Device and method for synthesis of gallium-containing garnet-structured scintillator poly crystalline material

Abstract

Provided are a device and a method for synthesis of a gallium-containing garnet-structured scintillator polycrystalline material. The synthesis device includes a polycrystalline material synthesis chamber (7) made of a thermal insulation material (1); a crucible (3) arranged at the center of the bottom of the polycrystalline material synthesis chamber; an induction coil (2) annularly arranged outside the polycrystalline material synthesis chamber at a position with a height corresponding to that of the crucible; an arc heating device (4) arranged on a central axis of the induction coil in the polycrystalline material synthesis chamber, so as to heat and melt raw materials at the center of the crucible by means of the high temperature generated by arc discharge; the induction coil is connected to a RF induction power supply.

Claims

1. A method for synthesis of a gallium-containing garnet-structured scintillator polycrystalline material, wherein raw materials for synthesis prepared in advance are uniformly mixed and put into a crucible, and then an arc heating device is started to heat the raw materials at the center of the crucible by using the heat generated by arc discharge, so that the raw materials at the center are melted first, and become conductive; then, a power supply connected to an induction coil is started to generate an alternating induction electromagnetic field, so that the raw materials in the crucible are continuously heated up by eddy current under the electromagnetic field of RF, gradually melt from the center outwards until a required melting boundary is reached, then held at the temperature for a certain period of time to ensure that the raw materials fully react and transited to be garnet phase, and finally cool down to room temperature, thereby obtaining a synthesized polycrystalline material in the crucible; the power supply of the arc heating device is turned off after the raw materials at the center are melted, and become conductive.

2. The method for synthesis of a gallium-containing garnet-structured scintillator polycrystalline material according to claim 1, wherein the method is carried out by using a device for synthesis of a gallium-containing garnet-structured scintillator polycrystalline material, and the device for synthesis of a gallium-containing garnet-structured scintillator polycrystalline material comprising a polycrystalline material synthesis chamber made of a thermal insulation material, with an openable cover plate arranged on the polycrystalline material synthesis chamber for picking and placing of raw materials; a crucible arranged at the center of the bottom of the polycrystalline material synthesis chamber; an induction coil annularly arranged outside the polycrystalline material synthesis chamber at a position with a height corresponding to that of the crucible, wherein an arc heating device is arranged on a central axis of the induction coil in the polycrystalline material synthesis chamber, and the arc heating device is connected to a power supply so as to heat and melt raw materials at the center of the crucible by means of the heat generated by arc discharge; the induction coil is connected to an induction power supply so as to heat the raw materials in the crucible from the center outwards by using the increased electric conductivity of the melt melted by the arc heating device under the electromagnetic field of RF; and the method comprises the following specific steps, 1) weighing each of powdery raw materials according to the stoichiometric ratio specified by the chemical molecular formula of the gallium-containing garnet-structured scintillator polycrystalline material to be synthesized, and uniformly mixing the weighed powdery raw materials to obtain a raw material mixture, wherein each of the powdery raw materials has a purity of ≥99.99%; 2) placing the raw material mixture from the step 1) in the crucible; 3) starting the arc heating device to heat the raw materials at the center of the crucible by the heat generated by arc discharge to melt the raw materials at the center first, and the electric conductivity of the melted raw materials in the center increases after melting of the raw materials, thus meeting the requirements on the electric conductivity of the raw materials for heating by the induction coil; 4) starting the power supply connected to the induction coil to generate an alternating induction electromagnetic field; 5) gradually increasing the output power of the induction coil, so that the raw materials in the crucible can be continuously heated up by eddy current under the electromagnetic field of RF; the power supply of the arc heating device is turned off after the raw materials at the center are melted, and become conductive; 6) Further increasing the output power of the induction coil to gradually melt the raw materials from the center outwards until the required melting boundary is reached, and then keeping a constant temperature for 0.5-4 h to ensure that the raw materials fully react and transited to be the garnet phase; 7) Cooling down to room temperature at a certain rate, thereby obtaining the synthesized polycrystalline material in the crucible.

3. The method for synthesis of a gallium-containing garnet-structured scintillator polycrystalline material according to claim 2, wherein the required melting boundary between the melt and the crucible in the step 6) is determined according to the following requirements: controlling the heating power of the induction coil to prevent direct contact between the crucible and the melt, and ensuring that a layer of powdery raw materials is left between the crucible and the melt to isolate the crucible from the melt, so that the polycrystalline material is not polluted by the crucible.

4. The method for synthesis of a gallium-containing garnet-structured scintillator polycrystalline material according to claim 2, wherein the above steps 1) to 7) are operated under an atmosphere of air or a mixed gas atmosphere formed by mixing O.sub.2 with any one, two or three of N.sub.2, Ar or CO.sub.2, wherein the content of O.sub.2 is higher than 3.0 vol. %, so as to inhibit the decomposition of Ga.sub.2O.sub.3.

5. The method for synthesis of a gallium-containing garnet-structured scintillator polycrystalline material according to claim 2, wherein the time required for reducing the power of the induction coil from the maximum value to zero in the step 7) is 0.1-200 h.

6. The method for synthesis of a gallium-containing garnet-structured scintillator polycrystalline material according to claim 2, wherein the induction coil has a hollow cross section, and a cooling water pipe is arranged at the bottom of the crucible; the cooling water pipe and the induction coil are supplied with cooling water for cooling the bottom and periphery of the crucible to prevent the crucible from being melted.

7. The method for synthesis of a gallium-containing garnet-structured scintillator polycrystalline material according to claim 2, wherein the thermal insulation material is ZrO.sub.2 ceramic or Al.sub.2O.sub.3 ceramic, or a combination thereof.

8. The method for synthesis of a gallium-containing garnet-structured scintillator polycrystalline material according to claim 2, wherein the crucible is made of quartz or corundum ceramic and fixed in the polycrystalline material synthesis chamber.

9. The method for synthesis of a gallium-containing garnet-structured scintillator polycrystalline material according to claim 2, wherein a positive pole of the arc heating device is located right above or right below the crucible, a negative pole of the arc heating device is located right below or right above the crucible, and the positive pole of the arc heating device is configured opposite to the negative pole of the arc heating device.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1—schematic diagram of the device for synthesis of a gallium-containing garnet-structured scintillator polycrystalline material of the present disclosure.

(2) Among them, 1—thermal insulation material; 2—induction coil; 3—crucible; 4—positive pole of arc heating device; 5—negative pole of arc heating device; 6—cooling water pipe; 7—polycrystalline material synthesis chamber.

DETAILED DESCRIPTION OF THE EMBODIMENTS

(3) The following is a further detailed description of the present disclosure with reference to the drawings and specific embodiments.

(4) With reference to FIG. 1, it can be seen that device for synthesis of a gallium-containing garnet-structured scintillator polycrystalline material of the present disclosure comprises a polycrystalline material synthesis chamber 7 made of a thermal insulation material 1, and an openable cover plate is arranged on the polycrystalline material synthesis chamber 7 for picking and placing raw materials; the thermal insulation material 1 is ZrO.sub.2 ceramic or Al.sub.2O.sub.3 ceramic, or a combination thereof. A crucible 3 is arranged in the center of the bottom of the polycrystalline material synthesis chamber 7, and the crucible 3 is made of quartz or corundum (Al.sub.2O.sub.3) ceramic and fixed in the polycrystalline material synthesis chamber 7. A (Radio Frequency) induction coil 2 is annularly arranged outside the polycrystalline material synthesis chamber 7 at a position with a height corresponding to that of the crucible 3. An arc heating device is arranged on a central axis of the induction coil 2 in the polycrystalline material synthesis chamber 7, and is connected to a power supply to heat and melt raw materials in the center of the crucible by using the high temperature generated by arc discharge. A positive pole 4 of the arc heating device is located right above the crucible 3, a negative pole 5 of the arc heating device is located right below the crucible 3, and the positive pole 4 of the arc heating device is configured opposite to the negative pole 5 of the arc heating device. The induction coil 2 is connected to an induction power supply (Radio Frequency) to heat the raw materials in the crucible from the center outwards by using the increased electric conductivity of the melt melted by the arc heating device under the electromagnetic field of RF.

(5) The cross section of the induction coil 2 is hollow, a cooling water pipe 6 is arranged at the bottom of the crucible 3, and the cooling water pipe 6 and the induction coil 2 are supplied with cooling water for cooling the bottom and periphery of the crucible to prevent the crucible from being melted, thereby preventing the melted materials from contacting with crucible and being polluted. The induction coil of the present disclosure is a pipe structure with a central hole, cooling water is passed through the central hole, and the cooling water is deionized water. Deionized water has great resistance, so it can be considered as an insulating material. According to the present disclosure, cooling water is introduced into the induction coil in order to prevent the induction coil and crucible from melting.

(6) Also, the present disclosure provides a method for synthesis of a gallium-containing garnet-structured scintillator polycrystalline material, wherein raw materials for synthesis prepared in advance are uniformly mixed and put into a crucible, and then an arc heating device is started to heat the raw materials at the center of the crucible by using the high temperature generated by arc discharge, so that the raw materials at the center are melted first, and become conductive; then, a power supply connected to an induction coil is started to generate an alternating induction electromagnetic field, so that the raw materials in the crucible are continuously heated up by eddy current under the electromagnetic field of RF, gradually melt from the center outwards until the required melting boundary is reached, then held at the temperature for a certain period of time to ensure that the raw materials fully react and transit to be garnet phase, and finally cool down to room temperature, thereby obtaining a synthesized polycrystalline material in the crucible; the power supply of the arc heating device is turned off after the raw materials at the center are melted, and become conductive.

(7) The synthesis method uses the above device for synthesis of a gallium-containing garnet-structured scintillator polycrystalline material, and includes the following specific steps,

(8) 1) weighing each of powdery raw materials according to the stoichiometric ratio specified by the chemical molecular formula of the gallium-containing garnet-structured scintillator polycrystalline material to be synthesized, and uniformly mixing the weighed powdery raw materials to obtain a raw material mixture, wherein each of the powdery raw materials has a purity of ≥99.99%; the molecular formula of the gallium-containing garnet-structured scintillator polycrystalline material to be synthesized is (Gd.sub.1-x-i-jA.sub.xB.sub.iC.sub.j).sub.3(Ga.sub.yAl.sub.1-y).sub.5O.sub.12, wherein A is one of Y, Lu and La; B is one of Ce and Pr; C is one of Mg, Ca, Sr, Ba and Zn, and wherein 0≤x≤1, 0.00001<i<0.05, 0.00001<j<0.05, 0.4<y<1, and x+i+j≤1;

(9) 2) placing the raw material mixture from the step 1) in the crucible;

(10) 3) starting the power supply connected to the induction coil to generate an alternating induction electromagnetic field;

(11) 4) starting the arc heating device to heat the raw materials at the center of the crucible by the high temperature generated by arc discharge to melt the raw materials at the center first, and become conductive, thus meeting the requirements on the electric conductivity of the raw materials for heating by the induction coil; there is no requirement on the starting sequence of the induction coil power supply and the arc heating device power supply; the arc heating device can be started to melt the raw materials at the center before turning on the induction coil, or the induction coil can be turned on first before turning on the arc heating device, or the arc heating device and the induction coil can be started at the same time;

(12) 5) gradually increasing the output power of the induction coil, so that the raw materials in the crucible can be continuously heated up by eddy current under the electromagnetic field of RF; the power supply of the arc heating device is turned off after the raw materials at the center are melted, and become conductive;

(13) 6) further increasing the output power of the induction coil to gradually melt the raw materials from the center outwards until the required melting boundary is reached, and then keeping a constant temperature for 0.5-4 h to ensure that the raw materials fully react and transit to be the garnet phase;

(14) 7) cooling down to room temperature at a certain rate, thereby obtaining the synthesized polycrystalline material in the crucible.

(15) Preferably, the required melting boundary between the melt and the crucible in the step 6) is determined according to the following requirements: controlling the heating power of the induction coil to prevent direct contact between the crucible and the melt, and ensuring that a layer of powdery raw materials is left between the crucible and the melt to isolate the crucible from the melt, so that the polycrystalline material is not polluted by the crucible.

(16) The above steps 1) to 7) are operated under an atmosphere of air or a mixed gas atmosphere formed by mixing O.sub.2 with any one, two or three of N.sub.2, Ar or CO.sub.2, wherein the content of O.sub.2 is higher than 3.0 vol. %, so as to inhibit the decomposition of Ga.sub.2O.sub.3.

(17) The time required for reducing the power of the induction coil from the maximum value to zero in the step 7) is 0.1-200 h, preferably 20-50 h.

(18) Several synthesis examples are given below to further help understand the present disclosure.

Example 1

(19) A corundum crucible with a size of Φ200 mm×150 mm was used, the inner diameter of the copper induction coil was 250 mm, the thermal insulation material was ZrO.sub.2 ceramic with a thickness of 30 mm, and a copper cooling water pipe was arranged at the bottom of the crucible. 5822.11 g Gd.sub.2O.sub.3, 1100.54 g Al.sub.2O.sub.3, 3034.83 g Ga.sub.2O.sub.3 and 40.59 g CeO.sub.2 powdery raw materials were weighed respectively, and then mixed uniformly. The mixed powdery raw materials were put into the corundum crucible and compacted. The induction coil power supply and arc heating power supply were started in turn. When the center of raw materials started to melt, the arc heating device was turned off and the heating power of the induction coil was increased at a rate of 3 kW/h, so that the raw materials gradually melted outwards from the center until the melting zone was close to the crucible wall. As the side wall and bottom of the crucible were both supplied with cooling water, it can be ensured that the crucible is not melted. After keeping a constant temperature (constant power) for 3 h, the peak power of the induction coil was reduced to zero in 40 h. The whole process was carried out in an air atmosphere. A yellow polycrystalline material was obtained after opening the crucible. XRD phase test showed that the polycrystalline material was garnet phase and there was no other impurity phase.

Example 2

(20) A corundum crucible with a size of Φ200 mm×150 mm was used, the inner diameter of the copper induction coil was 250 mm, the thermal insulation material was ZrO.sub.2 ceramic with a thickness of 30 mm, and a copper cooling water pipe was arranged at the bottom of the crucible. 5892.58 g Gd.sub.2O.sub.3, 1288.51 g Al.sub.2O.sub.3, 2770.12 g Ga.sub.2O.sub.3 and 50.52 g CeO.sub.2 powdery raw materials were weighed respectively, and then mixed uniformly. The mixed powdery raw materials were put into the corundum crucible and compacted. The induction coil power supply and arc heating power supply were started in turn. When the center of raw materials started to melt, the arc heating device was turned off and the heating power of the induction coil was increased at a rate of 3 kW/h, so that the raw materials gradually melted outwards from the center until the melting zone was close to the crucible wall. As the side wall and bottom of the crucible were both supplied with cooling water, it can be ensured that the crucible is not melted. After keeping a constant temperature (constant power) for 2 h, the peak power of the induction coil was reduced to zero in 30 h. The whole process was carried out in an air atmosphere. A yellow polycrystalline material was obtained after opening the crucible. XRD phase test showed that the polycrystalline material was garnet phase and there was no other impurity phase.

Example 3

(21) A quartz crucible with a size of Φ200 mm×150 mm was used, the inner diameter of the copper induction coil was 250 mm, the thermal insulation material was Al.sub.2O.sub.3 ceramic with a thickness of 30 mm, and a copper cooling water pipe was arranged at the bottom of the crucible. 5892.58 g Gd.sub.2O.sub.3, 1288.51 g Al.sub.2O.sub.3, 2770.12 g Ga.sub.2O.sub.3, 50.52 g CeO.sub.2 and 5 g MgCO.sub.3 powdery raw materials were weighed respectively, and then mixed uniformly. The mixed powdery raw materials were put into the corundum crucible and compacted. The induction coil power supply and arc heating power supply were started in turn. When the center of raw materials started to melt, the arc heating device was turned off and the heating power of the induction coil was increased at a rate of 3 kW/h, so that the raw materials gradually melted outwards from the center until the melting zone was close to the crucible wall. As the side wall and bottom of the crucible were both supplied with cooling water, it can be ensured that the crucible is not melted. After keeping a constant temperature (constant power) for 3.5 h, the peak power of the induction coil was reduced to zero in 45 h. The whole process was carried out in an air atmosphere. A yellow polycrystalline material was obtained after opening the crucible. XRD phase test showed that the polycrystalline material was garnet phase and there was no other impurity phase.

Example 4

(22) A corundum crucible with a size of Φ200 mm×150 mm was used, the inner diameter of the copper induction coil was 250 mm, the thermal insulation material was Al.sub.2O.sub.3 ceramic with a thickness of 30 mm, and a copper cooling water pipe was arranged at the bottom of the crucible. 5892.58 g Gd.sub.2O.sub.3, 1288.51 g Al.sub.2O.sub.3, 2770.12 g Ga.sub.2O.sub.3, 50.52 g CeO.sub.2 and 7 g CaCO.sub.3 powdery raw materials were weighed respectively, and then mixed uniformly. The mixed powdery raw materials were put into the corundum crucible and compacted. The induction coil power supply and arc heating power supply were started in turn. When the center of raw materials started to melt, the arc heating device was turned off and the heating power of the induction coil was increased at a rate of 3 kW/h, so that the raw materials gradually melted outwards from the center until the melting zone was close to the crucible wall. As the side wall and bottom of the crucible were both supplied with cooling water, it can be ensured that the crucible is not melted. After keeping a constant temperature (constant power) for 2 h, the peak power of the induction coil was reduced to zero in 50 h. The whole process was carried out in an air atmosphere. A yellow polycrystalline material was obtained after opening the crucible. XRD phase test showed that the polycrystalline material was garnet phase and there was no other impurity phase.

Example 5

(23) A quartz crucible with a size of Φ200 mm×150 mm was used, the inner diameter of the copper induction coil was 250 mm, the thermal insulation material was ZrO.sub.2 ceramic with a thickness of 30 mm, and a copper cooling water pipe was arranged at the bottom of the crucible. 5892.58 g Gd.sub.2O.sub.3, 1288.51 g Al.sub.2O.sub.3, 2770.12 g Ga.sub.2O.sub.3, 50.52 g CeO.sub.2 and 8 g BaCO.sub.3 powdery raw materials were weighed respectively, and then mixed uniformly. The mixed powdery raw materials were put into the corundum crucible and compacted. The induction coil power supply and arc heating power supply were started in turn. When the center of raw materials started to melt, the arc heating device was turned off and the heating power of the induction coil was increased at a rate of 3 kW/h, so that the raw materials gradually melted outwards from the center until the melting zone was close to the crucible wall. As the side wall and bottom of the crucible were both supplied with cooling water, it can be ensured that the crucible is not melted. After keeping a constant temperature (constant power) for 1.5 h, the peak power of the induction coil was reduced to zero in 25 h. The whole process was carried out in an air atmosphere. A yellow polycrystalline material was obtained after opening the crucible. XRD phase test showed that the polycrystalline material was garnet phase and there was no other impurity phase.

(24) The above-mentioned embodiments of the present disclosure are only examples to illustrate the present disclosure, and are not intended to limit the implementation of the present disclosure. For those of ordinary skill in the field, other changes and variations in different forms can be made on the basis of the above description. All embodiments cannot be exhaustive here. All obvious changes or variations derived from the technical solution of the present disclosure are still within the scope of protection of the present disclosure.