CN103449811A - Co-precipitation preparation method of ZrO2/Gd203 composite ceramic material for nuclear power - Google Patents
Co-precipitation preparation method of ZrO2/Gd203 composite ceramic material for nuclear power Download PDFInfo
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Abstract
The invention discloses a co-precipitation preparation method of a ZrO2/Gd203 composite ceramic material for nuclear power. The co-precipitation preparation method comprises a pre-preparation process of a zirconium-gadolinium mixed solution, a preparation process of zirconium-gadolinium mixed precipitates and the like. The co-precipitation preparation method comprises the following steps of: firstly dissolving and mixing zirconyl nitrate deionized water, gadolinium oxide powder, nitric acid and ammonia water which are used as raw materials, then precipitating and mixing so as to form uniformly mixed preparation raw materials, and finally carrying out follow-up reduction treatment so as to obtain the ZrO2/Gd203 Gd2O3 composite ceramic material. The co-precipitation preparation method has no strict requirements on processing equipment and is easy to realize. The vacuum sintering is carried out, and the sintering temperature is controlled at 1500 DEG C to 1650 DEG C. The ZrO2/Gd203 composite ceramic material prepared by the method has good sintering property and relatively good microstructure, mechanical strength and density (theoretical density greater than 96% T.D).
Description
Technical field
The invention belongs to composite ceramic material, be specifically related to the burnable poison composite ceramic material for pressurized water reactor, be i.e. a kind of nuclear power ZrO
2/ Gd
2o
3the co-precipitation preparation method of composite ceramic material.
Background technology
In nuclear power reactor, particularly in the pressurized-water reactor nuclear power plant reactor core, extensively adopt Al both at home and abroad
2o
3/ B
4c burnable poison material is controlled the reactor initial reactivity, realizes flattening core power and distributes, and improves burnup, extends the refulling cycle, thereby reduce nuclear power running cost, improves the safety and reliability of operation.Yet along with improving constantly of advanced nuclear reactor burnup of new generation and core power, Al
2o
3/ B
4c burnable poison material not only can accelerate swelling, also can reduce its chemical stability, thereby can affect security and the economy of nuclear reactor operation.ZrO
2/ Gd
2o
3burnable poison material and Al
2o
3/ B
4c compares the advantage with three aspects: the one, there is lower swelling rate; The 2nd, ZrO
2matrix and Gd
2o
3the sosoloid easily formed, be down to minimum by the homogeneity question of burnable poison material; The 3rd, ZrO
2matrix has splendid chemical stability to involucrum alloy and Main Coolant.
What pressurized-water reactor nuclear fuel element design at present adopted is zirconium alloy cladding, ZrO
2/ Gd
2o
3thereby composite ceramic material perforate gap is spent conference planar water steam and is caused the corrosion of zirconium alloy cladding material hydrogen embrittlement; ZrO
2matrix and Gd
2o
3the degree of solid solution is to ZrO
2/ Gd
2o
3the use properties of composite ceramic material under hot conditions has material impact.Therefore in order further to deepen fuel burnup, improve security and the economy of nuclear power, the ZrO of research and development high-density, good microtexture
2/ Gd
2o
3the burnable poison material will provide technical support for the nuclear power burnable poison investigation of materials research high with inherent safety.
Both at home and abroad about preparation ZrO
2/ Gd
2o
3the method of composite ceramic material mainly contains ball milled, powder metallurgic method etc.The economy of ball milled, powder metallurgic method perhaps can be better, but the composite ceramic material of preparation, its inner homogeneity is difficult to control, densification difficulty, internal porosity and the shortcoming such as defect is more, and produces a large amount of dust in preparation process, contaminate environment, the damage personnel's is healthy.
Therefore, patent of the present invention adopts coprecipitation method to prepare ZrO
2/ Gd
2o
3composite ceramics, just can overcome above-mentioned shortcoming to a certain extent.ZrO prepared by present method
2/ Gd
2o
3homogeneity, purity and the crystalline structure that composite ceramics has the Chemical Composition of resulting materials is good, sintering temperature low and the high advantages such as mechanical strength.Current coprecipitation method has been confirmed to be the more advanced technique of manufacturing stupalith, but prepares ZrO by coprecipitation method
2/ Gd
2o
3the research of composite ceramic material, through new patent searching, also do not have relevant report both at home and abroad.
Summary of the invention
The object of the present invention is to provide a kind of nuclear power ZrO
2/ Gd
2o
3the co-precipitation preparation method of composite ceramic material, the burnable poison investigation of materials research high with inherent safety for nuclear power lays the foundation and supplies technical support.
Implementation of the present invention is as follows: a kind of nuclear power ZrO
2/ Gd
2o
3the co-precipitation preparation method of composite ceramic material, comprise the pre-prepared technique of zirconium gadolinium mixing solutions, the pre-prepared technique of zirconium gadolinium mixing solutions comprises zirconyl nitrate solution preparation process and Gadolinium trinitrate solution preparation process and zirconium gadolinium mixing solutions preparation process, and concrete steps are as follows:
Zirconyl nitrate solution preparation process: get Zircosol ZN and be dissolved in deionized water, obtain zirconyl nitrate solution;
Gadolinium trinitrate solution preparation process: get three gadolinium sesquioxide powder and be dissolved in salpeter solution, obtain Gadolinium trinitrate solution;
Zirconium gadolinium mixing solutions preparation process: adopt two method mixed nitrate oxygen zirconium solution and Gadolinium trinitrate solution of dripping, obtain zirconium gadolinium mixing solutions.
Zircosol ZN is preferably: the analytical pure Zircosol ZN, its molecular formula is: ZrO (NO
3)
25H
2o; The molecular formula of three gadolinium sesquioxide powder is: Gd
2o
3; Nitric acid is preferably: analytical pure nitric acid.
The ZrO that the present invention is evenly distributed in order to obtain element
2/ Gd
2o
3composite ceramic material, be mixed to get equally distributed liquid-phase mixing raw material with liquid phase process, the recycling precipitator method, and precipitation generates the ZrO mixed
2/ Gd
2o
3the composite ceramic material powder, the ceramic preparation that recycles like this later stage prepares final finished product.The present invention compares with existing ball milled, powder metallurgic method, and the present invention can not produce pore, and inner homogeneity is better, and density is high.Ball milled, powder metallurgic method, in the process of mixing 2 kinds of materials, due to mechanically mixing, therefore can cause 2 kinds of materials when mixing, uniformity coefficient is inadequate, in smelting process, because 2 kinds of substance crystallization process difference are larger, so density is compared inequality with the present invention simultaneously.
The purpose of the pre-prepared technique of zirconium gadolinium mixing solutions is mainly the zirconium gadolinium mixing solutions that the production uniformity coefficient is high, makes zr element and gadolinium element obtain the mixing of height and reach uniform purpose in this mixing solutions.
Zircosol ZN is dissolved in deionized water and makes and avoid contaminating impurity, thereby three gadolinium sesquioxide powder are dissolved in nitric acid, prepares Gadolinium trinitrate solution, and because Gadolinium trinitrate solution and zirconyl nitrate solution belong to together, so the two can reach higher mixing uniformity when mixing.
Preferably, in the zirconyl nitrate solution preparation process, the amount of Zircosol ZN is: 261g～300g, wherein ZrO
2be calculated as 100g～120g.
Preferably, in Gadolinium trinitrate solution preparation process, the content of three gadolinium sesquioxide powder is 10g～20g.
Preferably, in zirconium gadolinium mixing solutions preparation process, when two method mixed nitrate oxygen zirconium solutions and Gadolinium trinitrate solution, need to constantly stir at least 20min.Adopting to stir makes zirconyl nitrate solution and Gadolinium trinitrate solution reach the purpose mixed.Preferred churning time is 20～30min.Adopt two ratios that method keeps zirconyl nitrate solution and Gadolinium trinitrate solution of dripping, avoid a kind of material wherein excessive.
Also comprise zirconium gadolinium mixed sediment preparation technology, zirconium gadolinium mixed sediment is preparation technology comprise the steps:
Reaction stoste preparation process: get ammoniacal liquor and slowly be titrated in zirconium gadolinium mixing solutions, controlling pH value remains in the scope of 6-8, carry out stir process in titration simultaneously, treat that ammoniacal liquor fully reacts with zirconium gadolinium mixing solutions, adularescent throw out A separates out, continue to stir 1.5 h～2.5h, obtaining sinking is the reaction stoste that white depositions A, upper strata are supernatant liquid A; After adding ammoniacal liquor, ammoniacal liquor respectively with zirconyl nitrate solution and Gadolinium trinitrate solution reaction, obtain white depositions A, white depositions A now is mixture, contain the throw out of zr element and the throw out that contains the gadolinium element, two kinds of throw outs, when generating, change solid phase into by liquid phase, reaction is synchronously carried out, and the throw out that therefore contains zr element and the throw out that contains the gadolinium element are mixed into one and form the white depositions A be evenly distributed.
Ageing separating step A: at least 10h of stoste ripening is answered in negate, and with supernatant liquid A and the white depositions A of absorption method separating reaction stoste, white depositions A keeps somewhere standby;
Ageing separating step B: get ammoniacal liquor and slowly be titrated in supernatant liquid A, separate out white depositions B, until separate out without white depositions B again;
Prepare white depositions B and white depositions A according to ageing separating step B and ageing separating step A, ageing separating step B can repeated multiple timesly carry out.
The mixing, washing step: extracting waste sediment B and white depositions A mix, and adopt deionized water repeatedly to rinse, and obtain the pure white throw out, i.e. zirconium gadolinium mixed sediment.Guarantee the pure of zirconium gadolinium mixed sediment, avoid ammoniacal liquor to disturb in late phase reaction and technique.
Also comprise the suction filtration technique, stoving process, insulation grinding technics, calcining process, the sintering process that carry out successively, get zirconium gadolinium mixed sediment and pass through successively suction filtration technique, stoving process, insulation grinding technics, calcining process, sintering process, finally obtain finished product, Gd in finished product
2o
3weight percent be 0-15%; Surplus is ZrO
2.
Zirconium gadolinium mixed sediment obtains filter cake through suction filtration technique, and filter cake obtains the precursor powder through stoving process.
The insulation grinding technics is: the box-type furnace that the precursor powder is placed in to 550～750 ℃ is incubated at least 3h to 5h, takes out after air cooling and grind to obtain powder.
Calcining process is: powder is obtained to the moulding powder through 550 ℃ to 750 ℃ and the environment calcining the compression moulding that are incubated 3～5h, and sintering process is: it is vacuum sintering under 1500 ℃ to 1650 ℃, the soaking time condition that at least 2h, temperature rise rate are at least 20 ℃/min that the moulding powder is placed in to temperature.
The vacuum tightness of vacuum sintering is 10
-2to 10
-3pa; Ammonia water titration speed is difficult for too fast, and preferably ammonia water titration speed is 1.5 ml to 2.5ml/min
.
The present invention includes the pre-prepared technique of zirconium gadolinium mixing solutions and zirconium gadolinium mixed sediment preparation technology etc.Take Zircosol ZN deionized water, three gadolinium sesquioxide powder, nitric acid, ammoniacal liquor is raw material, first dissolves mixing, then is mixed to form through precipitation the raw materials mixed, and recycles follow-up reduction and processes and obtain ZrO
2/ Gd
2o
3composite ceramic material, zirconium gadolinium mixed sediment reduces original raw material after suction filtration technique, stoving process, insulation grinding technics, calcining process, sintering process, and finished product is: ZrO
2/ Gd
2o
3mixture, because zirconium gadolinium mixed sediment is uniform mixture, the ZrO therefore prepared
2/ Gd
2o
3mixture is also uniform mixture.
Through aforesaid method, can prepare ZrO
2/ Gd
2o
3the nuclear power fuel that mixture is evenly distributed, thus the inherent safety of nuclear power with fuel improved.
The invention has the advantages that: the present invention does not have harsh requirement to processing unit, is easy to realize.Vacuum sintering, sintering temperature is controlled at 1500 ℃～1650 ℃.The ZrO prepared according to the present invention
2/ Gd
2o
3composite ceramics burnable poison material have good sintering character and preferably microtexture, mechanical strength and density (theoretical density is greater than 96%T.D.）。
The accompanying drawing explanation
Fig. 1 is the FB(flow block) that the present invention realizes.
Embodiment
Embodiment 1
As shown in Figure 1.
A kind of nuclear power ZrO
2/ Gd
2o
3the co-precipitation preparation method of composite ceramic material, comprise the pre-prepared technique of zirconium gadolinium mixing solutions, the pre-prepared technique of zirconium gadolinium mixing solutions comprises zirconyl nitrate solution preparation process and Gadolinium trinitrate solution preparation process and zirconium gadolinium mixing solutions preparation process, and concrete steps are as follows:
Zirconyl nitrate solution preparation process: get Zircosol ZN and be dissolved in deionized water, obtain zirconyl nitrate solution;
Gadolinium trinitrate solution preparation process: get three gadolinium sesquioxide powder and be dissolved in salpeter solution, obtain Gadolinium trinitrate solution;
Zirconium gadolinium mixing solutions preparation process: adopt two method mixed nitrate oxygen zirconium solution and Gadolinium trinitrate solution of dripping, obtain zirconium gadolinium mixing solutions.
Zircosol ZN is preferably: the analytical pure Zircosol ZN, its molecular formula is: ZrO (NO
3)
25H
2o; The molecular formula of three gadolinium sesquioxide powder is: Gd
2o
3; Nitric acid is preferably: analytical pure nitric acid.
The ZrO that the present invention is evenly distributed in order to obtain element
2/ Gd
2o
3composite ceramic material, be mixed to get equally distributed liquid-phase mixing raw material with liquid phase process, the recycling precipitator method, and precipitation generates the ZrO mixed
2/ Gd
2o
3the composite ceramic material powder, the ceramic preparation that recycles like this later stage prepares final finished product.The present invention compares with existing ball milled, powder metallurgic method, and the present invention can not produce pore, and inner homogeneity is better, and density is high.Ball milled, powder metallurgic method, in the process of mixing 2 kinds of materials, due to mechanically mixing, therefore can cause 2 kinds of materials when mixing, uniformity coefficient is inadequate, in smelting process, because 2 kinds of substance crystallization process difference are larger, so density is compared inequality with the present invention simultaneously.
The purpose of the pre-prepared technique of zirconium gadolinium mixing solutions is mainly the zirconium gadolinium mixing solutions that the production uniformity coefficient is high, makes zr element and gadolinium element obtain the mixing of height and reach uniform purpose in this mixing solutions.
Zircosol ZN is dissolved in deionized water and makes and avoid contaminating impurity, thereby three gadolinium sesquioxide powder are dissolved in nitric acid, prepares Gadolinium trinitrate solution, and because Gadolinium trinitrate solution and zirconyl nitrate solution belong to together, so the two can reach higher mixing uniformity when mixing.
Preferably, in the zirconyl nitrate solution preparation process, the amount of Zircosol ZN is: 261～300g, wherein ZrO
2be calculated as 100～120g.
Preferably, in Gadolinium trinitrate solution preparation process, the content of three gadolinium sesquioxide powder is 10g～20g.
Preferably, in zirconium gadolinium mixing solutions preparation process, when two method mixed nitrate oxygen zirconium solutions and Gadolinium trinitrate solution, need to constantly stir at least 20min.Adopting to stir makes zirconyl nitrate solution and Gadolinium trinitrate solution reach the purpose mixed.Preferred churning time is 20～30min.Adopt two ratios that method keeps zirconyl nitrate solution and Gadolinium trinitrate solution of dripping, avoid a kind of material wherein excessive.
Also comprise zirconium gadolinium mixed sediment preparation technology, zirconium gadolinium mixed sediment is preparation technology comprise the steps:
Reaction stoste preparation process: get ammoniacal liquor and slowly be titrated in zirconium gadolinium mixing solutions, controlling pH value remains in the scope of 6-8, carry out stir process in titration simultaneously, treat that ammoniacal liquor fully reacts with zirconium gadolinium mixing solutions, adularescent throw out A separates out, continue to stir 1.5 h～2.5h, obtaining sinking is the reaction stoste that white depositions A, upper strata are supernatant liquid A; After adding ammoniacal liquor, ammoniacal liquor respectively with zirconyl nitrate solution and Gadolinium trinitrate solution reaction, obtain white depositions A, white depositions A now is mixture, contain the throw out of zr element and the throw out that contains the gadolinium element, two kinds of throw outs, when generating, change solid phase into by liquid phase, reaction is synchronously carried out, and the throw out that therefore contains zr element and the throw out that contains the gadolinium element are mixed into one and form the white depositions A be evenly distributed.
Ageing separating step A: at least 10h of stoste ripening is answered in negate, and with supernatant liquid A and the white depositions A of absorption method separating reaction stoste, white depositions A keeps somewhere standby;
Ageing separating step B: get ammoniacal liquor and slowly be titrated in supernatant liquid A, separate out white depositions B, until separate out without white depositions B again;
Prepare white depositions B and white depositions A according to ageing separating step B and ageing separating step A, ageing separating step B can repeated multiple timesly carry out.
The mixing, washing step: extracting waste sediment B and white depositions A mix, and adopt deionized water repeatedly to rinse, and obtain the pure white throw out, i.e. zirconium gadolinium mixed sediment.Guarantee the pure of zirconium gadolinium mixed sediment, avoid ammoniacal liquor to disturb in late phase reaction and technique.
Also comprise the suction filtration technique, stoving process, insulation grinding technics, calcining process, the sintering process that carry out successively, get zirconium gadolinium mixed sediment and pass through successively suction filtration technique, stoving process, insulation grinding technics, calcining process, sintering process, finally obtain finished product, Gd in finished product
2o
3weight percent for being greater than 0-15%; Surplus is ZrO
2.
Zirconium gadolinium mixed sediment obtains filter cake through suction filtration technique, and filter cake obtains the precursor powder through stoving process.
The insulation grinding technics is: the box-type furnace that the precursor powder is placed in to 550～750 ℃ is incubated at least 3h to 5h, takes out after air cooling and grind to obtain powder.
Calcining process is: powder is obtained to the moulding powder through 550 ℃ to 750 ℃ and the environment calcining the compression moulding that are incubated 3～5h, and sintering process is: it is vacuum sintering under 1500 ℃ to 1650 ℃, the soaking time condition that at least 2h, temperature rise rate are at least 20 ℃/min that the moulding powder is placed in to temperature.
The vacuum tightness of vacuum sintering is 10
-2to 10
-3pa; Ammonia water titration speed is difficult for too fast, and preferably ammonia water titration speed is 1.5 ml to 2.5ml/min
.
Zirconium gadolinium mixed sediment reduces original raw material after suction filtration technique, stoving process, insulation grinding technics, calcining process, sintering process, and finished product is: ZrO
2/ Gd
2o
3mixture, because zirconium gadolinium mixed sediment is uniform mixture, the ZrO therefore prepared
2/ Gd
2o
3mixture is also uniform mixture.
Embodiment 2
Select analytical pure Zircosol ZN and three gadolinium sesquioxide powder as raw material.Take the Zircosol ZN (ZrO of 261g
2be calculated as 100g) be dissolved in appropriate deionization, take 10g tri-gadolinium sesquioxide powder and be dissolved in appropriate analytical pure salpeter solution.The Gadolinium trinitrate solution of preparation is mixed it with two methods with zirconyl nitrate solution, and constantly stir 25min, form homogeneous mixture solotion.Adopt ammoniacal liquor to be added drop-wise in mixing solutions with the speed of 1.5ml/min, regulate the pH value of mixing solutions, make the pH value remain on 6～8 left and right, dropping limit, limit strong stirring, fully react it, and the adularescent Precipitation continues to stir 1.5～2.5h.To react stoste static, carry out ripening 10～15h, draw supernatant liquid, in clear liquid, drip ammonia scrubbing until no longer produce white depositions in solution.The ageing after product is carried out repeatedly to the deionization washing, obtain filter cake after suction filtration.Filter cake is obtained to the precursor powder 130～150 ℃ of oven dry.By precursor 550～750 ℃ of insulation 3～5h in box-type furnace, take out after air cooling and grind and obtain ZrO
2/ Gd
2o
3the powder of composite ceramic material.By (typed pressure is 50MPa, and specimen size is 52mm * 10mm * 10mm) after the repressed moulding of the powder of drying and calcining, in vacuum tightness, be finally 10
-2～10
-3pa, sintering temperature are: 1500 ℃, 1550 ℃, 1600 ℃, 1650 ℃, soaking time are that under 2h, the temperature rise rate condition that is 20 ℃/min, vacuum sintering obtains fine and close ZrO
2/ Gd
2o
3composite ceramics burnable poison material.
Embodiment 3
Get 261g analytical pure Zircosol ZN (ZrO
2be calculated as 100g) be dissolved in deionized water the preparation zirconyl nitrate solution; Get 10g analytical pure three gadolinium sesquioxide powder and be dissolved in appropriate analytical pure salpeter solution, preparation Gadolinium trinitrate solution; The Gadolinium trinitrate solution of preparation is mixed it with two methods with zirconyl nitrate solution, and constantly stir 20min, form homogeneous mixture solotion.
Adopt ammoniacal liquor to be added drop-wise in mixing solutions with the speed of 2ml/min, regulate the pH value of mixing solutions, make it remain on 7 left and right, dropping limit, limit strong stirring, fully react it, and the adularescent Precipitation continues to stir 2h.To react stoste static, carry out ripening 10h, draw supernatant liquid, in clear liquid, drip ammonia scrubbing until no longer produce white depositions in solution; The ageing after product is carried out repeatedly to the deionization washing, obtain filter cake after suction filtration.Filter cake is obtained to the precursor powder 140 ℃ of oven dry.
By precursor powder 650 ℃ of insulation 4h in box-type furnace, take out after air cooling and grind and obtain ZrO
2/ Gd
2o
3the powder of composite ceramic material.By (typed pressure is 60MPa, and specimen size is 52mm * 10mm * 10mm) after the repressed moulding of the powder of drying and calcining, in sintering temperature, be finally: 1600 ℃, soaking time are that under 2h, the temperature rise rate condition that is 20 ℃/min, vacuum sintering obtains fine and close ZrO
2/ Gd
2o
3composite ceramics burnable poison material.The theoretical density of the pellet after sintering is not less than 96%T.D.
Embodiment 4
Get 261g analytical pure Zircosol ZN (ZrO
2be calculated as 100g) be dissolved in deionized water the preparation zirconyl nitrate solution; Get 10g analytical pure three gadolinium sesquioxide powder and be dissolved in appropriate analytical pure salpeter solution, preparation Gadolinium trinitrate solution; The Gadolinium trinitrate solution of preparation is mixed it with two methods with zirconyl nitrate solution, and constantly stir 23min, form homogeneous mixture solotion.
Adopt ammoniacal liquor to be added drop-wise in mixing solutions with the speed of 2.5ml/min, regulate the pH value of mixing solutions, the pH value is remained in the 7-8 scope, dropping limit, limit strong stirring, fully react it, and the adularescent Precipitation continues to stir 2.5h.To react stoste static, carry out ripening 15h or 12h, draw supernatant liquid, in clear liquid, drip ammonia scrubbing until no longer produce white depositions in solution; The ageing after product is carried out repeatedly to the deionization washing, obtain filter cake after suction filtration.Filter cake is obtained to the precursor powder 145-150 ℃ of oven dry.
By precursor powder 700-750 ℃ of insulation 4-5h in box-type furnace, take out after air cooling and grind and obtain ZrO
2/ Gd
2o
3the powder of composite ceramic material.By (typed pressure is 70MPa, and specimen size is 52mm * 10mm * 10mm) after the repressed moulding of the powder of drying and calcining, in sintering temperature, be finally: 1600 ℃, soaking time are that under 2h, the temperature rise rate condition that is 20 ℃/min, vacuum sintering obtains fine and close ZrO
2/ Gd
2o
3composite ceramics burnable poison material.The theoretical density of the pellet after sintering is not less than 96%T.D.
Composite ceramic material of the present invention meets the following conditions on preparation technology: in the mixing solutions preparation process, churning time is not less than 20min; The ammoniacal liquor rate of addition is moderate, and the pH value is strict controlled in 6～8 left and right; After reaction stoste is standing, digestion time is not less than 10h; Precursor powder calcining temperature is controlled at 550～750 ℃ and be incubated 3～5h; The vacuum powder sintering temperature of drying and calcining is 1500 ℃, and 1550 ℃, 1600 ℃, 1650 ℃, soaking time are that 2h, temperature rise rate are 20 ℃/min.The ZrO of preparation
2/ Gd
2o
3composite ceramic material have good sintering character and preferably microtexture, mechanical strength and density (theoretical density is greater than 96%T.D.）。
As mentioned above, can well realize the present invention.
Claims (10)
1. a nuclear power ZrO
2/ Gd
2o
3the co-precipitation preparation method of composite ceramic material, it is characterized in that: comprise the pre-prepared technique of zirconium gadolinium mixing solutions, the pre-prepared technique of zirconium gadolinium mixing solutions comprises zirconyl nitrate solution preparation process and Gadolinium trinitrate solution preparation process and zirconium gadolinium mixing solutions preparation process, and concrete steps are as follows:
Zirconyl nitrate solution preparation process: get Zircosol ZN and be dissolved in deionized water, obtain zirconyl nitrate solution;
Gadolinium trinitrate solution preparation process: get three gadolinium sesquioxide powder and be dissolved in salpeter solution, obtain Gadolinium trinitrate solution;
Zirconium gadolinium mixing solutions preparation process: adopt two method mixed nitrate oxygen zirconium solution and Gadolinium trinitrate solution of dripping, obtain zirconium gadolinium mixing solutions.
2. a kind of nuclear power ZrO according to claim 1
2/ Gd
2o
3the co-precipitation preparation method of composite ceramic material is characterized in that: in the zirconyl nitrate solution preparation process, the amount of Zircosol ZN is: 261～300g, wherein ZrO
2be calculated as 100～120g.
3. a kind of nuclear power ZrO according to claim 1
2/ Gd
2o
3the co-precipitation preparation method of composite ceramic material is characterized in that: in Gadolinium trinitrate solution preparation process, the content of three gadolinium sesquioxide powder is 10g～20g.
4. a kind of nuclear power ZrO according to claim 1
2/ Gd
2o
3the co-precipitation preparation method of composite ceramic material is characterized in that: in zirconium gadolinium mixing solutions preparation process, when two method mixed nitrate oxygen zirconium solutions and Gadolinium trinitrate solution, need to constantly stir at least 20min.
5. according to the described a kind of nuclear power ZrO of any one in claim 1-4
2/ Gd
2o
3the co-precipitation preparation method of composite ceramic material is characterized in that: also comprise zirconium gadolinium mixed sediment preparation technology, zirconium gadolinium mixed sediment is preparation technology comprise the steps:
Reaction stoste preparation process: get ammoniacal liquor and slowly be titrated in zirconium gadolinium mixing solutions, controlling pH value remains in the scope of 6-8, carry out stir process in titration simultaneously, treat that ammoniacal liquor fully reacts with zirconium gadolinium mixing solutions, adularescent throw out A separates out, continue to stir 1.5 h～2.5h, obtaining sinking is the reaction stoste that white depositions A, upper strata are supernatant liquid A;
Ageing separating step A: at least 10h of stoste ripening is answered in negate, and with supernatant liquid A and the white depositions A of absorption method separating reaction stoste, white depositions A keeps somewhere standby;
Ageing separating step B: get ammoniacal liquor and slowly be titrated in supernatant liquid A, separate out white depositions B, until separate out without white depositions B again;
The mixing, washing step: extracting waste sediment B and white depositions A mix, and adopt deionized water repeatedly to rinse, and obtain the pure white throw out, i.e. zirconium gadolinium mixed sediment.
6. a kind of nuclear power ZrO according to claim 5
2/ Gd
2o
3the co-precipitation preparation method of composite ceramic material, it is characterized in that: also comprise the suction filtration technique, stoving process, insulation grinding technics, calcining process, the sintering process that carry out successively, get zirconium gadolinium mixed sediment and pass through successively suction filtration technique, stoving process, insulation grinding technics, calcining process, sintering process, finally obtain finished product, Gd in finished product
2o
3weight percent be 0-15%; Surplus is ZrO
2.
7. a kind of nuclear power ZrO according to claim 6
2/ Gd
2o
3the co-precipitation preparation method of composite ceramic material is characterized in that: zirconium gadolinium mixed sediment obtains filter cake through suction filtration technique, and filter cake obtains the precursor powder through stoving process.
8. a kind of nuclear power ZrO according to claim 7
2/ Gd
2o
3the co-precipitation preparation method of composite ceramic material is characterized in that: the insulation grinding technics is: the box-type furnace that the precursor powder is placed in to 550～750 ℃ is incubated at least 3h to 5h, takes out after air cooling and grind to obtain powder.
9. a kind of nuclear power ZrO according to claim 8
2/ Gd
2o
3the co-precipitation preparation method of composite ceramic material, it is characterized in that: calcining process is: powder is obtained to the moulding powder through 550 ℃ to 750 ℃ and the environment calcining the compression moulding that are incubated 3～5h, and sintering process is: it is vacuum sintering under 1500 ℃ to 1650 ℃, the soaking time condition that at least 2h, temperature rise rate are at least 20 ℃/min that the moulding powder is placed in to temperature.
10. a kind of nuclear power ZrO according to claim 9
2/ Gd
2o
3the co-precipitation preparation method of composite ceramic material is characterized in that: the vacuum tightness of vacuum sintering is 10
-2to 10
-3pa; Ammonia water titration speed is 1.5 ml to 2.5ml/min
.
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| CN110606742A (en) * | 2019-10-24 | 2019-12-24 | 中国核动力研究设计院 | TiO for nuclear power2-Gd2O3Burnable poison ceramic material and preparation method thereof |
| CN110729064A (en) * | 2019-10-24 | 2020-01-24 | 中国核动力研究设计院 | Al for nuclear power2O3-Gd2O3Burnable poison ceramic material and preparation method thereof |
| CN116514541A (en) * | 2023-05-09 | 2023-08-01 | 有研资源环境技术研究院(北京)有限公司 | Preparation method of composite ceramic absorber material and application of material |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110606742A (en) * | 2019-10-24 | 2019-12-24 | 中国核动力研究设计院 | TiO for nuclear power2-Gd2O3Burnable poison ceramic material and preparation method thereof |
| CN110729064A (en) * | 2019-10-24 | 2020-01-24 | 中国核动力研究设计院 | Al for nuclear power2O3-Gd2O3Burnable poison ceramic material and preparation method thereof |
| CN110606742B (en) * | 2019-10-24 | 2022-02-22 | 中国核动力研究设计院 | TiO for nuclear power2-Gd2O3Burnable poison ceramic material and preparation method thereof |
| CN116514541A (en) * | 2023-05-09 | 2023-08-01 | 有研资源环境技术研究院(北京)有限公司 | Preparation method of composite ceramic absorber material and application of material |
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