CN102827605B - A kind of method preparing white emitting fluorescent powder - Google Patents

A kind of method preparing white emitting fluorescent powder Download PDF

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Publication number
CN102827605B
CN102827605B CN201110157112.4A CN201110157112A CN102827605B CN 102827605 B CN102827605 B CN 102827605B CN 201110157112 A CN201110157112 A CN 201110157112A CN 102827605 B CN102827605 B CN 102827605B
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China
Prior art keywords
fluorescent powder
emitting fluorescent
saline solution
white emitting
silicon dioxide
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CN201110157112.4A
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Chinese (zh)
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CN102827605A (en
Inventor
李东平
王暄
徐基磊
林广龙
郭晓峰
王宝
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哈尔滨理工大学
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    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02BCLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
    • Y02B20/00Energy efficient lighting technologies
    • Y02B20/16Gas discharge lamps, e.g. fluorescent lamps, high intensity discharge lamps [HID] or molecular radiators
    • Y02B20/18Low pressure and fluorescent lamps
    • Y02B20/181Fluorescent powders

Abstract

Preparing a method for white emitting fluorescent powder, is a kind of preparation method of white emitting fluorescent powder mixing manganese, europium magnesium barium silicate, with containing BaCl 2, Mg (NO 3) 2, Mn (CH 3cOO) 2, EuCl 3the aqueous solution be initial saline solution through mixing with silicon dioxide gel-lyophilize-pre-burning-roasting obtains the operational path of product, the production line time of the present invention is short, and cost is low, and maturing temperature is low, and security in production process, the feature of environmental protection are good.

Description

A kind of method preparing white emitting fluorescent powder

Technical field

The present invention relates to a kind of preparation method of white emitting fluorescent powder, specifically a kind of preparation method of white emitting fluorescent powder mixing manganese, europium magnesium barium silicate.

Background technology

White light LEDs is energy-conservation with it, long service life, all solid state, volume is little, complanation, lightweight, good directionality, response are fast, radiationless and the advantage such as antidetonation, will become 21 century and substitute the new type light source of conventional illumination sources.White-light LED illumination is used to save mass energy, and harmful heavy metal such as not mercurous, so have very great meaning to the theoretical investigation of white light LEDs and commercial application research.Mix manganese, europium magnesium barium silicate as fluorescent material for white light LED of new generation, have single-matrix and silicate substrate two kinds of advantages concurrently, colour stable, color reducibility are good, are the study hotspots of White-light LED illumination of new generation.High temperature solid-state method and aerosol spray method is generally adopted at present at this type of fluorescent material of preparation.High temperature solid-state method energy consumption is higher, aerosol spray method complicated operation.Patent of the present invention adopts freeze-drying to prepare the presoma of fluorescent material.Simple, each component of this method experimental implementation mixes, saves time again and the energy while having sol-gel method advantage.

Summary of the invention

The object of the present invention is to provide a kind of production process safety, environmental protection, and operational path simply prepares white emitting fluorescent powder method.

In order to achieve the above object, the technical solution used in the present invention is with containing BaCl 2, Mg (NO 3) 2, Mn (CH 3cOO) 2, EuCl 3the aqueous solution be initial saline solution through mixing with silicon dioxide gel-lyophilize-pre-burning-roasting obtains mixing the white emitting fluorescent powder of manganese, europium magnesium barium silicate.

Advantage of the present invention is:

1, the presoma that freeze-drying is obtained mixes.This is due to colloidal sol and does not get transformed into gel but be directly rapidly frozen, and does not so just need colloidal sol to the long-time conversion process of gel, so do not have the process of fractions crystallization, this ensures that theres presoma and mix.

2, freeze-drying is relative to the aerosol spray method reported, freezing method and microwave heating more save the energy.

3, also fairly simple in freeze-drying operation, what aerosol spray method also will control colloidal sol enters glue speed, microwave intensity factor, complicated operation.

4, raw material cleans, and we are mainly solvent with water, and raw materials usedly also all changes into product, does not have waste residue to produce.Environment is not polluted.

Embodiment

Be described in further detail below in conjunction with embodiments of the invention:

Prepare a method for white emitting fluorescent powder, with containing BaCl 2, Mg (NO 3) 2, Mn (CH 3cOO) 2, EuCl 3the aqueous solution be initial saline solution through mixing with silicon dioxide gel-lyophilize-pre-burning-roasting obtains the operational path of product.

The described method preparing white emitting fluorescent powder, BaCl in initial salt 2with Mg (NO 3) 2with Mn (CH 3cOO) 2with EuCl 3the ratio of amount of substance is 3: 1: 0.1: 0.01 ~ 3: 1: 0.1: 0.05, the mass percentage concentration of initial saline solution is 10% ~ 15%, the volume ratio of initial saline solution and silicon dioxide gel is 2: 1 ~ 3: 1, calcined temperature is 200 ~ 400 DEG C, burn-in time is 1 hour ~ 3 hours, and maturing temperature is 1100 ~ 1300 DEG C, roasting time is 4 hours ~ 6 hours.

The described method preparing white emitting fluorescent powder, tetraethoxy, ethanol are added in deionized water by the preparation method of silicon dioxide gel successively, and the volume ratio of tetraethoxy and ethanol and deionized water is 5: 10: 3, and the pH value controlling colloidal sol with hydrochloric acid equals 3.

Embodiment 1

Be added in deionized water by tetraethoxy, ethanol successively, volume ratio 5: 10: 3, with hydrochloric acid, the pH value controlling colloidal sol is 3.Be 3: 1: 0.1: 0.01 successively by BaCl by the ratio of amount 2, Mg (NO 3) 2, Mn (CH 3cOO) 2, EuCl 3be dissolved in deionized water, be made into the initial saline solution that mass percentage concentration is 15%.

With containing BaCl 2, Mg (NO 3) 2, Mn (CH 3cOO) 2, EuCl 3the aqueous solution be that initial saline solution slowly joins in silicon dioxide gel, Keep agitation, makes it mix, and period, hierarchy of control pH equaled 3, and the volume ratio of initial saline solution and silicon dioxide gel is 2: 1.To mix, and not have the complex sol of Precipitation to pour in sample sack, put into liquid nitrogen quick freezing.Solid sample after freezing is broken into fritter, processes under low-temp low-pressure with freeze drier, make moisture rapid sublimation wherein, obtain the precursor powder of homogeneous drying.Freeze drier working conditions sets: working temperature as-55 DEG C, operating pressure: 5mTorr.Above-mentioned precursor powder is placed in retort furnace, pre-burning 2 hours at 300 DEG C.By the sample grinding after above-mentioned pre-burning, be placed in atmosphere protection type tube furnace, adopt H 2atmosphere protection, control maturing temperature at 1200 DEG C, roasting 5 hours, takes out and obtains the white emitting fluorescent powder mixing manganese, europium magnesium barium silicate after naturally cooling.

Under excitation wavelength 375nm, with the fluorescence spectrum of HitachiF4500 type spectrophotofluorometer test products, product launches indigo plant, green, red trichromatism light simultaneously.

Embodiment 2

Be added in deionized water by tetraethoxy, ethanol successively, volume ratio 5: 10: 3, with hydrochloric acid, the pH value controlling colloidal sol is 3.Be 3: 1: 0.1: 0.02 successively by BaCl by the ratio of amount 2, Mg (NO 3) 2, Mn (CH 3cOO) 2, EuCl 3be dissolved in deionized water, be made into the initial saline solution that mass percentage concentration is 10%.

With containing BaCl 2, Mg (NO 3) 2, Mn (CH 3cOO) 2, EuCl 3the aqueous solution be that initial saline solution slowly joins in silicon dioxide gel, Keep agitation, makes it mix, and period, hierarchy of control pH equaled 3, and the volume ratio of initial saline solution and silicon dioxide gel is 3: 1.To mix, and not have the complex sol of Precipitation to pour in sample sack, put into liquid nitrogen quick freezing.Solid sample after freezing is broken into fritter, processes under low-temp low-pressure with freeze drier, make moisture rapid sublimation wherein, obtain the precursor powder of homogeneous drying.Freeze drier working conditions sets: working temperature as-55 DEG C, operating pressure: 5mTorr.Above-mentioned precursor powder is placed in retort furnace, pre-burning 1 hour at 400 DEG C.By the sample grinding after above-mentioned pre-burning, be placed in atmosphere protection type tube furnace, adopt H 2atmosphere protection, control maturing temperature at 1300 DEG C, roasting 4 hours, takes out and obtains the white emitting fluorescent powder mixing manganese, europium magnesium barium silicate after naturally cooling.

Under excitation wavelength 375nm, with the fluorescence spectrum of HitachiF4500 type spectrophotofluorometer test products, product launches indigo plant, green, red trichromatism light simultaneously.

Claims (2)

1. prepare a method for white emitting fluorescent powder, it is characterized in that: with containing BaCl 2, Mg (NO 3) 2, Mn (CH 3cOO) 2, EuCl 3the aqueous solution be initial saline solution through mixing with silicon dioxide gel-lyophilize-pre-burning-roasting obtains the operational path of product, BaCl in initial saline solution 2with Mg (NO 3) 2with Mn (CH 3cOO) 2with EuCl 3the ratio of amount be 3: 1: 0.1: 0.01 ~ 3: 1: 0.1: 0.05, the mass percentage concentration of initial saline solution is 10% ~ 15%, the volume ratio of initial saline solution and silicon dioxide gel is 2: 1 ~ 3: 1, calcined temperature is 200 ~ 400 DEG C, burn-in time is 1 hour ~ 3 hours, and maturing temperature is 1100 ~ 1300 DEG C, roasting time is 4 hours ~ 6 hours.
2. according to a kind of method preparing white emitting fluorescent powder according to claim 1, it is characterized in that: tetraethoxy, ethanol are added in deionized water by the preparation method of silicon dioxide gel successively, the volume ratio of tetraethoxy and ethanol and deionized water is 5: 10: 3, and the pH value controlling colloidal sol with hydrochloric acid equals 3.
CN201110157112.4A 2011-06-13 2011-06-13 A kind of method preparing white emitting fluorescent powder CN102827605B (en)

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CN103146387B (en) * 2013-03-19 2015-04-08 山东大学 Process for preparing porous rare-earth luminescent material by freeze-drying method

Citations (2)

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CN1585141A (en) * 2003-08-20 2005-02-23 刘行仁 White light LED and light converting luminophore
US7871542B2 (en) * 2001-10-30 2011-01-18 Hitachi, Ltd. Plasma display device, luminescent device and image and information display system using the same

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7871542B2 (en) * 2001-10-30 2011-01-18 Hitachi, Ltd. Plasma display device, luminescent device and image and information display system using the same
CN1585141A (en) * 2003-08-20 2005-02-23 刘行仁 White light LED and light converting luminophore

Non-Patent Citations (2)

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用于单芯片红蓝双光LED的Ba3MgSi2O8 : Eu2+ , Mn2+荧光体的荧光增强效应的研究;刘凌云;《天津理工大学硕士学位论文》;20100731;32-34 *
近紫外光激发的Ba3MgSi2 O8 : Eu2+ , Mn2+ 全色荧光材料的发光性质研究;毛智勇 等;《天津理工大学学报》;20081215;第24卷(第6期);9-12 *

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