CN107446580B - Preparation method of oxysulfide luminescent powder - Google Patents

Preparation method of oxysulfide luminescent powder Download PDF

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CN107446580B
CN107446580B CN201710656492.3A CN201710656492A CN107446580B CN 107446580 B CN107446580 B CN 107446580B CN 201710656492 A CN201710656492 A CN 201710656492A CN 107446580 B CN107446580 B CN 107446580B
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CN107446580A (en
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陈启伟
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Shanghai Shuopu New Material Co ltd
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    • C09K11/7771—Oxysulfides
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Abstract

The invention relates to sulfur oxideThe preparation method of the oxysulfide luminescent powder comprises the following steps: r2(1‑x)M2xO2S, wherein R is at least one of Y, Gd, La and Lu, M is at least one of Pr, Ce, Tb, Eu, Yb, Nd, Er and Ho, x is more than or equal to 0 and less than 1, and preferably, x is more than or equal to 1 and 10‑6≤x≤5×10‑2The synthesis method comprises the following steps: (1) r is to be2O3And stoichiometric ratio of M2O3Dissolving the mixture in nitric acid to prepare a rare earth nitrate solution; (2) mixing the obtained rare earth nitrate solution with a precipitator to obtain a precipitate suspension, and separating, washing and drying the precipitate to obtain precursor powder; (3) and vulcanizing the obtained precursor powder at 600-1300 ℃ in a sulfur-containing atmosphere to obtain the sulfur oxide luminescent powder. The invention has simple and easy process and high reaction efficiency, and can obtain the oxysulfide luminescent powder with high purity, superfine property, high specific surface area and high sintering activity.

Description

Preparation method of oxysulfide luminescent powder
Technical Field
The invention relates to a synthesis method of oxysulfide luminescent powder, belonging to the field of ceramic preparation.
Background
The rare earth sulfur oxide fluorescent powder and the ceramic scintillator are widely used in the fields of medical imaging, national defense security inspection, industrial nondestructive inspection and the like due to the excellent optical performance and density characteristics of the rare earth sulfur oxide fluorescent powder and the ceramic scintillator, wherein Gd is used for the fields2O2Pr is a scintillator commonly used in the medical x-CT at present, and the scintillator integrates light output (1.8 xCdWO)4) Low afterglow<100ppm @100ms), and high density (7.34 g/cm)3) And the like. The synthesis of rare earth oxysulfide is significant for preparing high-performance ceramic scintillators. Currently, GOS scintillators are basically controlled by three companies, i.e., Siemens, Hitachi and Toshiba, and the powder synthesis technology is different from one company to another, wherein Siemens adopts a Sulfite precipitation reduction method (Sulfite precipitation reduction), Hitachi adopts oxalate precipitation combined with a flux method, and Toshiba adopts rare earth oxide and flux methods. However, the conventional sulfite precipitation method is inefficient in reaction, and heating causes SO2The environment is polluted by volatilization; and the oxysulfide prepared by the traditional fluxing agent method has large particles, low specific surface area and poor sintering activity.
Disclosure of Invention
To overcome the traditionInefficient reaction in sulfite precipitation and SO caused by heating2The invention provides a synthesis method of oxysulfide luminescent powder, which has high reaction efficiency, is environment-friendly, and has high purity, superfine property, high specific surface area and high sintering activity, oxysulfide luminescent powder synthesized by the synthesis method, and an oxysulfide ceramic scintillator prepared by the oxysulfide luminescent powder.
In one aspect, the present invention provides a method for synthesizing sulfur oxide luminescent powder, wherein the sulfur oxide luminescent powder has a chemical composition general formula: r2(1-x)M2xO2S, wherein R is at least one of Y, Gd, La and Lu, M is at least one of Pr, Ce, Tb, Eu, Yb, Nd, Er and Ho, and x is more than or equal to 0 and less than 1, preferably more than 0 and less than 1, and more preferably more than 1 multiplied by 10-6≤x≤5×10-2，
The synthesis method comprises the following steps:
(1) r is to be2O3And stoichiometric ratio of M2O3Dissolving the mixture in nitric acid to prepare a rare earth nitrate solution;
(2) mixing the obtained rare earth nitrate solution with a precipitator to obtain a precipitate suspension, and separating, washing and drying the precipitate to obtain precursor powder;
(3) and vulcanizing the obtained precursor powder at 600-1300 ℃ in a sulfur-containing atmosphere to obtain the sulfur oxide luminescent powder.
The invention adopts a method for directly vulcanizing a precursor, namely, a coprecipitation process is adopted to obtain a required rare earth precipitation precursor, and then a sulfur source is adopted to directly vulcanize to obtain the oxysulfide luminescent powder. The invention has simple and easy process and high reaction efficiency, and can obtain the oxysulfide luminescent powder with high purity, superfine property, high specific surface area and high sintering activity.
Preferably, in the step (1), the concentration of the nitric acid is 30-90%, and in the rare earth nitrate solution, the concentration of the R ions is 0.001-10 mol/L.
Preferably, in the step (2), the precipitant is at least one of oxalic acid, ammonium oxalate, ammonia water, ammonium bicarbonate, ammonium carbonate, sodium hydroxide and potassium hydroxide.
Preferably, the molar ratio of precipitant to all metal ions in the rare earth nitrate solution is 0.5: 1-5: 1.
preferably, in the step (2), the drying temperature is 40 to 120 ℃.
Preferably, in step (3), the sulfur-containing atmosphere is SO2、H2S or Ar gas is taken as at least one of sulfur elementary vapor carried by carrier gas.
Preferably, in step (3), the temperature is maintained at 600-1300 ℃ for 0.5-8 hours.
On the other hand, the invention also provides the oxysulfide luminescent powder synthesized by the synthesis method, the particle size of the oxysulfide luminescent powder is less than 10 μm, and the specific surface area is 5m2More than g.
In another aspect, the present invention further provides a sulfur oxide ceramic scintillator, wherein the sulfur oxide ceramic scintillator is obtained by sintering the sulfur oxide luminescent powder.
The preparation method of the oxysulfide provided by the invention has the process characteristics that:
(1) the direct vulcanization method of the precursor has the advantages of simple process, one-step operation, energy conservation and environmental protection;
(2) the oxysulfide powder synthesized by the technical route of the invention has higher specific surface area and purity and higher sintering activity, so that the powder obtained by the process can realize complete densification at lower temperature through pressureless presintering and hot isostatic pressing or single hot-pressing sintering.
Drawings
FIG. 1 is an XRD pattern of the oxysulfide powder prepared by the present invention, showing that the product is a single hexagonal phase of oxysulfide;
FIG. 2 is a typical morphology of sulfur oxides obtained by the process of the present invention, wherein the powder particles have a sphere-like morphology.
Detailed Description
The present invention is further described below in conjunction with the following embodiments and the accompanying drawings, it being understood that the drawings and the following embodiments are illustrative of the invention only and are not limiting.
The invention provides a synthesis method of oxysulfide luminescent powder. The chemical composition of the oxysulfide luminescent powder can be expressed by a general formula as follows: r2(1-x)M2xO2S and R are one or more of Y, Gd, La and Lu, M is one or more of Pr, Ce, Tb, Eu, Yb, Nd, Er and Ho, x is more than or equal to 0 and less than 1, preferably, x is more than 0 and less than 1, and more preferably, the concentration of the S and the R is 1 multiplied by 10-6≤x≤5×10-2Further preferably, 2 × 10-6≤x≤5×10-3. The invention adopts a method for directly vulcanizing a precursor, namely, a coprecipitation process is adopted to obtain a required rare earth precipitation precursor, and then a sulfur source is adopted to directly vulcanize to obtain the oxysulfide luminescent powder. Hereinafter, the method of the present invention will be specifically described as an example.
Firstly, R is put in2O3And stoichiometric ratio of M2O3The mixture is dissolved in nitric acid to prepare a rare earth nitrate solution. I.e. M2O3Account for M2O3And R2O3The ratio of the sum of the amounts of the substances (i.e., the molar ratio) of (a) to (b) may be 1X 10-6To 5X 10-2In the meantime. R2O3Commercially available, and may have a purity of 4N or greater. M2O3Commercially available, and may have a purity of 4N or greater. The nitric acid used may be dilute nitric acid, for example, the concentration may be 30% to 90%. R2O3And M2O3The volume ratio of the total mass of the mixture to nitric acid of (a) may be 1 g: (1-5) mL. In one example, the ratio of nitric acid to rare earth oxide powder is about 1.5ml (65% nitric acid): 1g of oxide. In the prepared rare earth nitrate solution, the concentration of R ions can be 0.001-10 mol/L, and the concentration of M ions can be 0.001-10 mol/L. The rare earth nitrate solution contains rare earth nitrate and may contain the remaining nitric acid of the reaction (i.e., nitric acid may generally be in excess), and the precipitant is added to preferentially neutralize excess nitric acid. Compared with the method of directly dissolving the rare earth nitrate in water to prepare the rare earth nitrate solutionThe rare earth oxide is dissolved in nitric acid to prepare the rare earth nitrate solution, so that the cost can be saved. Because the purchased nitrates all contain crystal water with different degrees, the relative cost performance is not high.
Then, adopting coprecipitation process to prepare R2(1-x)M2xO3The precursor of (1). Specifically, the rare earth nitrate solution is mixed with a precipitant under stirring to react to generate a precipitate (e.g., a white precipitate). The reaction temperature may be RT (room temperature) to 100 ℃. The reaction time may be 1 to 1000 minutes. In the present invention, the precipitant can be oxalic acid, ammonium oxalate, or alkaline precipitant, such as one or more of ammonia water, ammonium bicarbonate, ammonium carbonate, sodium hydroxide, potassium hydroxide, and urea. The precipitant can be prepared into water solution and then mixed with the rare earth nitrate solution. The concentration of the precipitant aqueous solution can be 0.1-10 mol/L. The mixing order of the rare earth nitrate solution and the precipitant is not limited, and for example, the rare earth nitrate solution may be added to the precipitant, or the precipitant may be added to the rare earth nitrate solution. In the mixing, the components may be mixed directly or may be mixed in a dropwise manner (both forward and backward). The molar ratio of precipitant to all metal ions in the rare earth nitrate solution can be 0.5: 1-10: 1, preferably 1: 1-5: 1, more preferably 3:1 to 6:1, and still more preferably 3.5:1 to 4.5: 1. When an alkaline precipitant is used, the precipitant may be used in an amount such that the pH of the mixed solution is 7.0 to 14.0, preferably 8.0 to 12. And separating, washing and drying the obtained precipitate to obtain precursor powder. For example, the obtained precipitate can be filtered, washed with water and the filter cake washed with alcohol can be dried. The drying temperature can be 40-120 ℃.
And directly vulcanizing the obtained precursor powder to obtain the oxysulfide luminescent powder. The sulfur source can be one or more of elemental sulfur, hydrogen sulfide or sulfur dioxide, and from the viewpoint of environmental protection, elemental sulfur is preferred, and the other two gases are toxic and harmful. Gas sulfiding processes may be employed in the present invention. Specifically, a sulfur-containing gas is introduced into a container containing the precursor powder. The sulfur-containing gas may be SO2、H2S or Ar gas is taken as sulfur elementary vapor carried by carrier gas. The vulcanization temperature can be 600-1300 ℃, and the optimization is carried outIs 800 to 1200 ℃. The heat preservation time can be 0.5-8 hours. In the invention, the precursor powder is directly vulcanized without calcining before vulcanization, so that the process can be simplified, and the sulfur oxide obtained by vulcanization has high phase purity and relatively finer particles.
In the vulcanization process, the generated tail gas can be completely absorbed by an absorption tower containing NaOH and cannot be discharged into the atmosphere to pollute the environment.
The oxysulfide luminescent powder prepared by the invention has high purity which can be more than 99.5% by XRD, is spherical-like in morphology and has fine particle size, such as d<10 μm, even d<500nm, and a high Specific Surface Area (SSA)>5m2/g)。
Moreover, the oxysulfide luminescent powder prepared by the method has high sintering activity, and can be completely densified by combining pressureless presintering with hot isostatic pressing or by independently adopting a hot pressing process. In one example, the oxysulfide powder is mixed with a low melting point sintering aid, which can be LiF, Li, and ball milled to obtain a mixed powder2GeF6、LiBF4、Li2B4O7At least one of (1). The addition amount of the low-melting-point sintering aid is 0.01-5 wt% of the sulfur oxide powder. During ball milling, the ball milling medium is alumina or zirconia balls, the solvent is water or ethanol, the ball milling bead ratio is 1: 1-10: 1, the rotating speed is 50-500 rpm, and the duration time is 1-50 hours. Then, the obtained mixed powder is molded to obtain a biscuit. The molding can be dry pressing molding and cold isostatic pressing molding in sequence, wherein the dry pressing molding pressure is 20-50 MPa, and the cold isostatic pressing molding pressure is 100-200 MPa. And carrying out pressureless sintering on the biscuit in vacuum or protective atmosphere, wherein the sintering temperature can be 1100-1500 ℃, and the heat preservation time can be 1-10 hours, so as to obtain a pre-sintered body. And carrying out hot isostatic pressing sintering on the obtained presintered body in a protective atmosphere, wherein the sintering temperature can be 1100-1500 ℃, the pressure can be 100-250 Mpa, and the heat preservation time can be 1-20 hours, so as to obtain the oxysulfide ceramic scintillator.
The present invention will be described in detail by way of examples. It is also to be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the invention, and that certain insubstantial modifications and adaptations of the invention by those skilled in the art may be made in light of the above teachings. The specific process parameters and the like of the following examples are also only one example of suitable ranges, i.e., those skilled in the art can select the appropriate ranges through the description herein, and are not limited to the specific values exemplified below.
The test method comprises the following steps:
purity: an XRD X-ray diffractometer;
particle size: an LPS laser particle size analyzer;
specific surface area: BET nitrogen adsorption method.
Example 1
50g of Gd are weighed2O3，0.1g Pr6O11And 0.01g of CeO2And mixed and added into 30mL of nitric acid (with the concentration of 68%) to obtain a rare earth nitrate solution. And adding the rare earth nitrate solution into 45mL of ammonia water (the concentration is 2mol/l), enabling the pH of the mixed solution to be 10, reacting at room temperature to 50 ℃ for about 0.5 hour to obtain white precipitate, repeatedly performing suction filtration on the white suspension solution, and drying at 100 ℃ to obtain the precursor. Then the precursor is placed in a 850 ℃ tubular furnace, and H is introduced2S gas is kept for 3 hours to obtain Gd2O2Pr, Ce pure phase luminescent powder.
Fig. 1 shows the XRD pattern of the oxysulfide powder obtained in example 1, indicating that the product is a single hexagonal phase of oxysulfide. FIG. 2 is a diagram showing the morphology of oxysulfide obtained in example 1, and it can be seen that the powder particles have a sphere-like morphology. The sulfur oxide powder obtained by the test has the purity of 100 percent, the average grain diameter of 30nm and the specific surface area of 10m2/g。
Example 2:
50g of Gd are weighed2O3，0.15g Pr6O11And 0.02g of CeO2And mixed and added into 30mL of nitric acid (with the concentration of 68%) to obtain a rare earth nitrate solution. The above rare earth nitrate solution was added to 50ml of ammonium hydrogencarbonate (concentration: 1.5mol/l) to prepare a mixed solutionThe pH value of the suspension is 9, the reaction is carried out for about 0.5 hour at the room temperature of 40 ℃, white precipitates can appear, the white suspension solution is repeatedly filtered, and the precursor is obtained after drying at the temperature of 100 ℃. Then the precursor is placed in a 900 ℃ tube furnace, and SO is introduced2Gas is kept for 3 hours to obtain Gd2O2Pr, Ce pure phase luminescent powder. XRD showed pure phase (essentially the same as in example 1), particle size of about 100nm, specific surface area of about 8m2/g。
Example 3:
50g of Gd are weighed2O3，0.8Pr6O11And 0.015g CeO2And mixed and added into 50mL of nitric acid (with the concentration of 68%) to obtain a rare earth nitrate solution. Adding the rare earth nitrate solution into 100g of urea (the concentration is 3mol/l), enabling the pH of the mixed solution to be 9, reacting for about 6 hours at 85-90 ℃, generating white precipitate, repeatedly filtering the white suspended solution, and drying at 100 ℃ to obtain the precursor. Then the precursor and sulfur powder are continuously reacted for 3 hours in a 1100 ℃ tubular furnace under the protection of Ar gas in inert atmosphere to obtain Gd2O2Pr, Ce pure phase luminescent powder. XRD showed pure phase (essentially the same as in example 1), particle size about 500nm, specific surface area about 5m2/g。

Claims (4)

1. A synthesis method of sulfur oxide luminescent powder is characterized in that the chemical composition general formula of the sulfur oxide luminescent powder is as follows: r2(1-x)M2xO2S, wherein R is Gd, M is Pr and Ce, 2X 10-6≤x≤5×10-3，
The synthesis method comprises the following steps:
(1) r is to be2O3And stoichiometric ratio of M2O3Dissolving the mixture in nitric acid to prepare a rare earth nitrate solution; m2O3Account for M2O3And R2O3The ratio of the sum of the amounts of the substances of (a) to (b) is 2X 10-6To 5X 10-3 To (c) to (d); the concentration of nitric acid is 30-90%, in the rare earth nitrate solution, the concentration of R ions is 0.001-10 mol/L, and the concentration of M ions is 0.001-10 mol/L;
(2) mixing the obtained rare earth nitrate solution with a precipitator, and obtaining a precipitation suspension through coprecipitation; the reaction temperature is between room temperature and 100 ℃, and the reaction time is 1 to 1000 minutes; separating, washing and drying the precipitate to obtain precursor powder; the molar ratio of the precipitant to all metal ions in the rare earth nitrate solution is 0.5: 1-5: 1;
(3) vulcanizing the obtained precursor powder in a sulfur-containing atmosphere at 800-1200 ℃ for 0.5-8 hours to obtain the oxysulfide luminescent powder;
the oxysulfide luminescent powder has a sphere-like shape, the particle size is less than 10 mu m, and the specific surface area is 5m2More than g.
2. The synthesis method according to claim 1, wherein in the step (2), the precipitant is at least one of oxalic acid, ammonium oxalate, ammonia water, ammonium bicarbonate, ammonium carbonate, sodium hydroxide and potassium hydroxide.
3. The synthesis method according to claim 1, wherein in the step (2), the drying temperature is 40-120 ℃.
4. The method of claim 1, wherein in step (3), the sulfur-containing atmosphere is SO2、H2S or Ar gas is taken as at least one of sulfur elementary vapor carried by carrier gas.
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