CN101665694B - Solid solution scintillation material of cubic phrase and preparation method thereof - Google Patents

Abstract

The invention discloses a solid solution scintillation material of cubic phrase, which has the following general formula: HfO2-Sc2O3: Eu<3+>, and is prepared by the following steps of: a) preparing Sc(NO3) 3 solution and Eu(NO3) 3 solution; b) adding HfOCl2 powder into a container and dissolving by distilled water, adding the Sc(NO3) 3 solution and the Eu(NO3) 3 solution into the HfOCl2 powder solution, and adjusting the PH value to be 1-2; c) when stirring the solution obtained in the step b, adding the blended fuel of glycine and urea into the solution; after intense agitation, heating for 20-30min at the temperature of 200 DEG C and removing moisture; and after being burnt for 40-70min in a muffle furnace at the temperature of 450 DEG C, obtaining the precursor; and d) sintering the precursor for 2h in a high-temperature furnace at the temperature of 800 DEG C, and obtaining the HfO2-Sc2O3: Eu<3+> solid solution scintillation material of the cubic phrase. The solid solution scintillation material of cubic phase is an optical function material which can give out visible light after absorbing high-energy photon, and can be applied to the fields such as high energy physics, nuclear medicine, industrial application, space physics, geological exploration and the like; furthermore, the preparation method has the advantages of being safe, time-saving, energy-saving and the like.

Description

Sosoloid scintillation material of cube phase and preparation method thereof

Technical field

The present invention relates to inorganic materials and preparing technical field thereof, particularly prepare a kind of cube of phase HfO with combustion method ₂-Sc ₂O ₃: Eu ³⁺The sosoloid scintillation material.

Background technology

Scintillation material is a kind of optical function material that sends visible light behind the high-energy photon that absorbs, and is widely used in fields such as high energy physics (like accurate electromagnetic calorimeter), nuclear medicine (like X-CT, PET), industrial application (CT flaw detection), space physics, geological prospecting.Working as that quantity is maximum, application is the widest pushes away inorganic scintillator.

It is flash detection important research direction at present that development high-performance flickering ceramic material comes progressively to replace present widely used monocrystalline scintillation material; The research emphasis content comprises: high-performance scintillating ceramic novel material system is explored in (1); Mainly be high-density, have a cube crystalline phase, the output of high light and the novel material system of shorter fall time, like lutecia based material, hafnates material etc.(2) the advanced preparation technology of research and development scintillation material comprises wet chemical method such as combustion method, the scintillating ceramic powder that the synthetic composition of coprecipitation method is controlled, sintering character is good, luminescent properties is good.(3) all kinds of different alloying elements of research are to the influence of material scintillation properties and influence mechanism.Because different doping agent is different to influences such as the light output of material, decay, twilight sunset, radiation injuries, therefore normally in a kind of scintillation material, mixing several kinds of different ions could the excellent scintillator of obtained performance.

HfO ₂Therefore material becomes the focus of people's concern day by day owing to have high k value (about 25), wide band gap (5.7eV), low-dielectric loss, low-leakage current and good capacitance-voltage characteristics, satisfactory stability property and excellent lattice matching characteristic.And HfO ₂Bigger ordination number, but density is big and characteristics doping with rare-earth ions also make it become important scintillation material.HfO ₂Have three kinds of thing phases: cube phase, monocline phase, cubic phase.Scintillation material requirement crystal is a cube phase generally speaking, however HfO ₂Be difficult to be stabilized in a cube phase.

Summary of the invention

Sosoloid scintillation material of a kind of cube of phase that the objective of the invention is to be directed against the deficiency of prior art and provide and preparation method thereof; It is fast and temperature of reaction is low that its method has resultant velocity; Energy-saving effect is obvious; The characteristics such as flicker powder that synthetic composition is controlled, sintering character is good, luminescent properties is good, 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:

The sosoloid scintillation material of a kind of cube of phase, characteristics are: this material general expression is: HfO ₂-Sc ₂O ₃: Eu ³⁺, and preparation according to the following steps:

A), get Sc ₂O ₃Be dissolved in HNO ₃In be made into the Sc (NO of 0.1～1mol/L ₃) ₃Solution is got Eu ₂O ₃Be dissolved in HNO ₃In be made into the Eu (NO of 0.08～0.1mol/L ₃) ₃Solution;

B), with HfOCl ₂Powder put into container with dissolved in distilled water after, to wherein adding Sc (NO ₃) ₃Solution after stirring, adds Eu (NO ₃) ₃Solution, the pH value that uses nitric acid to reconcile solution again is 1～2; Sc wherein ³⁺Molar content account for Sc ³⁺And Hf ⁴⁺The x% of total molar content, Hf ⁴⁺Molar content account for Sc ³⁺And Hf ⁴⁺(1-x) % of total molar content, Eu ³⁺Molar content account for Sc ³⁺And Hf ⁴⁺0.5% of total molar content, and x=13～90;

C), to b step solution while stirring to the propellant combination that wherein adds glycocoll and urea, after powerful the stirring, 200 ℃ down heating 20～30min remove moisture, the 40～70min that in 450 ℃ retort furnace, burns obtains presoma; Wherein glycocoll and urea integral molar quantity: Gd ³⁺And Hf ⁴⁺Integral molar quantity=y, and y=0.9～1.5, the molar weight of glycocoll is 40%～50% of glycocoll and a urea integral molar quantity; Remaining is a urea;

D), with presoma 800 ℃ of sintering 2h in High Temperature Furnaces Heating Apparatus, obtain the HfO of cube phase ₂-Sc ₂O ₃: Eu ³⁺The sosoloid scintillation material.

Scintillation material is a kind of optical function material that sends visible light behind the high-energy photon that absorbs, and is widely used in fields such as high energy physics (like accurate electromagnetic calorimeter), nuclear medicine (like HX-CT, PET), industrial application (CT flaw detection), space physics, geological prospecting.Combustion method has safely, saves time, advantage such as energy-conservation, is a very promising novel method.

The present invention is at HfO ₂In mix Sc ³⁺, make HfO ₂Be very stable cube phase, thereby obtain the very strong scintillation material of a kind of luminescent properties.This material itself is white in color; Can be excited well by the UV-light of the UV-light of 240～280nm wavelength region and 380～480nm wavelength region and visible light; Under 254nm and 397nm ultraviolet excitation, luminescent material presents bright redness, but along with Sc ³⁺The different luminous intensities of add-on also can be different.The emission peak wavelength is positioned at 593～595nm and 612～614nm.Work as Sc ³⁺Molar content account for Sc ³⁺And Hf ⁴⁺13%～90% o'clock of total molar content is a cube phase all, and works as Sc ³⁺Incorporation be that the symmetry of 17% o'clock cube of phase is best.

Description of drawings

Fig. 1 is the XRD of the embodiment of the invention 1 luminescent material

Fig. 2 is the XRD of the embodiment of the invention 2 luminescent materials

Fig. 3 is the emmission spectrum figure of the embodiment of the invention 3 luminescent materials

Fig. 4 is the exciting light spectrograms of the embodiment of the invention 3 luminescent materials at the 254nm wavelength

Fig. 5 is the exciting light spectrograms of the embodiment of the invention 3 luminescent materials in 380～580nm wavelength region

Embodiment

Embodiment 1

A), take by weighing 6g Sc ₂O ₃Be dissolved in HNO ₃In be made into the Sc (NO of 0.2837mol/L ₃) ₃Solution takes by weighing 15g Eu ₂O ₃Be dissolved in HNO ₃In be made into the Eu (NO of 0.09569mol/L ₃) ₃Solution;

B), take by weighing the HfOCl of 4.8832g ₂Powder put into beaker with dissolved in distilled water after, to the Sc (NO that wherein adds 9.0ml ₃) ₃Solution, Sc at this moment ³⁺Molar content account for Sc ³⁺And Hf ⁴⁺13% of total molar content after stirring, adds the Eu (NO of 1.0ml ₃) ₃Solution is measured the pH value of solution, with nitric acid it is adjusted to and approximates 1;

C), above-mentioned solution adds the glycocoll of 0.7320g and the propellant combination of 0.8565g urea to it while stirring, the powerful stirring fully dissolved it, 200 ℃ down heating 0.5h remove moisture, burning 1h obtains presoma in 450 ℃ retort furnace;

D), with presoma 800 ℃ of sintering 2h in High Temperature Furnaces Heating Apparatus, obtain the HfO of cube phase ₂-Sc ₂O ₃: Eu ³⁺The sosoloid scintillation material.

Embodiment 2

A), take by weighing 6g Sc ₂O ₃Be dissolved in HNO ₃In be made into the Sc (NO of 0.2837mol/L ₃) ₃Solution takes by weighing 15g Eu ₂O ₃Be dissolved in HNO ₃In be made into the Eu (NO of 0.09569mol/L ₃) ₃Solution;

B), take by weighing the HfOCl of 4.0870g ₂Powder put into beaker with dissolved in distilled water after, to the Sc (NO that wherein adds 16.0ml ₃) ₃Solution, Sc at this moment ³⁺Molar content account for Sc ³⁺And Hf ⁴⁺23% of total molar content after stirring, adds the Eu (NO of 1.0ml ₃) ₃Solution is measured the pH value of solution, with nitric acid it is adjusted to and approximates 1.

C), above-mentioned solution adds the glycocoll of 0.7320g and the propellant combination of 0.8565g urea to it while stirring, the powerful stirring fully dissolved it, 200 ℃ down heating 0.5h remove moisture, burning 1h obtains presoma in 450 ℃ retort furnace;

D), with presoma 800 ℃ of sintering 2h in High Temperature Furnaces Heating Apparatus, obtain the HfO of cube phase ₂-Sc ₂O ₃: Eu ³⁺The sosoloid scintillation material.

Embodiment 3

A), take by weighing 6g Sc ₂O ₃Be dissolved in HNO ₃In be made into the Sc (NO of 0.2837mol/L ₃) ₃Solution takes by weighing 15g Eu ₂O ₃Be dissolved in HNO ₃In be made into the Eu (NO of 0.09569mol/L ₃) ₃Solution;

B), take by weighing the HfOCl of 2.6539g ₂Powder put into beaker with dissolved in distilled water after, to the Sc (NO that wherein adds 35ml ₃) ₃Solution, Sc at this moment ³⁺Molar content account for Sc ³⁺And Hf ⁴⁺50% of total molar content after stirring, adds the Eu (NO of 1.0ml ₃) ₃Solution is measured the pH value of solution, with nitric acid it is adjusted to and approximates 1.

C), above-mentioned solution adds the glycocoll of 0.7320g and the propellant combination of 0.8565g urea to it while stirring, the powerful stirring fully dissolved it, 200 ℃ down heating 0.5h remove moisture, burning 1h obtains presoma in 450 ℃ retort furnace;

D), with presoma 800 ℃ of sintering 2h in High Temperature Furnaces Heating Apparatus, obtain the HfO of cube phase ₂-Sc ₂O ₃: Eu ³⁺The sosoloid scintillation material.

Embodiment 4

A), take by weighing 6g Sc ₂O ₃Be dissolved in HNO ₃In be made into the Sc (NO of 0.2837mol/L ₃) ₃Solution takes by weighing 15g Eu ₂O ₃Be dissolved in HNO ₃In be made into the Eu (NO of 0.09569mol/L ₃) ₃Solution;

B), take by weighing the HfOCl of 0.5308g ₂Powder put into beaker with dissolved in distilled water after, to the Sc (NO that wherein adds 63ml ₃) ₃Solution, Sc at this moment ³⁺Molar content account for Sc ³⁺And Hf ⁴⁺90% of total molar content after stirring, adds the Eu (NO of 1.0ml ₃) ₃Solution is measured the pH value of solution, with nitric acid it is adjusted to and approximates 1;

C), above-mentioned solution adds the glycocoll of 0.7320g and the propellant combination of 0.8565g urea to it while stirring, the powerful stirring fully dissolved it, 200 ℃ down heating 0.5h remove moisture, burning 1h obtains presoma in 450 ℃ retort furnace;

D), with presoma 800 ℃ of sintering 2h in High Temperature Furnaces Heating Apparatus, obtain the HfO of cube phase ₂-Sc ₂O ₃: Eu ³⁺The sosoloid scintillation material.

Claims (1)

1. the sosoloid scintillation material of one kind of cube of phase is characterized in that this material general expression is: HfO ₂-Sc ₂O ₃: Eu ³⁺, and preparation according to the following steps:

A), get Sc ₂O ₃Be dissolved in HNO ₃In be made into the Sc (NO of 0.1～1mol/L ₃) ₃Solution is got Eu ₂O ₃Be dissolved in HNO ₃In be made into the Eu (NO of 0.08～0.1mol/L ₃) ₃Solution;

B), with HfOCl ₂Powder put into container with dissolved in distilled water after, to wherein adding Sc (NO ₃) ₃Solution after stirring, adds Eu (NO ₃) ₃Solution, the pH value of using nitric acid to reconcile solution again is 1～2; Sc wherein ³⁺Molar content account for Sc ³⁺And Hf ⁴⁺The x% of total molar content, Hf ⁴⁺Molar content account for Sc ³⁺And Hf ⁴⁺(100-x) % of total molar content, Eu ³⁺Molar content account for Sc ³⁺And Hf ⁴⁺0.5% of total molar content, and x=13～90;

C), to b step solution while stirring to the propellant combination that wherein adds glycocoll and urea, after powerful the stirring, 200 ℃ down heating 20～30min remove moisture, the 40～70min that in 450 ℃ retort furnace, burns obtains presoma; Wherein glycocoll and urea integral molar quantity: Gd ³⁺And Hf ⁴⁺Integral molar quantity=y, and y=0.9～1.5, the molar weight of glycocoll is 40%～50% of glycocoll and a urea integral molar quantity; Remaining is a urea;

D), with presoma 800 ℃ of sintering 2h in High Temperature Furnaces Heating Apparatus, obtain the HfO of cube phase ₂-Sc ₂O ₃: Eu ³⁺The sosoloid scintillation material.

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