CN102351205A - Preparation method of scintillation bismuth silicate powder - Google Patents

Abstract

The invention, relating to the preparation of a scintillation crystalline material, discloses a preparation method of scintillation bismuth silicate powder, comprising the following steps: using absolute ethyl alcohol as a ball milling medium, carrying out ball milling on Bi2O3 and SiO2 for 5 h with the molar ratio of 1:1.5 to 1:2, carrying out ball milling on KCl and K2SO4 for 5 h with the molar ratio of 0.65:0.35 to 0.9:0.1, then carrying out hand grinding on the dried mixture of Bi2O3 and SiO2 and the KCl-K2SO4 composite salt for 30 min with the weight ratio of 1:4 to 4:1; putting the hand grinded mixed batch in an alumina crucible, then putting the alumina crucible in a muffle furnace, keeping warm for 0.5-3 h at the temperature of 750-850 DEG C, taking out, and cooling; finally cleaning the cooled sample in ultrasonic waves with deionized water and drying to obtain the Bi4Si3O12 powder. According to the invention, Bi4Si3O12 can be prepared rapidly and simply with high product purity, and the invention is convenient for large scale production.

Description

A kind of preparation method of the bismuth silicate powder that glimmers

Technical field

The present invention relates to the preparation of scintillator crystal materials, disclose a kind of preparation method of the bismuth silicate powder that glimmers.

Background technology

Bi ₄Si ₃O ₁₂Crystal mainly has flashing function, and it is transparent at visible light and near infrared region, and its response speed is than the scintillator Bi of present widespread use ₄Ge ₃O ₁₂Fast 3 times, half-width (FWHM) energy resolution of locating at 662keV (37Cs) is Bi ₄Ge ₃O ₁₂32%, anti-60Co gamma-rays radiating performance is greater than 105rad at emission peak 460nm place, radiation hardness compares Bi ₄Ge ₃O ₁₂A high one magnitude.Machinery and the chemical stability of height, the good characteristics of luminescence and low-cost advantage make Bi ₄Si ₃O ₁₂Crystal becomes one of rising scintillator.Can replace Bi in some aspects ₄Ge ₃O ₁₂, for example the high energy positron-electron is stored the calorimeter in the loop detection device.In addition, Bi ₄Si ₃O ₁₂Crystal also has performances such as electric light, thermoluminescence.

Although people are familiar with eulytite (Bi ₄Si ₃O ₁₂) there be more than 180 year, but just utilize Czochralski grown to go out Bi up to Philipsborn in 1971 etc. ₄Si ₃O ₁₂Monocrystalline.Because many advantages of this method, crystal pulling method are the main method of BSO monocrystalline of growing both at home and abroad always.What another kind was commonly used is falling crucible method, through prolonging platinum crucible smelting time and the suitable crystal growth furnace temperature that reduces, has obviously reduced defectives such as platinum inclusion, has finally obtained good monocrystalline.L. Armelao in 1998 etc. have prepared Bi with sol-gel method ₄Si ₃O ₁₂Film.Jin-Seong Kim equals to synthesize Bi with solid sintering technology in 2008 ₄Si ₃O ₁₂Pottery.

The conventional solid state reaction sintering process can be a raw materials mix with bismuth oxide and silicon oxide powder, makes bismuth silicate powder through solid state reaction.The shortcoming of this method is that the mixing of two kinds of raw materials is difficult to reach complete and homogeneous, and grain growing at high temperature, reunion, is difficult to obtain the desirable amount powder granule.Field clear spring, Zhang Zhengguang etc. have prepared Bi with solid phase method ₄Si ₃O ₁₂Powder is discovered, Bi ₄Si ₃O ₁₂Crystallite always distributes in pairs, and arranges in a row, and forms high orderly brilliant array structure.Employing solid phase methods such as Wang Yan have synthesized Bi ₂SiO ₅Powder, research is illustrated in the metastable phase Bi that generates in the solid state reaction process ₂SiO ₅Along with reaction times prolongation diffraction peak weakens, be increased in 900 ℃ of processes Bi by 700 ℃ in the solid state reaction temperature ₂SiO ₅Change Bi gradually into ₄Si ₃O ₁₂

Ba Xuewei, Bai Chaohui etc. are with tetraethoxy and Bi ₂O ₃Be raw material, adopt sol-gel method to prepare basic configuration and be bismuth silicate (Bi spherical, particle diameter 40-100nm ₄Si ₃O ₁₂) nano-powder, and studied the excitation spectrum and the emmission spectrum of powder.Bi ₄Si ₃O ₁₂Exciting of nano-powder mainly occurs between 250～275nm, and its maximum excitation wavelength is 261nm.The emmission spectrum of sample is a wideband spectrum, and maximum emission wavelength is positioned at 468nm.Compare with crystal, blue shift has taken place in the excitation spectrum and the emmission spectrum of BSO nano-powder.Infer that reason is that nanometer material structure groups of grains elemental size is very little, surface tension is very big, and distortion takes place granule interior shortens the bond distance, and the nano material average bond length is shortened, and the key chattering frequency raises as a result, causes blue shift.

People such as Zhu Changren are raw material with tetraethoxy and five water Bismuth trinitrates, adopt the chemical solution decomposition method to prepare Bi ₄Si ₃O ₁₂Powder.With X-ray diffractometer and scanning electron microscope analysis the phase structure and the pattern of powder, studied of the influence of the consumption of tetraethoxy to the powder phase composite.The result shows that the precursor powder was calcined 1 hour down at 650 ℃, had obtained single Bi ₄Si ₃O ₁₂Powder; Granular size is 3～5 μ m, is that the crystal grain of 300～500nm consists of the porous reticulated structure by several sizes; When bismuth silicon is 1: 2 than the consumption of (mol ratio), can prepares phase composite and be entirely Bi ₄Si ₃O ₁₂Powder.Consuming time when this method prepares precursor, it is poisonous to be used for the ethylene glycol monomethyl ether of regulator solution viscosity, and proportioning raw materials is not to generate Bi ₄Si ₃O ₁₂The proportioning of crystalline phase is unfavorable for big production.

Summary of the invention

In order to overcome the deficiency of above-mentioned prior art, the object of the present invention is to provide a kind of method for preparing the bismuth silicate powder that glimmers, can prepare Bi simply fast ₄Si ₃O ₁₂, and product purity is high, is convenient to scale operation.

To achieve these goals, the technical scheme of the present invention's employing is:

A kind of preparation method of the bismuth silicate powder that glimmers may further comprise the steps:

The first step is a ball-milling medium with the dehydrated alcohol, with Bi ₂O ₃And SiO ₂Ball milling was 5 hours in 1: 1.5 in molar ratio～1: 2, as reaction raw materials;

Second step was a ball-milling medium with the dehydrated alcohol, with KCl and K ₂SO ₄Ball milling was 5 hours in 0.65: 0.35 in molar ratio～0.9: 0.1, obtained KCl-K ₂SO ₄Composite salt;

The 3rd step is with the Bi of oven dry ₂O ₃And SiO ₂Compound and KCl-K ₂SO ₄Composite salt is with 1: 4～4: 1 hand mill 30min in mortar of mass ratio;

The 4th step, the admixtion behind the hand mill is put into alumina crucible, then crucible is put into retort furnace, be incubated 0.5～3 hour under 750 ℃～850 ℃ conditions, take out, be cooled to room temperature;

The 5th the step, with the refrigerative sample in ultrasonic wave with drying after the washed with de-ionized water, promptly get Bi ₄Si ₃O ₁₂Powder.

Wherein, more than the cleaning in the 5th step can be carried out once repeatedly.

Compared with prior art, advantage of the present invention is:

(1) method is easy, easy handling, and reaction conditions is gentle;

(2) production cost is low, the short about 13～25h of preparation cycle;

(3) product purity is high, can reach 85%～100%.

Embodiment

Below in conjunction with embodiment the present invention is explained further details.

Embodiment one

A kind of preparation method of the bismuth silicate powder that glimmers may further comprise the steps:

The first step is a ball-milling medium with the dehydrated alcohol, with Bi ₂O ₃And SiO ₂Ball milling was 5 hours in 2: 3 in molar ratio, as reaction raw materials;

Second step was a ball-milling medium with the dehydrated alcohol, with KCl and K ₂SO ₄Ball milling was 5 hours in 0.74: 0.26 in molar ratio, obtained KCl-K ₂SO ₄Composite salt;

The 3rd step is with the Bi of oven dry ₂O ₃And SiO ₂Compound and KCl-K ₂SO ₄Composite salt is with 3: 2 hand mill 30min in mortar of mass ratio;

The 4th step, the admixtion behind the hand mill is put into alumina crucible, then crucible is put into retort furnace, insulation is 3 hours under 750 ℃ of conditions, takes out, and is cooled to room temperature;

The 5th the step, with the refrigerative sample in ultrasonic wave with drying after the washed with de-ionized water, promptly get Bi ₄Si ₃O ₁₂Powder.

Embodiment two

A kind of preparation method of the bismuth silicate powder that glimmers may further comprise the steps:

The first step is a ball-milling medium with the dehydrated alcohol, with Bi ₂O ₃And SiO ₂Ball milling was 5 hours in 2: 3 in molar ratio, as reaction raw materials;

Second step was a ball-milling medium with the dehydrated alcohol, with KCl and K ₂SO ₄Ball milling was 5 hours in 0.74: 0.26 in molar ratio, obtained KCl-K ₂SO ₄Composite salt;

The 3rd step is with the Bi of oven dry ₂O ₃And SiO ₂Compound and KCl-K ₂SO ₄Composite salt is with 3: 2 hand mill 30min in mortar of mass ratio;

The 4th step, the admixtion behind the hand mill is put into alumina crucible, then crucible is put into retort furnace, insulation is 3 hours under 800 ℃ of conditions, takes out, and is cooled to room temperature;

The 5th the step, with the refrigerative sample in ultrasonic wave with drying after the washed with de-ionized water, promptly get Bi ₄Si ₃O ₁₂Powder.

Embodiment three

A kind of preparation method of the bismuth silicate powder that glimmers may further comprise the steps:

The first step is a ball-milling medium with the dehydrated alcohol, with Bi ₂O ₃And SiO ₂Ball milling was 5 hours in 2: 3 in molar ratio, as reaction raw materials;

Second step was a ball-milling medium with the dehydrated alcohol, with KCl and K ₂SO ₄Ball milling was 5 hours in 0.74: 0.26 in molar ratio, obtained KCl-K ₂SO ₄Composite salt;

The 3rd step is with the Bi of oven dry ₂O ₃And SiO ₂Compound and KCl-K ₂SO ₄Composite salt is with 4: 1 hand mill 30min in mortar of mass ratio;

The 4th step, the admixtion behind the hand mill is put into alumina crucible, then crucible is put into retort furnace, insulation is 3 hours under 820 ℃ of conditions, takes out, and is cooled to room temperature;

The 5th the step, with the refrigerative sample in ultrasonic wave with drying after the washed with de-ionized water, promptly get Bi ₄Si ₃O ₁₂Powder.

Embodiment four

A kind of preparation method of the bismuth silicate powder that glimmers may further comprise the steps:

The first step is a ball-milling medium with the dehydrated alcohol, with Bi ₂O ₃And SiO ₂Ball milling was 5 hours in 1: 2 in molar ratio, as reaction raw materials;

Second step was a ball-milling medium with the dehydrated alcohol, with KCl and K ₂SO ₄Ball milling was 5 hours in 0.29: 0.11 in molar ratio, obtained KCl-K ₂SO ₄Composite salt;

The 3rd step is with the Bi of oven dry ₂O ₃And SiO ₂Compound and KCl-K ₂SO ₄Composite salt is with 1: 4 hand mill 30min in mortar of mass ratio;

The 4th step, the admixtion behind the hand mill is put into alumina crucible, then crucible is put into retort furnace, insulation is 0.5 hour under 850 ℃ of conditions, takes out, and is cooled to room temperature;

The 5th the step, with the refrigerative sample in ultrasonic wave with drying after the washed with de-ionized water, promptly get Bi ₄Si ₃O ₁₂Powder.

Embodiment five

A kind of preparation method of the bismuth silicate powder that glimmers may further comprise the steps:

The first step is a ball-milling medium with the dehydrated alcohol, with Bi ₂O ₃And SiO ₂Ball milling was 5 hours in 1: 1.8 in molar ratio, as reaction raw materials;

Second step was a ball-milling medium with the dehydrated alcohol, with KCl and K ₂SO ₄Ball milling was 5 hours in 0.31: 0.09 in molar ratio, obtained KCl-K ₂SO ₄Composite salt;

The 3rd step is with the Bi of oven dry ₂O ₃And SiO ₂Compound and KCl-K ₂SO ₄Composite salt is with 1: 1 hand mill 30min in mortar of mass ratio;

The 4th step, the admixtion behind the hand mill is put into alumina crucible, then crucible is put into retort furnace, insulation is 2 hours under 780 ℃ of conditions, takes out, and is cooled to room temperature;

The 5th the step, with the refrigerative sample in ultrasonic wave with drying after the washed with de-ionized water, promptly get Bi ₄Si ₃O ₁₂Powder.

Embodiment six

A kind of preparation method of the bismuth silicate powder that glimmers may further comprise the steps:

The first step is a ball-milling medium with the dehydrated alcohol, with Bi ₂O ₃And SiO ₂Ball milling was 5 hours in 1: 2 in molar ratio, as reaction raw materials;

Second step was a ball-milling medium with the dehydrated alcohol, with KCl and K ₂SO ₄Ball milling was 5 hours in 9: 1 in molar ratio, obtained KCl-K ₂SO ₄Composite salt;

The 3rd step is with the Bi of oven dry ₂O ₃And SiO ₂Compound and KCl-K ₂SO ₄Composite salt is with 1: 1 hand mill 30min in mortar of mass ratio;

The 4th step, the admixtion behind the hand mill is put into alumina crucible, then crucible is put into retort furnace, insulation is 2 hours under 780 ℃ of conditions, takes out, and is cooled to room temperature;

The 5th the step, with the refrigerative sample in ultrasonic wave with drying after the washed with de-ionized water, promptly get Bi ₄Si ₃O ₁₂Powder.

Embodiment seven

A kind of preparation method of the bismuth silicate powder that glimmers may further comprise the steps:

The first step is a ball-milling medium with the dehydrated alcohol, with Bi ₂O ₃And SiO ₂Ball milling was 5 hours in 1: 1.8 in molar ratio, as reaction raw materials;

Second step was a ball-milling medium with the dehydrated alcohol, with KCl and K ₂SO ₄Ball milling was 5 hours in 65: 35 in molar ratio, obtained KCl-K ₂SO ₄Composite salt;

The 3rd step is with the Bi of oven dry ₂O ₃And SiO ₂Compound and KCl-K ₂SO ₄Composite salt is with 1: 1 hand mill 30min in mortar of mass ratio;

The 4th step, the admixtion behind the hand mill is put into alumina crucible, then crucible is put into retort furnace, insulation is 2 hours under 780 ℃ of conditions, takes out, and is cooled to room temperature;

The 5th the step, with the refrigerative sample in ultrasonic wave with drying after the washed with de-ionized water, promptly get Bi ₄Si ₃O ₁₂Powder.

More than among each embodiment, the cleaning in the 5th step can be carried out repeatedly, effect is better.Bi to above each embodiment preparation ₄Si ₃O ₁₂The powder analysis that makes an experiment, its purity can reach 85%～100%.

Claims (7)

1. the preparation method of the bismuth silicate powder that glimmers is characterized in that, may further comprise the steps:

The first step is a ball-milling medium with the dehydrated alcohol, with Bi ₂O ₃And SiO ₂Ball milling was 5 hours in 1: 1.5 in molar ratio～1: 2, as reaction raw materials;

Second step was a ball-milling medium with the dehydrated alcohol, with KCl and K ₂SO ₄Ball milling was 5 hours in 0.65: 0.35 in molar ratio～0.9: 0.1, obtained KCl-K ₂SO ₄Composite salt;

The 3rd step is with the Bi of oven dry ₂O ₃And SiO ₂Compound and KCl-K ₂SO ₄Composite salt is with 1: 4～4: 1 hand mill 30min in mortar of mass ratio;

The 4th step, the admixtion behind the hand mill is put into alumina crucible, then crucible is put into retort furnace, be incubated 0.5～3 hour under 750 ℃～850 ℃ conditions, take out, be cooled to room temperature;

The 5th the step, with the refrigerative sample in ultrasonic wave with drying after the washed with de-ionized water, promptly get Bi ₄Si ₃O ₁₂Powder.

2. the preparation method of the bismuth silicate powder that glimmers is characterized in that, may further comprise the steps:

The first step is a ball-milling medium with the dehydrated alcohol, with Bi ₂O ₃And SiO ₂Ball milling was 5 hours in 2: 3 in molar ratio, as reaction raw materials;

Second step was a ball-milling medium with the dehydrated alcohol, with KCl and K ₂SO ₄Ball milling was 5 hours in 0.74: 0.26 in molar ratio, obtained KCl-K ₂SO ₄Composite salt;

The 3rd step is with the Bi of oven dry ₂O ₃And SiO ₂Compound and KCl-K ₂SO ₄Composite salt is with 3: 2 hand mill 30min in mortar of mass ratio;

The 4th step, the admixtion behind the hand mill is put into alumina crucible, then crucible is put into retort furnace, insulation is 3 hours under 750 ℃ of conditions, takes out, and is cooled to room temperature;

The 5th the step, with the refrigerative sample in ultrasonic wave with drying after the washed with de-ionized water, promptly get Bi ₄Si ₃O ₁₂Powder.

3. the preparation method of the bismuth silicate powder that glimmers is characterized in that, may further comprise the steps:

The first step is a ball-milling medium with the dehydrated alcohol, with Bi ₂O ₃And SiO ₂Ball milling was 5 hours in 2: 3 in molar ratio, as reaction raw materials;

Second step was a ball-milling medium with the dehydrated alcohol, with KCl and K ₂SO ₄Ball milling was 5 hours in 0.74: 0.26 in molar ratio, obtained KCl-K ₂SO ₄Composite salt;

The 3rd step is with the Bi of oven dry ₂O ₃And SiO ₂Compound and KCl-K ₂SO ₄Composite salt is with 3: 2 hand mill 30min in mortar of mass ratio;

The 4th step, the admixtion behind the hand mill is put into alumina crucible, then crucible is put into retort furnace, insulation is 3 hours under 800 ℃ of conditions, takes out, and is cooled to room temperature;

The 5th the step, with the refrigerative sample in ultrasonic wave with drying after the washed with de-ionized water, promptly get Bi ₄Si ₃O ₁₂Powder.

4. the preparation method of the bismuth silicate powder that glimmers is characterized in that, may further comprise the steps:

The first step is a ball-milling medium with the dehydrated alcohol, with Bi ₂O ₃And SiO ₂Ball milling was 5 hours in 2: 3 in molar ratio, as reaction raw materials;

Second step was a ball-milling medium with the dehydrated alcohol, with KCl and K ₂SO ₄Ball milling was 5 hours in 0.74: 0.26 in molar ratio, obtained KCl-K ₂SO ₄Composite salt;

The 3rd step is with the Bi of oven dry ₂O ₃And SiO ₂Compound and KCl-K ₂SO ₄Composite salt is with 4: 1 hand mill 30min in mortar of mass ratio;

The 4th step, the admixtion behind the hand mill is put into alumina crucible, then crucible is put into retort furnace, insulation is 3 hours under 820 ℃ of conditions, takes out, and is cooled to room temperature;

The 5th the step, with the refrigerative sample in ultrasonic wave with drying after the washed with de-ionized water, promptly get Bi ₄Si ₃O ₁₂Powder.

5. the preparation method of the bismuth silicate powder that glimmers is characterized in that, may further comprise the steps:

The first step is a ball-milling medium with the dehydrated alcohol, with Bi ₂O ₃And SiO ₂Ball milling was 5 hours in 1: 2 in molar ratio, as reaction raw materials;

Second step was a ball-milling medium with the dehydrated alcohol, with KCl and K ₂SO ₄Ball milling was 5 hours in 0.29: 0.11 in molar ratio, obtained KCl-K ₂SO ₄Composite salt;

The 3rd step is with the Bi of oven dry ₂O ₃And SiO ₂Compound and KCl-K ₂SO ₄Composite salt is with 1: 4 hand mill 30min in mortar of mass ratio;

The 4th step, the admixtion behind the hand mill is put into alumina crucible, then crucible is put into retort furnace, insulation is 0.5 hour under 850 ℃ of conditions, takes out, and is cooled to room temperature;

The 5th the step, with the refrigerative sample in ultrasonic wave with drying after the washed with de-ionized water, promptly get Bi ₄Si ₃O ₁₂Powder.

6. the preparation method of the bismuth silicate powder that glimmers is characterized in that, may further comprise the steps:

The first step is a ball-milling medium with the dehydrated alcohol, with Bi ₂O ₃And SiO ₂Ball milling was 5 hours in 1: 1.8 in molar ratio, as reaction raw materials;

Second step was a ball-milling medium with the dehydrated alcohol, with KCl and K ₂SO ₄Ball milling was 5 hours in 0.31: 0.09 in molar ratio, obtained KCl-K ₂SO ₄Composite salt;

The 3rd step is with the Bi of oven dry ₂O ₃And SiO ₂Compound and KCl-K ₂SO ₄Composite salt is with 1: 1 hand mill 30min in mortar of mass ratio;

The 4th step, the admixtion behind the hand mill is put into alumina crucible, then crucible is put into retort furnace, insulation is 2 hours under 780 ℃ of conditions, takes out, and is cooled to room temperature;

The 5th the step, with the refrigerative sample in ultrasonic wave with drying after the washed with de-ionized water, promptly get Bi ₄Si ₃O ₁₂Powder.

7. according to the preparation method of the described flicker bismuth silicate powder of the arbitrary claim of claim 1 to 6, it is characterized in that, carry out once above cleaning in said the 5th step.