucible, put into box-type furnace, 500 ℃ of pre-burnings 4 hours, cooling is taken out, and regrinding is about 15 minutes, and the speed with 5 ℃ of per minutes is raised to 1200 ℃ again, and be incubated 5 hours, take out behind the naturally cooling, grind gently, promptly get product.Through XRD analysis is the MgZn of pure phase
2(PO
4)
2, product shone 5 minutes under 254nm or 366nm ultraviolet lamp, produced red fluorescence.Close ultraviolet lamp, in dark situation, obvious red color visible twilight sunset, twilight sunset continues about 2.5 hours.
Example 5
Accurately take by weighing magnesium oxide (MgO) 0.2015g, zinc oxide (ZnO) 0.8139g, primary ammonium phosphate (NH
4H
2PO
4) 1.1502g, manganous carbonate (MnCO
3) 0.0574g, Praseodymium trioxide (Pr
6O
11) 0.0851g, boric acid (H
3BO
3) 0.0694g, in agate mortar, ground about 30 minutes, raw material is mixed.The raw material that mixes is transferred in the monkey, again monkey is put into a big crucible that activated carbon granule is housed, covered the lid of big crucible, put into box-type furnace, 500 ℃ of pre-burnings 3 hours, cooling is taken out, and regrinding is about 15 minutes, and the speed with 5 ℃ of per minutes is raised to 850 ℃ again, and be incubated 5 hours, take out behind the naturally cooling, grind gently, promptly get product.Through XRD analysis is the MgZn of pure phase
2(PO
4)
2, product shone 5 minutes under 254nm or 366nm ultraviolet lamp, produced red fluorescence.Close ultraviolet lamp, in dark situation, obvious red color visible twilight sunset, twilight sunset continues about 2 hours.
Example 6
Accurately take by weighing magnesium oxide (MgO) 0.2015g, zinc oxide (ZnO) 0.8139g, primary ammonium phosphate (NH
4H
2PO
4) 1.1502g, manganous carbonate (MnCO
3) 0.0574g, gadolinium sesquioxide (Gd
2O
3) 0.0905g, boric acid (H
3BO
3) 0.0694g, in agate mortar, ground about 30 minutes, raw material is mixed.The raw material that mixes is transferred in the monkey, again monkey is put into a big crucible that activated carbon granule is housed, covered the lid of big crucible, put into box-type furnace, 500 ℃ of pre-burnings 3 hours, cooling is taken out, and regrinding is about 15 minutes, and the speed with 5 ℃ of per minutes is raised to 950 ℃ again, and be incubated 5 hours, take out behind the naturally cooling, grind gently, promptly get product.Through XRD analysis is the MgZn of pure phase
2(PO
4)
2, product shone 5 minutes under 254nm or 366nm ultraviolet lamp, produced red fluorescence.Close ultraviolet lamp, in dark situation, obvious red color visible twilight sunset, twilight sunset continues about 2 hours.
Example 7
Accurately take by weighing magnesium oxide (MgO) 0.2015g, zinc oxide (ZnO) 0.8139g, primary ammonium phosphate (NH
4H
2PO
4) 1.1502g, manganous carbonate (MnCO
3) 0.0574g, cerium oxide (CeO
2) 0.0858g, boric acid (H
3BO
3) 0.0694g, in agate mortar, ground about 30 minutes, raw material is mixed.The raw material that mixes is transferred in the monkey, again monkey is put into a big crucible that activated carbon granule is housed, covered the lid of big crucible, put into box-type furnace, 200 ℃ of pre-burnings 3 hours, cooling is taken out, and regrinding is about 15 minutes, and the speed with 5 ℃ of per minutes is raised to 950 ℃ again, and be incubated 5 hours, take out behind the naturally cooling, grind gently, promptly get product.Through XRD analysis is the MgZn of pure phase
2(PO
4)
2, product shone 5 minutes under 254nm or 366nm ultraviolet lamp, produced red fluorescence.Close ultraviolet lamp, in dark situation, obvious red color visible twilight sunset, twilight sunset continues about 2 hours.
Example 8
Accurately take by weighing magnesium oxide (MgO) 0.2015g, zinc oxide (ZnO) 0.8139g, primary ammonium phosphate (NH
4H
2PO
4) 1.1502g, manganous carbonate (MnCO
3) 0.0574g, cerium oxide (CeO
2) 0.0858g, boric acid (H
3BO
3) 0.0694g, in agate mortar, ground about 30 minutes, raw material is mixed.The raw material that mixes is transferred in the monkey, again monkey is put into a big crucible that activated carbon granule is housed, covered the lid of big crucible, put into box-type furnace, 500 ℃ of pre-burnings 4 hours, cooling is taken out, and regrinding is about 15 minutes, and the speed with 5 ℃ of per minutes is raised to 1000 ℃ again, and be incubated 5 hours, take out behind the naturally cooling, grind gently, promptly get product.Through XRD analysis is the MgZn of pure phase
2(PO
4)
2, product shone 5 minutes under 254nm or 366nm ultraviolet lamp, produced red fluorescence.Close ultraviolet lamp, in dark situation, obvious red color visible twilight sunset, twilight sunset continues about 2.5 hours.
Example 9
Accurately take by weighing magnesium oxide (MgO) 0.2015g, zinc oxide (ZnO) 0.8139g, primary ammonium phosphate (NH
4H
2PO
4) 1.1502g, manganous carbonate (MnCO
3) 0.0574g, terbium sesquioxide (Tb
4O
7) 0.0934g, boric acid (H
3BO
3) 0.0694g, in agate mortar, ground about 30 minutes, raw material is mixed.The raw material that mixes is transferred in the monkey, again monkey is put into a big crucible that activated carbon granule is housed, covered the lid of big crucible, put into box-type furnace, 400 ℃ of pre-burnings 5 hours, cooling is taken out, and regrinding is about 15 minutes, and the speed with 5 ℃ of per minutes is raised to 850 ℃ again, and be incubated 5 hours, take out behind the naturally cooling, grind gently, promptly get product.Through XRD analysis is the MgZn of pure phase
2(PO
4)
2, product shone 5 minutes under 254nm or 366nm ultraviolet lamp, produced red fluorescence.Close ultraviolet lamp, in dark situation, obvious red color visible twilight sunset, twilight sunset continues about 2 hours.
Example 10
Accurately take by weighing magnesium oxide (MgO) 0.2015g, zinc oxide (ZnO) 0.8139g, primary ammonium phosphate (NH
4H
2PO
4) 1.1502g, manganous carbonate (MnCO
3) 0.01148g, terbium sesquioxide (Tb
4O
7) 0.0934g, boric acid (H
3BO
3) 0.0694g, in agate mortar, ground about 30 minutes, raw material is mixed.The raw material that mixes is transferred in the monkey, again monkey is put into a big crucible that activated carbon granule is housed, covered the lid of big crucible, put into box-type furnace, 400 ℃ of pre-burnings 5 hours, cooling is taken out, and regrinding is about 15 minutes, and the speed with 5 ℃ of per minutes is raised to 850 ℃ again, and be incubated 10 hours, take out behind the naturally cooling, grind gently, promptly get product.Through XRD analysis is the MgZn of pure phase
2(PO
4)
2, product shone 5 minutes under 254nm or 366nm ultraviolet lamp, produced red fluorescence.Close ultraviolet lamp, in dark situation, obvious red color visible twilight sunset, twilight sunset continues about 1 hour.
Example 11
Accurately take by weighing magnesium oxide (MgO) 0.2015g, zinc oxide (ZnO) 0.8139g, primary ammonium phosphate (NH
4H
2PO
4) 1.1502g, manganous carbonate (MnCO
3) 0.1148g, terbium sesquioxide (Tb
4O
7) 0.0934g, boric acid (H
3BO
3) 0.0694g, in agate mortar, ground about 30 minutes, raw material is mixed.The raw material that mixes is transferred in the monkey, again monkey is put into a big crucible that activated carbon granule is housed, covered the lid of big crucible, put into box-type furnace, 400 ℃ of pre-burnings 5 hours, cooling is taken out, and regrinding is about 15 minutes, and the speed with 5 ℃ of per minutes is raised to 850 ℃ again, and be incubated 10 hours, take out behind the naturally cooling, grind gently, promptly get product.Through XRD analysis is the MgZn of pure phase
2(PO
4)
2, product shone 5 minutes under 254nm or 366nm ultraviolet lamp, produced red fluorescence.Close ultraviolet lamp, in dark situation, obvious red color visible twilight sunset, twilight sunset continues about 1 hour.
Example 12
Accurately take by weighing magnesium oxide (MgO) 0.2015g, zinc oxide (ZnO) 0.8139g, primary ammonium phosphate (NH
4H
2PO
4) 1.1502g, manganous carbonate (MnCO
3) 0.0574g, terbium sesquioxide (Tb
4O
7) 0.01868g, boric acid (H
3BO
3) 0.0694g, in agate mortar, ground about 30 minutes, raw material is mixed.The raw material that mixes is transferred in the monkey, again monkey is put into a big crucible that activated carbon granule is housed, covered the lid of big crucible, put into box-type furnace, 400 ℃ of pre-burnings 5 hours, cooling is taken out, and regrinding is about 15 minutes, and the speed with 5 ℃ of per minutes is raised to 950 ℃ again, and be incubated 5 hours, take out behind the naturally cooling, grind gently, promptly get product.Through XRD analysis is the MgZn of pure phase
2(PO
4)
2, product shone 5 minutes under 254nm or 366nm ultraviolet lamp, produced red fluorescence.Close ultraviolet lamp, in dark situation, obvious red color visible twilight sunset, twilight sunset continues about 1.5 hours.
Example 13
Accurately take by weighing magnesium oxide (MgO) 0.2015g, zinc oxide (ZnO) 0.8139g, primary ammonium phosphate (NH
4H
2PO
4) 1.1502g, manganous carbonate (MnCO
3) 0.0574g, terbium sesquioxide (Tb
4O
7) 0.0934g, boric acid (H
3BO
3) 0.0694g, in agate mortar, ground about 30 minutes, raw material is mixed.The raw material that mixes is transferred in the monkey, again monkey is put into a big crucible that activated carbon granule is housed, covered the lid of big crucible, put into box-type furnace, 400 ℃ of pre-burnings 5 hours, cooling is taken out, and regrinding is about 15 minutes, and the speed with 5 ℃ of per minutes is raised to 850 ℃ again, and be incubated 10 hours, take out behind the naturally cooling, grind gently, promptly get product.Through XRD analysis is the MgZn of pure phase
2(PO
4)
2, product shone 5 minutes under 254nm or 366nm ultraviolet lamp, produced red fluorescence.Close ultraviolet lamp, in dark situation, obvious red color visible twilight sunset, twilight sunset continues about 1.5 hours.
Example 14
Accurately take by weighing magnesium oxide (MgO) 0.2015g, zinc oxide (ZnO) 0.8139g, primary ammonium phosphate (NH
4H
2PO
4) 1.1502g, manganous carbonate (MnCO
3) 0.0574g, terbium sesquioxide (Tb
4O
7) 0.0934g, boric acid (H
3BO
3) 0.0694g, in agate mortar, ground about 30 minutes, raw material is mixed.The raw material that mixes is transferred in the monkey, again monkey is put into a big crucible that activated carbon granule is housed, covered the lid of big crucible, put into box-type furnace, 400 ℃ of pre-burnings 4 hours, cooling is taken out, and regrinding is about 15 minutes, and the speed with 5 ℃ of per minutes is raised to 850 ℃ again, and be incubated 12 hours, take out behind the naturally cooling, grind gently, promptly get product.Through XRD analysis is the MgZn of pure phase
2(PO
4)
2, product shone 5 minutes under 254nm or 366nm ultraviolet lamp, produced red fluorescence.Close ultraviolet lamp, in dark situation, obvious red color visible twilight sunset, twilight sunset continues about 1.5 hours.
Example 15
Accurately take by weighing magnesium oxide (MgO) 0.2015g, zinc oxide (ZnO) 0.8139g, primary ammonium phosphate (NH
4H
2PO
4) 1.1502g, manganous carbonate (MnCO
3) 0.0574g, terbium sesquioxide (Tb
4O
7) 0.0934g, boric acid (H
3BO
3) 0.0694g, in agate mortar, ground about 30 minutes, raw material is mixed.The raw material that mixes is transferred in the monkey, again monkey is put into a big crucible that activated carbon granule is housed, covered the lid of big crucible, put into box-type furnace, 400 ℃ of pre-burnings 5 hours, cooling is taken out, and regrinding is about 15 minutes, and the speed with 5 ℃ of per minutes is raised to 850 ℃ again, and be incubated 4 hours, take out behind the naturally cooling, grind gently, promptly get product.Through XRD analysis is the MgZn of pure phase
2(PO
4)
2, product shone 5 minutes under 254nm or 366nm ultraviolet lamp, produced red fluorescence.Close ultraviolet lamp, in dark situation, obvious red color visible twilight sunset, twilight sunset continues about 1 hour.
Example 16
Accurately take by weighing magnesium oxide (MgO) 0.2015g, zinc oxide (ZnO) 0.8139g, primary ammonium phosphate (NH
4H
2PO
4) 1.1502g, manganous carbonate (MnCO
3) 0.0574g, plumbous oxide (PbO) 0.1112g, boric acid (H
3BO
3) 0.0694g, in agate mortar, ground about 30 minutes, raw material is mixed.The raw material that mixes is transferred in the monkey, again monkey is put into a big crucible that activated carbon granule is housed, covered the lid of big crucible, put into box-type furnace, 400 ℃ of pre-burnings 5 hours, cooling is taken out, and regrinding is about 15 minutes, and the speed with 5 ℃ of per minutes is raised to 1000 ℃ again, and be incubated 5 hours, take out behind the naturally cooling, grind gently, promptly get product.Through XRD analysis is the MgZn of pure phase
2(PO
4)
2, product shone 5 minutes under 254nm or 366nm ultraviolet lamp, produced red fluorescence.Close ultraviolet lamp, in dark situation, obvious red color visible twilight sunset, twilight sunset continues about 1 hour.
Example 17
Accurately take by weighing magnesium oxide (MgO) 0.2015g, zinc oxide (ZnO) 0.8139g, primary ammonium phosphate (NH
4H
2PO
4) 1.1502g, manganous carbonate (MnCO
3) 0.0574g, dysprosium oxide (Dy
2O
3) 0.0921g, boric acid (H
3BO
3) 0.0694g, in agate mortar, ground about 30 minutes, raw material is mixed.The raw material that mixes is transferred in the monkey, again monkey is put into a big crucible that activated carbon granule is housed, covered the lid of big crucible, put into box-type furnace, 400 ℃ of pre-burnings 3 hours, cooling is taken out, and regrinding is about 15 minutes, and the speed with 5 ℃ of per minutes is raised to 1000 ℃ again, and be incubated 8 hours, take out behind the naturally cooling, grind gently, promptly get product.Through XRD analysis is the MgZn of pure phase
2(PO
4)
2, product shone 5 minutes under 254nm or 366nm ultraviolet lamp, produced red fluorescence.Close ultraviolet lamp, in dark situation, obvious red color visible twilight sunset, twilight sunset continues about 1 hour.
Example 18
Accurately take by weighing magnesium oxide (MgO) 0.2015g, zinc oxide (ZnO) 0.8139g, primary ammonium phosphate (NH
4H
2PO
4) 1.1502g, manganous carbonate (MnCO
3) 0.0574g, terbium sesquioxide (Tb
4O
7) 0.0934g, in agate mortar, ground about 30 minutes, make the raw material thorough mixing even.The raw material that mixes is transferred in the monkey, again monkey is put into a big crucible that activated carbon granule is housed, covered the lid of big crucible, put into box-type furnace, 500 ℃ of pre-burnings 3 hours, cooling is taken out, and regrinding is about 15 minutes, and the speed with 5 ℃ of per minutes is raised to 850 ℃ again, and be incubated 5 hours, take out behind the naturally cooling, grind gently, promptly get product.Through XRD analysis is the MgZn of pure phase
2(PO
4)
2, product shone 5 minutes under 254nm or 366nm ultraviolet lamp, produced red fluorescence.Close ultraviolet lamp, in dark situation, obvious red color visible twilight sunset, twilight sunset continues about 1.5 hours.
As mentioned above, can better realize the present invention.
Claims (4)
1, a kind of red long afterglow luminous material is characterized in that, with Mn
2+Ion is active ions, with the MgZn of monocline
2(PO
4)
2Be matrix, its chemical general formula is MgZn
2(PO
4)
2: xMn
2+, yM, Mn in the formula
2+Mole number x be 0.01～0.1, co-activation ion M is Tb
3+, Pb
3+, Ce
3+, Dy
3+, Pr
3+, Gd
3+In a kind of, the mole number y of M is 0.01～0.05; The material fluorescence that under ultra violet lamp, takes on a red color.
2, the preparation method of the described red long afterglow luminous material of a kind of claim 1 is characterized in that, with MgO, ZnO, NH
4H
2PO
4For feedstock production matrix, in matrix, with MnCO
3For raw material mixes active ions, with Tb
3+, Pb
3+, Ce
3+, Dy
3+, Pr
3+, Gd
3+In the pairing oxide compound of a kind of ion be that raw material mixes coactivator, grind mixing, in hot carbon reduction atmosphere, pre-burning is 3～5 hours under 200～500 ℃ of conditions, take out the cooling back, grind and mix, be incubated 4～12 hours again under 850～1200 ℃ of conditions, the cooling back grinds to sieve and gets product;
MgO, ZnO, NH
4H
2PO
4And MnCO
3The mol ratio of add-on is 1: 1: 2: 0.01～0.1, and the add-on of coactivator is 1～5% of a MgO add-on mole number.
3, the preparation method of a kind of red long afterglow luminous material according to claim 2 is characterized in that, described matrix is also mixed fusing assistant, and described fusing assistant is boric acid or ammonium chloride, and its consumption is 0.1～3.0% of a raw material total mass.
4, the preparation method of a kind of red long afterglow luminous material according to claim 2, it is characterized in that, described hot carbon reduction atmosphere is meant, the mixture that grinds mixing is put into monkey, monkey is put into a big crucible that activated carbon granule is housed again.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108892504A (en) * | 2018-06-12 | 2018-11-27 | 闽南师范大学 | A kind of blue-green multicomponent light storage ceramic material and preparation method thereof |
| CN109161968A (en) * | 2018-08-27 | 2019-01-08 | 中山大学 | A kind of red long-afterglow single crystal material and preparation method thereof |
| CN109777419A (en) * | 2019-03-28 | 2019-05-21 | 新疆大学 | Phosphoric acid zinc-magnesium single-substrate white fluorescent powder and preparation method thereof |
| CN110591707A (en) * | 2019-09-05 | 2019-12-20 | 常州工程职业技术学院 | Mn (manganese)2+Activated vanadium phosphate inorganic fluorescent powder and preparation method and application thereof |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011004722A1 (en) * | 2009-07-09 | 2011-01-13 | 株式会社村田製作所 | Method for producing complex oxide powder, and complex oxide powder |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5788881A (en) * | 1995-10-25 | 1998-08-04 | Micron Technology, Inc. | Visible light-emitting phosphor composition having an enhanced luminescent efficiency over a broad range of voltages |
| CN1150296C (en) * | 2000-06-22 | 2004-05-19 | 大连路明科技集团有限公司 | Light-accumulation long-afterglow luminous material |
| US6809781B2 (en) * | 2002-09-24 | 2004-10-26 | General Electric Company | Phosphor blends and backlight sources for liquid crystal displays |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108892504A (en) * | 2018-06-12 | 2018-11-27 | 闽南师范大学 | A kind of blue-green multicomponent light storage ceramic material and preparation method thereof |
| CN108892504B (en) * | 2018-06-12 | 2020-12-29 | 闽南师范大学 | Blue-green multi-component light-storing ceramic material and preparation method thereof |
| CN109161968A (en) * | 2018-08-27 | 2019-01-08 | 中山大学 | A kind of red long-afterglow single crystal material and preparation method thereof |
| CN109777419A (en) * | 2019-03-28 | 2019-05-21 | 新疆大学 | Phosphoric acid zinc-magnesium single-substrate white fluorescent powder and preparation method thereof |
| CN110591707A (en) * | 2019-09-05 | 2019-12-20 | 常州工程职业技术学院 | Mn (manganese)2+Activated vanadium phosphate inorganic fluorescent powder and preparation method and application thereof |
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