CN115233001B - Preparation method of high-performance zirconium gadolinium alloy - Google Patents
Preparation method of high-performance zirconium gadolinium alloy Download PDFInfo
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- C22F1/16—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of other metals or alloys based thereon
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Abstract
The invention discloses a preparation method of a high-performance zirconium gadolinium alloy, which comprises the following steps: 1. mixing a zirconium raw material and a gadolinium raw material, and then smelting to obtain an ingot; 2. carrying out solution treatment and water quenching on the cast ingot to obtain a water-quenched cast ingot; 3. brushing an antioxidant protective coating on the surface of the water-quenched ingot to obtain an ingot with the coating on the surface; 4. heating the cast ingot, and then mechanically processing the cast ingot while the cast ingot is hot to obtain a mechanically processed cast ingot; 5. and sequentially carrying out annealing treatment and surface finishing on the cast ingot to obtain the zirconium-gadolinium alloy. The zirconium gadolinium alloy is prepared by mixing a zirconium raw material and a gadolinium raw material, smelting the mixture into an ingot, performing beta-phase solution treatment, quenching the ingot with water, performing heating machining on the surface of the ingot after antioxidant protective coating treatment to obtain the zirconium gadolinium alloy with coexisting alpha-phase and beta-phase.
Description
Technical Field
The invention belongs to the technical field of nonferrous metallurgy and nuclear materials, and particularly relates to a preparation method of a high-performance zirconium gadolinium alloy.
Background
In various reactors of various countries in the world, a pressurized water reactor of a nuclear fission route is mainly used, uranium 235 fuel blocks with 3% -5% abundance are used as fission fuel, the fission fuel is bombarded by neutrons to generate energy, and through liquid heat circulation, the spent fuel post-processing equipment faces the problems of corrosion, neutron radiation and the like, which always troubles the design of key equipment. Neutrons present a significant hazard to both equipment and operators. The adoption of the super-corrosion-resistant alloy material with neutron absorption performance to manufacture related equipment and instruments becomes a reliable solution for relieving and guaranteeing the safety of nuclear chemical industry, and the high operation reliability of the related equipment at high temperature, high-level emission and boiling nitric acid is ensured. Meanwhile, the development of devices such as a spent fuel dry storage container, a spent fuel transport container, a dissolver, an evaporator and the like has great demand on neutron absorption materials.
The existing experiments prove that the zirconium gadolinium alloy with the designed components can meet the performance requirements of corrosion resistance and neutron shielding, but a specific preparation method for the alloy has not been reported. Because the alloy has no research at home and abroad, how to realize the obtainment of ideal alloy components and target performance needs to explore the preparation process and the heat treatment system for solidifying the alloy.
Therefore, a preparation method of the high-performance zirconium gadolinium alloy is needed, a scientific zirconium gadolinium alloy preparation process flow is provided, and important data support is provided for subsequent actual production.
Disclosure of Invention
The invention aims to solve the technical problem of providing a preparation method of a high-performance zirconium gadolinium alloy aiming at the defects of the prior art. The method comprises the steps of mixing a zirconium raw material and a gadolinium raw material, smelting the mixture into an ingot, performing beta-phase solution treatment, performing water quenching, performing heating machining on the surface of the ingot after antioxidant protective coating treatment to obtain the alpha-phase and beta-phase coexisting zirconium-gadolinium alloy, and providing a preparation process and a heat treatment system of the zirconium-gadolinium alloy.
In order to solve the technical problems, the invention adopts the technical scheme that: the preparation method of the high-performance zirconium gadolinium alloy is characterized by comprising the following steps of:
step one, mixing a zirconium raw material and a gadolinium raw material, and then smelting to obtain an ingot;
step two, carrying out solid solution treatment and water quenching on the ingot obtained in the step one in sequence to obtain a water-quenched ingot;
step three, brushing an antioxidant protective coating on the surface of the water-quenched cast ingot obtained in the step two to obtain a cast ingot with the coating on the surface;
step four, heating the ingot with the coating on the surface obtained in the step three, and then machining to obtain a machined ingot; the mechanical processing is rolling or forging;
and step five, sequentially carrying out annealing treatment and surface finishing on the machined cast ingot obtained in the step four to obtain the zirconium-gadolinium alloy.
The invention mixes zirconium raw material and gadolinium raw material and then melts them into cast ingot, so that the raw materials are mixed uniformly, the invention adopts beta-phase solution treatment mainly through solution treatment, and water quenching is carried out immediately after the solution treatment, so that the beta-phase with better performance is dissolved into low-temperature alpha-phase, and better performance is achieved at low temperature or normal temperature, the zirconium is alpha-phase below 873 ℃, the temperature needs to be raised continuously to generate beta-phase when the beta-phase is wanted to be obtained, but the beta-phase can not be cooled slowly and naturally when the temperature is reduced, otherwise the beta-phase can have enough time and power to be converted into alpha-phase, the water quenching is characterized in that the temperature is rapidly reduced, the temperature is instantly reduced to normal temperature water from thousands of degrees, so that the beta-phase can not be sufficiently converted into alpha-phase, the alpha-phase and beta-phase can coexist after the water quenching, and the performance carried by the beta-phase is fixed at the normal temperature region, the method realizes that gadolinium atoms are solid-dissolved in HCP zirconium crystal lattices in the maximum content of an HCP structure, and simultaneously leads beta-Zr phase for improving the performance of zirconium alloy to remain in alpha-Zr phase, gadolinium atoms exceeding solid solubility are precipitated at crystal boundary, and the obtained water quenching cast ingot is the alloy cast ingot with beta solid solution zirconium gadolinium, the method prevents the cast ingot from being oxidized in subsequent treatment by coating anti-oxidation protective coating, heats the cast ingot, the heating mainly refers to heating to the temperature above alpha phase transformation point and preserving heat, so that the alloy material generates softening effect, simultaneously, beta phase still exists, and does not influence the beta phase, thereby ensuring the effect of subsequent mechanical processing, the method rolls or forges the cast ingot when hot, refines crystal grains, reduces defects, improves the mechanical property of the alloy material, carries out annealing treatment for eliminating processing stress, carries out surface finishing and mainly grinds off surface oxide skin, and cutting off the edge cracking part to obtain the zirconium gadolinium alloy with target performance, wherein the obtained zirconium gadolinium alloy is a plate or other forms according to the use requirement.
The preparation method of the high-performance zirconium gadolinium alloy is characterized in that in the step one, the zirconium raw material is sponge zirconium, and the gadolinium raw material is gadolinium chips. The invention adopts the sponge zirconium and the gadolinium scraps, is convenient for preliminary mixing of raw materials and smelting, and ensures that the zirconium and the gadolinium in the prepared ingot are preliminarily and uniformly mixed.
The preparation method of the high-performance zirconium gadolinium alloy is characterized in that the smelting in the step one is carried out by adopting a non-consumable arc smelting furnace, a consumable smelting furnace, an induction smelting furnace or a suspension smelting furnace, and when the consumable smelting furnace is adopted, the smelting voltage is 200V-5000V; when a non-consumable arc melting furnace is adopted, the melting voltage is 50V-1000V, and the melting current is 50A-700A; when an induction smelting furnace is adopted, the working frequency is 15 KHz-150 KHz, when a suspension smelting furnace is adopted, the oscillation current is 200A-800A, and the oscillation frequency is 15 KHz-50 KHz; the smelting times are 3-6 times. The smelting method is suitable for various smelting modes, raw materials with the mass of 50 kg-3000 kg in a wide range are melted by controlling smelting parameters, and the raw materials are repeatedly smelted for 3-6 times to obtain ingots with uniform components.
The preparation method of the high-performance zirconium gadolinium alloy is characterized in that the solution treatment process in the second step is as follows: heating to 1050-1400 ℃ and then preserving the heat for 20-300 min; and immediately performing water quenching after the solution treatment, brushing an anti-oxidation protective coating which can resist the high temperature of not less than 1200 ℃ on the surface of the cast ingot before the solution treatment, and drying. The method is placed in an atmospheric high-temperature furnace for solution treatment, the beta-phase solution temperature is reached by controlling the parameters of the solution treatment, water quenching is carried out immediately after the solution treatment, and water-quenched ingots, namely the alloy ingots with beta-solution-state zirconium gadolinium, are obtained.
The preparation method of the high-performance zirconium gadolinium alloy is characterized in that the antioxidant protective coating in the step three is an antioxidant protective coating which can resist the high temperature of not less than 1200 ℃, and the water-quenched ingot is dried after being coated with the antioxidant protective coating. The zirconium alloy is easy to generate oxidation reaction at high temperature to generate brittle zirconium dioxide phase, wherein the zirconium alloy is hard, the zirconium alloy is brittle and the zirconium alloy is lost, the cost of the zirconium alloy is high, solid solution, rolling, annealing and the like in a heat treatment stage face an oxidation environment of more than 500 ℃, the outer surface is seriously oxidized to cause great loss of high-price materials, and the difficulty is increased for processing the materials.
The preparation method of the high-performance zirconium gadolinium alloy is characterized in that the heating process in the fourth step is as follows: heating to 750-850 deg.c and maintaining for 20-100 min. The method heats the ingot after the solution treatment to the temperature above the alpha phase transition point by controlling the thermal parameters, and ensures the effect of subsequent mechanical processing.
The preparation method of the high-performance zirconium gadolinium alloy is characterized in that the mechanical processing in the fourth step is multi-pass rolling or multi-pass forging, the pressing amount of each pass of rolling or forging in the multi-pass rolling or multi-pass forging is 20% -50%, and after each pass of rolling or forging, the alloy needs to be reheated to 750-850 ℃ and kept warm for at least 10min. The invention carries out multi-pass hot rolling or forging, the reduction amount of the zirconium gadolinium alloy after the hot rolling or forging is controlled to be 20-50 percent so as to ensure that the reduction of each pass can provide enough time and energy to break crystal grains, eliminate dislocation and reduce other hole defects, the zirconium gadolinium alloy needs to be reheated to 750-850 ℃ after each pass and is kept warm for at least 10min to soften the zirconium gadolinium alloy, and the zirconium gadolinium alloy is taken out to continue rolling and forging until the required thickness is specified.
The preparation method of the high-performance zirconium gadolinium alloy is characterized in that the annealing treatment in the fifth step is carried out at the temperature of 500-650 ℃ for 30-300 min. According to the invention, the zirconium-gadolinium alloy after hot rolling or forging is subjected to annealing heat treatment, the annealing temperature is controlled to be 500-650 ℃, the treatment temperature is required to be higher according to the force requirement, if the elongation is required to be improved, and is selected to be lower, otherwise, the annealing time is 30-300 min, and the annealing time is determined according to the thickness of the rolled material.
The preparation method of the high-performance zirconium gadolinium alloy is characterized in that the surface finishing process in the fifth step is as follows: and (4) grinding off surface oxide scale and cutting off edge cracking parts. The invention obtains the roughness required by regulation through surface finishing.
The preparation method of the high-performance zirconium gadolinium alloy is characterized in that in the fifth step, the mass fraction ratio of zirconium to gadolinium in the zirconium gadolinium alloy is 87-99: 1-13, wherein the corrosion rate of the zirconium gadolinium alloy in boiling concentrated nitric acid with the concentration of 6mol/L is not more than 0.01 mm/year, and the neutron shielding rate is not less than 99.9%.
Compared with the prior art, the invention has the following advantages:
1. the invention mixes zirconium raw material and gadolinium raw material, then smelts the mixture into cast ingot, then carries out beta-phase solution treatment, then carries out water quenching, and then carries out machining after heating to obtain the zirconium gadolinium alloy with coexisting alpha-phase and beta-phase.
2. The invention makes beta phase with better performance solid-solved to low-temperature alpha phase by solid solution treatment and water quenching immediately after the solid solution treatment, and the invention has better performance at low temperature or normal temperature, refines crystal grains, reduces defects, improves the mechanical property of alloy materials by heating cast ingots and rolling or forging the cast ingots while the cast ingots are hot, and eliminates processing stress by annealing treatment.
3. According to the invention, raw materials are uniformly mixed through multiple times of smelting, oxidation of cast ingots in subsequent treatment is prevented by brushing an antioxidant protective coating, surface oxide skin is removed through surface finishing and grinding, edge cracking parts are cut off, the zirconium gadolinium alloy with target performance is obtained, and the obtained zirconium gadolinium alloy is in a plate or other forms according to use requirements.
4. The invention controls the parameters of solution treatment, heating, mechanical processing and annealing treatment. According to the performance requirement, the heat treatment system is modulated to obtain the zirconium gadolinium alloy with different strength and elongation.
The technical solution of the present invention is further described in detail by examples below.
Detailed Description
Example 1
The embodiment comprises the following steps:
step one, mixing zirconium sponge and gadolinium chips, and then smelting by adopting a non-consumable arc tungsten electrode smelting furnace and an external direct current arc smelting power supply to obtain an ingot; the smelting voltage is 600V, and the smelting times are 4 times;
step two, coating an antioxidant protective coating on the surface of the ingot obtained in the step one, drying, then carrying out solid solution treatment, and immediately carrying out water quenching to obtain a water-quenched ingot; the process of the solution treatment comprises the following steps: heating to 1050 deg.C, and maintaining the temperature for 120min; the anti-oxidation protective coating is an anti-oxidation protective coating which can resist the high temperature of not less than 1200 ℃;
step three, coating an antioxidant protective coating on the surface of the water quenching cast ingot obtained in the step two to obtain a cast ingot with the coating on the surface; the anti-oxidation protective coating is resistant to high temperature of not less than 1200 ℃;
step four, heating the ingot with the coating on the surface obtained in the step three, and then mechanically processing the ingot while the ingot is hot to obtain a mechanically processed ingot; the heating process comprises the following steps: heating to 800 deg.C, and keeping the temperature for 50min; the mechanical processing is multi-pass rolling, the pressing amount of each pass of rolling is 30%, and after each pass of rolling, the steel is required to be reheated to 800 ℃ and kept warm for at least 10min;
step five, sequentially annealing and surface finishing the machined cast ingot obtained in the step four to obtain a zirconium-gadolinium alloy; the temperature of the annealing treatment is 550 ℃, and the time is 40min; the surface finishing process comprises the following steps: and (5) grinding off surface oxide scale, and cutting off edge cracking parts.
Through detection, the mass fraction ratio of zirconium to gadolinium in the zirconium gadolinium alloy prepared in the embodiment is 99:1, tensile strength A 15 Is 460MPa, wherein A 15 The corrosion rate of the zirconium gadolinium alloy in boiling concentrated nitric acid with the concentration of 6mol/L is less than 0.01 mm/year, and the neutron shielding rate is more than 99.9 percent.
Comparative example 1
This comparative example comprises the following steps:
step one, mixing zirconium sponge and gadolinium chips, and then smelting by adopting a non-consumable arc tungsten electrode smelting furnace and an external direct current arc smelting power supply to obtain an ingot; the smelting voltage is 600V, and the smelting times are 4 times;
step two, coating an antioxidant protective coating on the surface of the ingot obtained in the step one, drying, then carrying out solid solution treatment, and immediately carrying out water quenching to obtain a water-quenched ingot; the process of the solution treatment comprises the following steps: heating to 1050 deg.C, and maintaining the temperature for 120min; the anti-oxidation protective coating is resistant to high temperature of not less than 1200 ℃;
step three, coating anti-oxidation protective coating on the surface of the water-quenched ingot obtained in the step two to obtain an ingot with the coating on the surface; the anti-oxidation protective coating is an anti-oxidation protective coating which can resist the high temperature of not less than 1200 ℃;
step four, heating the ingot with the coating on the surface obtained in the step three, and then mechanically processing the ingot while the ingot is hot to obtain a mechanically processed ingot; the heating process comprises the following steps: heating to 800 deg.C, and keeping the temperature for 50min; the mechanical processing is multi-pass rolling, the rolling reduction of each pass is 30%, and after each pass of rolling, the steel is reheated to 800 ℃ and kept for at least 10min;
step five, sequentially annealing and surface finishing the machined cast ingot obtained in the step four to obtain a zirconium-gadolinium alloy; the temperature of the annealing treatment is 550 ℃, and the time is 40min; the surface finishing process comprises the following steps: and (5) grinding off surface oxide scale, and cutting off edge cracking parts.
Through detection, the mass fraction ratio of zirconium to gadolinium in the zirconium gadolinium alloy prepared in the comparative example is 85:15, the zirconium gadolinium alloy of the comparative example is cracked after machining, cannot be formed, and cannot be prepared into a sample for detection.
When the mass fraction of gadolinium in the zirconium gadolinium alloy exceeds 13%, the prepared zirconium gadolinium alloy cannot be molded and cannot be used for preparing the zirconium gadolinium alloy material as can be seen by comparing example 1 with comparative example 1.
Example 2
The embodiment comprises the following steps:
step one, mixing sponge zirconium and gadolinium scraps, and then smelting by using a consumable smelting furnace to obtain an ingot, wherein the smelting voltage is 500V, and the smelting times are 5 times;
step two, immediately performing water quenching on the ingot obtained in the step one after performing solid solution treatment to obtain a water-quenched ingot; the process of the solution treatment comprises the following steps: heating to 1400 deg.C, and maintaining the temperature for 20min;
step three, brushing an antioxidant protective coating on the surface of the water-quenched ingot obtained in the step two to obtain an ingot with the coating on the surface; the anti-oxidation protective coating is an anti-oxidation protective coating which can resist the high temperature of not less than 1200 ℃;
step four, heating the ingot with the coating on the surface obtained in the step three, and then mechanically processing the ingot while the ingot is hot to obtain a mechanically processed ingot; the heating process comprises the following steps: heating to 750 deg.C, and keeping the temperature for 100min; the mechanical processing is multi-pass forging, the pressing amount of each pass of forging is 20%, and after each pass of forging, the steel plate needs to be reheated to 750 ℃ and kept warm for at least 10min;
step five, sequentially annealing and surface finishing the machined cast ingot obtained in the step four to obtain a zirconium-gadolinium alloy; the temperature of the annealing treatment is 650 ℃, and the time is 30min; the surface finishing process comprises the following steps: and (5) grinding off surface oxide scale, and cutting off edge cracking parts.
Through detection, the mass fraction ratio of zirconium to gadolinium in the zirconium gadolinium alloy prepared in the embodiment is 97:3, tensile strength of A 15 Is 510MPa, wherein A 15 The corrosion rate of the zirconium gadolinium alloy in boiling concentrated nitric acid with the concentration of 6mol/L is less than 0.01 mm/year, and the neutron shielding rate is more than 99.9 percent.
Example 3
The embodiment comprises the following steps:
step one, mixing zirconium sponge and gadolinium chips, and then smelting by using a consumable smelting furnace to obtain an ingot; the smelting voltage is 1500V, and the smelting times are 3 times;
step two, coating an antioxidant protective coating on the surface of the ingot obtained in the step one, drying, then performing solid solution treatment, and immediately performing water quenching to obtain a water-quenched ingot; the process of the solution treatment comprises the following steps: heating to 1200 deg.C, and keeping the temperature for 300min; the anti-oxidation protective coating is an anti-oxidation protective coating which can resist the high temperature of not less than 1200 ℃;
step three, coating anti-oxidation protective coating on the surface of the water-quenched ingot obtained in the step two to obtain an ingot with the coating on the surface;
step four, heating the ingot with the coating on the surface obtained in the step three, and then mechanically processing the ingot while the ingot is hot to obtain a mechanically processed ingot; the heating process comprises the following steps: heating to 850 deg.C, and keeping the temperature for 70min; the mechanical processing is multi-pass rolling, the rolling reduction of each pass is 50%, and the rolling or forging of each pass needs to be reheated to 850 ℃ and kept for at least 10min;
step five, sequentially annealing and surface finishing the machined cast ingot obtained in the step four to obtain a zirconium-gadolinium alloy; the temperature of the annealing treatment is 500 ℃, and the time is 300min; the surface finishing process comprises the following steps: and (5) grinding off surface oxide scale, and cutting off edge cracking parts.
Through detection, the mass fraction ratio of zirconium to gadolinium in the zirconium gadolinium alloy prepared in the embodiment is 95:5 tensile strength of A 15 Is 525MPa, wherein A 15 The corrosion rate of the zirconium gadolinium alloy in boiling concentrated nitric acid with the concentration of 6mol/L is less than 0.01 mm/year, and the neutron shielding rate is more than 99.9 percent.
Example 4
The embodiment comprises the following steps:
step one, mixing zirconium sponge and gadolinium scraps, and then smelting by using an induction smelting furnace to obtain an ingot; the working frequency is 75KHz, and the smelting times are 6 times;
step two, coating an antioxidant protective coating on the surface of the ingot obtained in the step one, drying, then carrying out solid solution treatment, and immediately carrying out water quenching to obtain a water-quenched ingot; the process of the solution treatment comprises the following steps: heating to 1300 deg.C, and maintaining the temperature for 200min; the anti-oxidation protective coating is an anti-oxidation protective coating which can resist the high temperature of not less than 1200 ℃;
step three, coating an antioxidant protective coating on the surface of the water quenching cast ingot obtained in the step two to obtain a cast ingot with the coating on the surface; the anti-oxidation protective coating is resistant to high temperature of not less than 1200 ℃;
step four, heating the ingot with the coating on the surface obtained in the step three, and then mechanically processing the ingot while the ingot is hot to obtain a mechanically processed ingot; the heating process comprises the following steps: heating to 830 deg.C, and maintaining the temperature for 40min; the mechanical processing is multi-pass forging, the pressing amount of each pass of forging is 40%, and after each pass of forging, the forging is required to be reheated to 830 ℃ and kept for at least 10min;
step five, sequentially annealing and surface finishing the machined cast ingot obtained in the step four to obtain a zirconium-gadolinium alloy; the temperature of the annealing treatment is 530 ℃, and the time is 200min; the surface finishing process comprises the following steps: and (5) grinding off surface oxide scale, and cutting off edge cracking parts.
Through detection, the mass fraction ratio of zirconium to gadolinium in the zirconium-gadolinium alloy prepared in the embodiment is 95:5 tensile strength of A 15 Is 529MPa, wherein A 15 The corrosion rate of the zirconium gadolinium alloy in boiling concentrated nitric acid with the concentration of 6mol/L is less than 0.01 mm/year, and the neutron shielding rate is more than 99.9 percent.
Example 5
The embodiment comprises the following steps:
step one, mixing zirconium sponge and gadolinium scraps, and then smelting by using a suspension smelting furnace to obtain cast ingots; the oscillation current is 300A-400A, the oscillation frequency is 25 KHz-40 KHz, and the smelting times are 6 times;
step two, coating an antioxidant protective coating on the surface of the ingot obtained in the step one, drying, then carrying out solid solution treatment, and immediately carrying out water quenching to obtain a water-quenched ingot; the process of the solution treatment comprises the following steps: heating to 1100 deg.C, and maintaining the temperature for 40min; the anti-oxidation protective coating is an anti-oxidation protective coating which can resist the high temperature of not less than 1200 ℃;
step three, coating an antioxidant protective coating on the surface of the water quenching cast ingot obtained in the step two to obtain a cast ingot with the coating on the surface; the anti-oxidation protective coating is an anti-oxidation protective coating which can resist the high temperature of not less than 1200 ℃;
step four, heating the ingot with the coating on the surface obtained in the step three, and then mechanically processing the ingot while the ingot is hot to obtain a mechanically processed ingot; the heating process comprises the following steps: heating to 780 deg.C, and keeping the temperature for 60min; the mechanical processing is multi-pass rolling, the pressing amount of each pass of rolling is 35%, and after each pass of rolling, the steel is required to be reheated to 780 ℃ and kept warm for at least 10min;
step five, sequentially annealing and surface finishing the machined cast ingot obtained in the step four to obtain a zirconium-gadolinium alloy; the temperature of the annealing treatment is 600 ℃, and the time is 100min; the surface finishing process comprises the following steps: and (5) grinding off surface oxide scale, and cutting off edge cracking parts.
Through detection, the mass fraction ratio of zirconium to gadolinium in the zirconium-gadolinium alloy prepared in the embodiment is 91:9 tensile strength A 15 Is 460MPa, wherein A 15 The corrosion rate of the zirconium gadolinium alloy in boiling concentrated nitric acid with the concentration of 6mol/L is less than 0.01 mm/year, and the neutron shielding rate is more than 99.9 percent.
Example 6
The embodiment comprises the following steps:
step one, mixing zirconium sponge and gadolinium scraps, and then smelting by using a consumable smelting furnace to obtain an ingot, wherein the smelting voltage is 1000V, and the smelting times are 5 times;
step two, coating an antioxidant protective coating on the surface of the ingot obtained in the step one, drying, then carrying out solid solution treatment, and immediately carrying out water quenching to obtain a water-quenched ingot; the process of the solution treatment comprises the following steps: heating to 1250 deg.C, and keeping the temperature for 150min; the anti-oxidation protective coating is an anti-oxidation protective coating which can resist the high temperature of not less than 1200 ℃;
step three, coating anti-oxidation protective coating on the surface of the water-quenched ingot obtained in the step two to obtain an ingot with the coating on the surface; the anti-oxidation protective coating is an anti-oxidation protective coating which can resist the high temperature of not less than 1200 ℃;
step four, heating the ingot with the coating on the surface obtained in the step three, and then mechanically processing the ingot while the ingot is hot to obtain a mechanically processed ingot; the heating process comprises the following steps: heating to 820 deg.C, and keeping the temperature for 80min; the mechanical processing is multi-pass forging, the pressing amount of each pass of forging is 45%, and after each pass of forging, the forging is required to be reheated to 820 ℃ and the temperature is preserved for at least 10min;
step five, sequentially annealing and surface finishing the machined cast ingot obtained in the step four to obtain a zirconium-gadolinium alloy; the temperature of the annealing treatment is 580 ℃, and the time is 250min; the surface finishing process comprises the following steps: and (5) grinding off surface oxide scale, and cutting off edge cracking parts.
Through detection, the mass fraction of zirconium and gadolinium in the zirconium gadolinium alloy prepared in the embodimentThe ratio is 89:11, tensile strength A 15 Is 410MPa, wherein A 15 The corrosion rate of the zirconium gadolinium alloy in boiling concentrated nitric acid with the concentration of 6mol/L is less than 0.01 mm/year, and the neutron shielding rate is more than 99.9 percent.
Example 7
The embodiment comprises the following steps:
step one, mixing zirconium sponge and gadolinium chips, and then smelting by using a consumable smelting furnace to obtain an ingot; the smelting voltage is 800V, and the smelting times are 4 times; (ii) a
Step two, coating an antioxidant protective coating on the surface of the ingot obtained in the step one, drying, then carrying out solid solution treatment, and immediately carrying out water quenching to obtain a water-quenched ingot; the process of the solution treatment comprises the following steps: heating to 1150 deg.C, and keeping the temperature for 100min; the anti-oxidation protective coating is resistant to high temperature of not less than 1200 ℃;
step three, coating anti-oxidation protective coating on the surface of the water-quenched ingot obtained in the step two to obtain an ingot with the coating on the surface; the anti-oxidation protective coating is an anti-oxidation protective coating which can resist the high temperature of not less than 1200 ℃;
step four, heating the ingot with the coating on the surface obtained in the step three, and then mechanically processing the ingot while the ingot is hot to obtain a mechanically processed ingot; the heating process comprises the following steps: heating to 810 deg.C, and keeping the temperature for 20min; the mechanical processing is multi-pass rolling, the rolling reduction of each pass is 35%, and after each pass of rolling, the steel is reheated to 810 ℃ and kept for at least 10min;
step five, sequentially annealing and surface finishing the machined cast ingot obtained in the step four to obtain a zirconium-gadolinium alloy; the temperature of the annealing treatment is 530 ℃, and the time is 150min; the surface finishing process comprises the following steps: and (5) grinding off surface oxide scale, and cutting off edge cracking parts.
Through detection, the mass fraction ratio of zirconium to gadolinium in the zirconium-gadolinium alloy prepared in the embodiment is 87:13 tensile strength A 15 Is 390MPa, wherein A 15 Represents zirconiumThe tensile sample made of gadolinium alloy is measured by adopting a gauge length of 15cm, the corrosion rate of the zirconium gadolinium alloy in boiling concentrated nitric acid with the concentration of 6mol/L is less than 0.01 mm/year, and the neutron shielding rate is more than 99.9%.
The above description is only for the preferred embodiment of the present invention, and is not intended to limit the present invention in any way. Any simple modifications, alterations and equivalent changes of the above embodiments according to the technical essence of the invention are still within the protection scope of the technical solution of the invention.
Claims (7)
1. The preparation method of the high-performance zirconium gadolinium alloy is characterized by comprising the following steps of:
step one, mixing a zirconium raw material and a gadolinium raw material, and then smelting to obtain an ingot;
step two, carrying out solid solution treatment and water quenching on the ingot obtained in the step one in sequence to obtain a water-quenched ingot; the process of the solution treatment comprises the following steps: heating to 1050-1400 ℃, and then preserving the temperature for 20-300min; water quenching is carried out immediately after the solution treatment;
step three, brushing an antioxidant protective coating on the surface of the water-quenched ingot obtained in the step two to obtain an ingot with the coating on the surface;
step four, heating the ingot with the coating on the surface obtained in the step three, and then machining to obtain a machined ingot; the mechanical processing is rolling or forging; the heating process comprises the following steps: heating to 750-850 ℃, and then preserving the heat for 20-100min; the mechanical processing is multi-pass rolling or multi-pass forging, the pressing amount of each pass of rolling or forging in the multi-pass rolling or multi-pass forging is 20% -50%, and the rolling or forging of each pass needs to be reheated to 750-850 ℃ and kept warm for at least 10min;
step five, sequentially annealing and surface finishing the machined cast ingot obtained in the step four to obtain a zirconium-gadolinium alloy; the mass fraction ratio of zirconium to gadolinium in the zirconium gadolinium alloy is 87 to 99:1 to 13; the annealing treatment temperature is 500-650 ℃, and the time is 30min-300min.
2. The method according to claim 1, wherein in the first step, the zirconium raw material is sponge zirconium, and the gadolinium raw material is gadolinium chips.
3. The preparation method of the high-performance zirconium gadolinium alloy according to claim 1, wherein the melting in the first step is performed by a non-consumable arc melting furnace, a consumable melting furnace, an induction melting furnace or a suspension melting furnace, and when the non-consumable arc melting furnace is used, the melting voltage is 50V to 1000V, and the melting current is 50A to 700A; when a consumable smelting furnace is adopted, the smelting voltage is 200V to 5000V; when an induction smelting furnace is adopted, the working frequency is 15KHz to 150KHz, when a suspension smelting furnace is adopted, the oscillation current is 200A to 800A, and the oscillation frequency is 15KHz to 50KHz; the smelting frequency is 3-6 times.
4. The method for preparing the high-performance zirconium gadolinium alloy according to claim 1, wherein before the solution treatment in the second step, the surface of the ingot is coated with an antioxidant protective coating resistant to high temperature of not less than 1200 ℃ and dried.
5. The preparation method of the high-performance zirconium gadolinium alloy according to claim 1, wherein the antioxidant protective coating in step three is an antioxidant protective coating resistant to high temperatures of not less than 1200 ℃, and the water-quenched ingot is dried after being coated with the antioxidant protective coating.
6. The method for preparing the high-performance zirconium gadolinium alloy according to claim 1, wherein the surface finishing process in the fifth step is as follows: and (4) grinding off surface oxide scale and cutting off edge cracking parts.
7. The method for preparing the high-performance zirconium gadolinium alloy according to claim 1, wherein in the fifth step, the corrosion rate of the zirconium gadolinium alloy in boiling concentrated nitric acid with the concentration of 6mol/L is not more than 0.01 mm/year, and the neutron shielding rate is not less than 99.9%.
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