CN101445725B

CN101445725B - Hafnate luminescent material and preparation method thereof

Info

Publication number: CN101445725B
Application number: CN2008102049426A
Authority: CN
Inventors: ***; 孟婧
Original assignee: East China Normal University
Current assignee: East China Normal University
Priority date: 2008-12-30
Filing date: 2008-12-30
Publication date: 2012-05-09
Anticipated expiration: 2028-12-30
Also published as: CN101445725A

Abstract

The invention discloses a hafnate luminescent material which has the general formula of Y2-xHf7O17:Eux, wherein, X is 0.01-0.3; the invention also discloses a method for preparing the hafnate luminescent material, which comprises the steps: solid yttrium nitrate and hafnyl chloride are put into a container by taking the mol ratio of 3:25-3:10 as the mixture ratio and dissolved by distilled water; Eu(NO3)3 solution is added into the mixture, and the molar weight of Eu is 1%-30% of the molar weight of Y; the pH value of the solution is regulated to be 1 by using nitric acid; the blended fuel ofglycin and urea is added into the solution, and ethylenediamine tetracetic acid (EDTA) having the mass accounting for millesimal of the total mass of the raw material is taken as chelating agent and added into the solution; the mixture is burnt in a furnace at the temperature of 450 DEG C to obtain precursor, and then sintered for 2 hours at 800 DEG C in a high temperature furnace, thereby obtaining the Y2-xHf7O17:Eux material. The material obtained by the invention can be used in an X-ray intensifying screen of high-energy physics, medical use or safety inspection. The preparing method has the advantages of safety, time-saving, energy-efficiency, etc.

Description

A kind of hafnates luminescent material and preparation method

Technical field

The present invention relates to inorganic materials and preparing technical field thereof, particularly a kind of can be as scintillator, be used for high energy physics or medical or safety check X ray sensitizing inorganic hafnates luminescent material and its preparation method is provided.

Background technology

Scintillation material is meant and can absorbs the material that high energy particle or ray send optical photon.Inorganic scintillation material is widely used in ionizing rays and surveys.In decades in the past, scintillation material increases rapidly in accurate mensuration of high energy physics heat and imaging of medical field.The development of scintillator is divided into 3 stages, and when at first the roentgen had found X ray with calcium wolframate, Becquerel had found radioactivity with uranium phthalein salt, during Crooke research Zns, finds and calculated radioactivity during Rutherford research a particle scattering.The discovery of the scintillation of naphthalene makes scintillation material development get into subordinate phase, and then has caused Hofstadters and excite the Nal crystal with engraving.Scientist has started the research climax to many blinking characteristics pure or adulterated alkali halate in subsequently several years.Contain the file compound in the 1950's and be used for detected neutron and first and mix the Ce scintillation glass and also begun research, comprise fast scintillator BaF2 etc.Phase III; In the past 20 in the period of; Because study of high energy physics needs accurate thermal flow measurement, digital medical imaging to need scintillation material, geophysical survey and the various science industrial application of high light yield, the scintillation material development has got into the real recovery stage like this.

High-temperature solid phase reaction method is the domestic method of preparation luminescent material; This method is that raw material is even by certain proportioning ball mill mixing; Then under reducing atmosphere or protection (inertia) atmosphere in 1000-1600 ℃ of high-temperature calcination stoichiometric number hour, the final powder breakdown mill obtains product.But high temperature solid-state method also has certain shortcoming: this method need let crystal slowly grow at several hours under the condition of high temperature, the general crystal grain of the product that obtains is bigger, and hardness is big; And need through ball milling, crystalline form can be destroyed so, forms inhomogeneous; Luminosity descends significantly; Also have energy consumption big in addition, preparation cycle is long, is difficult to avoid second phase; Sol-gel method is inorganic salt and metal alkoxide or other organic salt to be dissolved in form uniform solution in water or the organic solvent; Solute and solvent produce hydrolysis, alcoholysis or integrating remark and form colloidal sol; After evaporation drying is transformed into gel, gel obtains product through processes such as super-dry, thermal treatments.The shortcoming of sol-gel method is that cost is high because use metal, and the production cycle is long, and the luminescent properties aspect does not improve significantly.

Summary of the invention

The purpose of this invention is to provide a kind of hafnates luminescent material and preparation method thereof; It is fast and temperature of reaction is low that this method has resultant velocity; The tangible characteristics of energy-saving effect, the phosphor that is obtained can be used in the X ray intensifying screen of high energy physics or medical or safety check.

The objective of the invention is to realize like this:

A kind of hafnates luminescent material is characterized in that this material general expression is: Y _2-xHf ₇O ₁₇: Eu _x, in the formula: X is 0.01～0.3; And preparation according to the following steps:

A), solid nitric acid yttrium and hafnyl chloride are put into container by its molar weight than 3: 25～3: 10 proportioning, use dissolved in distilled water, in it, add Eu (NO ₃) ₃Solution, its Eu (NO ₃) ₃In the solution molar content of Eu account for yttrium molar content 1～30%, the pH value that uses nitric acid to reconcile solution again is 1.

B), above-mentioned solution adds the propellant combination of glycocoll and urea while stirring to it; And the millesimal YD 30 (EDTA) that adds the raw material total mass is done sequestrant; After powerful the stirring, under 200 ℃, remove moisture, burning obtains presoma in 450 ℃ retort furnace.

C), with presoma 800 ℃ of sintering 2 hours in High Temperature Furnaces Heating Apparatus, obtain Y _2-xHf ₇O ₁₇: Eu _xMaterial.

Advantages such as the phosphor that the present invention obtains can be used in the X ray intensifying screen of high energy physics or medical or safety check, and its preparation method has safely, saves time, energy-conservation are very promising novel methods.

Description of drawings

Fig. 1 is the XRD of embodiment 1 luminescent material

Fig. 2 is the emmission spectrum figure of embodiment 1 luminescent material

Fig. 3 is the exciting light spectrogram of embodiment 1 luminescent material

Fig. 4 is the concentration quenching curve of embodiment 1 luminescent material

Fig. 5 is the Electronic Speculum spectrogram of embodiment 1 luminescent material

Embodiment

Embodiment 1

Y (NO ₃) ₃6H ₂O 4.7880g, HfOCl ₂11.6110g, the Eu (NO of 0.095mol/l ₃) ₃Solution 4.0ml, C ₂H ₅NO ₂0.7820g, CH ₄N ₂O 0.9384g.

Take by weighing 4.7880g Y (NO ₃) ₃6H ₂O powder and 11.6110g HfOCl ₂Powder put into beaker with dissolved in distilled water after, to the Eu (NO that wherein adds 4.0ml ₃) ₃Solution is measured the pH value of solution, with nitric acid it is adjusted to and approximates 1.Beaker is put on the magnetic stirring apparatus, while stirring to the glycocoll C that wherein adds 0.7820g ₂H ₅NO ₂With 0.9384g urea CH ₄N ₂O, and add 0.015 gram EDTA as sequestrant powerful stirs for some time up to raw material and fuel mixing.Mixture is put in 200 ℃ the baking oven and boils off moisture, put it into then and be heated to 450 ℃ in the retort furnace, make its foaming, burning, 800 ℃ of heating 2 hours in High Temperature Furnaces Heating Apparatus more finally obtain required luminescent material.

Consult accompanying drawing, present embodiment gained material structure does not have other dephasigns to disturb, and thing is very pure mutually.This luminescent material itself is white in color, and can be excited well by the UV-light of 370～460nm wavelength region and visible light, excites down at 400nm, and glow color presents bright redness, and the emission peak wavelength is positioned at about 614nm.

Embodiment 2

Y (NO ₃) ₃6H ₂O 4.7880g, HfOCl ₂11.6110g, the Eu (NO of 0.095mol/l ₃) ₃Solution 6.0ml, C ₂H ₅NO ₂0.7820g, CH ₄N ₂O 0.9384g.

Take by weighing 4.7880g Y (NO ₃) ₃6H ₂O powder and 11.6110g HfOCl ₂Powder put into beaker with dissolved in distilled water after, to the Eu (NO that wherein adds 6.0ml ₃) ₃Solution.Measure the pH value of solution, with nitric acid it is adjusted to and approximates 1.Beaker is put on the magnetic stirring apparatus, while stirring to the glycocoll C that wherein adds 0.7820g ₂H ₅NO ₂With 0.9384g urea CH ₄N ₂O, and add 0.015 gram EDTA as sequestrant powerful stirs for some time up to raw material and fuel mixing.Mixture is put in 200 ℃ the baking oven and boils off moisture, put it into then and be heated to 450 ℃ in the retort furnace, make its foaming, burning, 800 ℃ of heating 2 hours in High Temperature Furnaces Heating Apparatus more finally obtain required luminescent material.Present embodiment institute synthetic luminescent material structure is identical with embodiment 1.

Embodiment 3

Y (NO ₃) ₃6H ₂O 4.7880g, HfOCl ₂11.6110g, the Eu (NO of 0.095mol/l ₃) ₃Solution 8.0ml, C ₂H ₅NO ₂0.7820g, CH ₄N ₂O 0.9384g.

Take by weighing 4.7880g Y (NO ₃) ₃6H ₂O powder and 11.6110g HfOCl ₂Powder put into beaker with dissolved in distilled water after, to the Eu (NO that wherein adds 8.0ml ₃) ₃Solution.Measure the pH value of solution, with nitric acid it is adjusted to and approximates 1.Beaker is put on the magnetic stirring apparatus, while stirring to the glycocoll C that wherein adds 0.7820g ₂H ₅NO ₂With 0.9384g urea CH ₄N ₂O, and add 0.015 gram EDTA as sequestrant powerful stirs for some time up to raw material and fuel mixing.Mixture is put in 200 ℃ the baking oven and boils off moisture, put it into then and be heated to 450 ℃ in the retort furnace, make its foaming, burning, 800 ℃ of heating 2 hours in High Temperature Furnaces Heating Apparatus more finally obtain required luminescent material.Present embodiment institute synthetic scintillation material structure is identical with embodiment 1.

Claims

1. a hafnates luminescent material is characterized in that this material general expression is: Y _2-xHf ₇O ₁₇: Eu _x, in the formula: X is 0.01～0.3; And preparation according to the following steps:

A), solid nitric acid yttrium and hafnyl chloride are put into container by 3: 25～3: 10 proportioning of its mol ratio, use dissolved in distilled water, in it, add Eu (NO ₃) ₃Solution, its Eu (NO ₃) ₃In the solution molar content of Eu account for yttrium molar content 1～30%, the pH value of using the nitric acid regulator solution again is 1;

B), above-mentioned solution adds the propellant combination of glycocoll and urea while stirring to it; And the millesimal YD 30 of adding raw material total mass is done sequestrant; After powerful the stirring, under 200 ℃, remove moisture, burning obtains presoma in 450 ℃ retort furnace;