CN102923947A - Novel white light glass and preparation method thereof - Google Patents

Abstract

The invention relates to novel white light glass and a preparation method thereof. The novel white light glass and the preparation method thereof make Sb3+ ions and Mn2+ ions as luminous centers, enable the Sb3+ ions and the Mn2+ ions to be mixed into phosphate glass matrixes to prepare the white light glass, and have the advantages of being unleaded, free of radioactivity, good in glass formation, capable of giving out white light and the like. The preparation method of the novel white light glass comprises the following steps: (a) selection of raw materials; (b) weighing and mixing of glass batch; and (c) founding and annealing of the glass. The Sb3+ and the Mn2+ being mixed into the phosphate glass prepared in the method can effectively be activated by ultraviolet lights. The lighting centers of the Sb3+ and the Mn2+ ions can respectively emit characteristic light and energy transfer from the Sb3+ to the Mn2+ exists. Emitting occurs in blue light (B), green light (G), and read light (R) which are all combined to white light. The white light glass is a novel material capable of emitting white light with high application value.

Description

A kind of novel white light glass and preparation method thereof

Technical field

The present invention relates to luminescent material of emitting electron, illuminating engineering sciemtifec and technical sphere and preparation method thereof, relate in particular to a kind of with Sb ³⁺And Mn ²⁺Be white light glass of luminescence center and preparation method thereof.

Background technology

From first red LED lamp invention in 1969 till now, in short time decades, the LED industry is accompanied by the development of semiconductor technology and develop rapidly, and Application Areas constantly enlarges, and the demand of LED is also increasing.The LED conventional light source has been compared many advantages,, less energy consumption little such as volume, response is fast, the life-span is long, pollution-free etc., therefore be called the 4th generation lighting source.Particularly the invention of white light LEDs makes LED be used for interior lighting becomes possibility, the second revolution of incandescent lighting developing history since 120 years that continue of being known as.

LED luminescent material majority all adopts rare-earth ion activated fluorescent material at present.Rare earth element is expensive, and it is luminous to be line spectrum, and in use emission wavelength can be offset, and causes the compound white light colour temperature that goes out to change.Therefore, the Sb of cheap, excellent performance ³⁺/ Mn ²⁺Mixing altogether halogen-phosphate fluorescent material is widely used.But at high temperature easily burn-in effects is luminous for the Resins, epoxy that encapsulates fluorescent material.

With Sb ³⁺And Mn ²⁺Can avoid the shortcoming of above-mentioned white-light illuminating for the white light glass of luminescence center.Three oxidations, two ladders and manganese oxide belong to glass network intermediate, can introduce with higher concentration in glass, improve luminous intensity, and cost are low.Sb ³⁺And Mn ²⁺Luminous be wide range, wavelength shift is little on the impact of white color temperature.Glass possesses good photopermeability, chemical stability is high, preparation cost is low.Especially glass material is easily processed, and can become white light parts with the direct etching of led chip " spiral-lock ", and is therefore significant to simplifying resin package technique, raising thermostability and light extraction efficiency.

Summary of the invention

The technical issues that need to address of the present invention are to disclose a kind of novel white light glass and preparation method thereof, with the candidate material of using as the White-light LED illumination except fluorescent material.

The phosphate glass that described antimony-manganese of the present invention is mixed altogether is characterized in that its component and mole percent level thereof are as follows:

P in the said components ₂O ₅With the RO sum be 100mol%; R=Mg wherein, Ca, one or more mixing wherein such as Sr, Ba, Zn etc.

Change within the specific limits the ratio of composition and the dopant ion of host glass, can adjust the luminous intensity of its blue light, green glow, ruddiness, thereby obtain the white light of different-colour.

White light glass that above-mentioned antimony-manganese is mixed altogether and preparation method thereof is characterized in that comprising following steps:

A) raw material chooses

The phosphate glass raw material sources are in analytically pure primary ammonium phosphate, carbonate, oxide compound.Sb ³⁺The antimonous oxide that Analysis about Selection is pure, Mn ²⁺The carbonate that Analysis about Selection is pure.

B) weighing of glass batch and mixing

Accurately take by weighing glass batch, in ceramic mortar, grind and fully mix.

C) glass founding and annealing

Admixtion is put into the melting furnace that is warming up to 1000-1350 ℃ and was founded 1-2 hour, anneals a few hours about 300-450 ℃ subsequently, cools to room temperature with the furnace.

The white light glass of the present invention preparation can send blue light (400-500nm) and orange red light (550-650nm) under UV-irradiation, thereby compoundly goes out white light.According to the doping ratio of different calcium halophosphate activated by antimony andmanganese ions, obtain the white light of different-colour.Increase the doping content of antimony, can greatly improve the luminous intensity of this fluorescent glass.In addition, the workability that the glass forming ability of glass is good, preparation technology is simple, good.White light glass of the present invention can be applied to the productive life lighting field, and is energy-conservation to the exploitation of China's new forms of energy, reduces and pollutes, and realizes that the Sustainable development of national economy is significant.

Description of drawings

Fig. 1 is the utilizing emitted light spectrogram of glass under the 277nm wavelength excites of embodiment 1

Fig. 2 is the utilizing emitted light spectrogram of glass under the 277nm wavelength excites of embodiment 2 and 3

Embodiment

The present invention is further described by the following examples, but should this restriction protection scope of the present invention.

Embodiment 1

Adopt analytically pure primary ammonium phosphate (NH ₄H ₂PO ₄), light magnesium oxide (MgO), antimonous oxide (Sb ₂O ₃), manganous carbonate (MnCO ₃) be main raw material, according to stoichiometric ratio, design component is as follows:

The glass of table 1 embodiment 1 forms (mol%):

P 2O 5	MgO	8b 2O 3	MnO
				60	40	1.5	2

Proportioning according to above mixes load weighted raw material.Admixtion places 1250 ℃ electric furnace to found 1 hour.After the glass metal clarification, injection shifts to an earlier date preheated punching block moulding, then anneals 4 hours in 400 ℃ of retort furnaces, cools to room temperature with the furnace and namely gets product.

This glass under the ultraviolet excitation of 277nm, Sb ³⁺Can be effectively with transmission ofenergy to Mn ²⁺, there are two broadband emission peaks in glass, and peak value lays respectively at 428nm (indigo plant), 596nm (red), and relative intensity ratio is 1.06: 1, and chromaticity coordinates is (0.3277,0.3037).The utilizing emitted light spectrogram of embodiment 1 is seen Fig. 1.

Embodiment 2-7

In following each example, method for glass preparation is with embodiment 1, and the different glass compositions and fluorometric investigation and chromaticity coordinates calculation result of adopting listed in respectively table 2 and table 3.Embodiment 2 and 3 utilizing emitted light spectrogram are seen Fig. 2.

The glass of table 2 embodiment 2-5 forms (mol%):

Embodiment	P 2O 5	MgO	SrO	Sb 2O 3	MnO
						2	60	40	?	1	2
3	60	40	?	2.5	2
						4	60	?	40	1.5	2
5	75	?	25	2	2

The fluorometric investigation of table 3 embodiment 2-5 and chromaticity coordinates calculation result:

Embodiment	Excitation wavelength (nm)	Emission peak position (nm)	Chromaticity coordinates
				2	277	Sb 3+(428)，Mn 2+(596)	(0.3199，0.2979)
3	277	Sb 3+(428)，Mn 2+(596)	(0.3175，0.2943)
				4	277	Sb 3+(440)，Mn 2+(596)	(0.3033，0.3291)
5	277	Sb 3+(440)，Mn 2+(596)	(0.3156，0.3318)

Claims (4)

1. novel phosphoric acid salt white light glass is characterized in that its component and mole percent level are as follows:

P in the said components ₂O ₅With the RO sum be 100mol%; R=Mg wherein, Ca, one or more mixing wherein such as Sr, Ba, Zn etc.Transparent ionic conducting glass according to claim 1 is characterized in that, under the prerequisite that guarantees glass transparency, glass possesses the macroion conductivity.

2. novel white light glass according to claim 1 is characterized in that the luminescence center ion is Sb ³⁺And Mn ²⁺Ion.

3. novel white light glass according to claim 1 is characterized in that, glass can be excited effectively by UV-light, and has Sb ³⁺To Mn ²⁺Transmission ofenergy.

4. according to claim 1, the preparation method of 2,3 described novel white-light glass, its preparation method and being characterised in that may further comprise the steps:

A) raw material chooses

The phosphate glass raw material sources are in analytically pure primary ammonium phosphate, carbonate, oxide compound.Sb ³⁺The antimonous oxide that Analysis about Selection is pure, Mn ²⁺The carbonate that Analysis about Selection is pure;

B) weighing of glass batch and mixing

Accurately take by weighing glass batch, grinding fully mixes;

C) glass founding and annealing

Admixtion is put into the melting furnace that is warming up to 1000-1350 ℃ and was founded 1-2 hour, anneals a few hours about 300-450 ℃ subsequently, cools to room temperature with the furnace.

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