CN111690864B - Preparation method of nuclear grade stainless steel for high-level waste glass curing container - Google Patents
Preparation method of nuclear grade stainless steel for high-level waste glass curing container Download PDFInfo
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Abstract
The nuclear-grade stainless steel for the high-level waste glass curing container prepared by the method can ensure that rare earth elements in the nuclear-grade stainless steel are stable and controllable, harmful impurity elements are greatly reduced, the structure is uniform and compact, the processing performance of the alloy is greatly improved, the yield is improved, and the nuclear-grade stainless steel has good mechanical property, high temperature resistance, corrosion resistance, oxidation resistance and other properties, excellent hot and cold processing performance, welding performance and machining performance, and has wide popularization and application prospects in the field of nuclear waste treatment.
Description
Technical Field
The invention belongs to the field of metal material metallurgy, and particularly relates to a preparation method of nuclear-grade stainless steel for a high-level waste glass solidification container.
Background
The utilization of nuclear energy includes power generation or nuclear power supply (nuclear power plants, ship-borne or satellite-borne nuclear reactors), activation analysis (analysis of material composition), radioactive reconnaissance, detection and flaw detection, medical killing or elimination of cancer cells, agricultural improvement of new species, seawater desalination, manufacture of nuclear weapons (atomic bombs, hydrogen bombs) and the like, and has important roles and roles in national economy and national defense safety. Throughout the industrial process of nuclear energy development and utilization, a large amount of waste material is produced that is no longer needed (at least not effectively utilized by humans at present) and is radioactive. The nuclear waste includes medium-low radioactive nuclear waste and high radioactive nuclear waste, the former mainly refers to radioactive waste liquid and waste generated in the power generation process of the nuclear power station, and accounts for 99% of all the nuclear waste, and the latter mostly generates from the manufacturing of military equipment and the post-treatment of spent fuel (i.e. nuclear fuel which is irradiated by radiation and used) of the nuclear power station, and is called high radioactive waste because of high radioactivity.
The high-level radioactive wastes contain radioactive nuclides of neptunium, plutonium, americium, technetium, iodine, strontium, cesium and the like, and are mainly characterized by high radioactive level, long half-decay period, high nuclide toxicity, high heating property and the like. The specific activity of the high-level waste (liquid waste) reaches 3.7 x 109Bq/L. The half-life periods of the neptunium-237, the plutonium-239 and the like are more than 10 ten thousand years, the neptunium-237 and the plutonium-239 cannot be degraded or eliminated by common physical, chemical or biological methods, and the harm can be reduced only by slow radioactive decay of the neptunium-237 and the plutonium-239. The time for high-level waste to be harmless is thousands of years, thousands of years or even longer. Once inside the biosphere, these radionuclides are extremely hazardous, and therefore disposal of high level waste has become a worldwide concern. The treatment of high-level waste materials is one of the hundreds of engineering projects in China and has been improved to the national height. The technological route of treating the high level waste in China adopts glass solidification-geological disposal, and a high level waste glass solidification container is a first safety barrier. The manufacturing of the high-level waste glass curing container can fill the domestic blank, and has important significance for the development of the nuclear waste treatment project in China.
According to the technical requirements of high-level waste liquid glass solidification, the glass solidification container is made of a metal material with high strength, toughness and plasticity, corrosion resistance and heat resistance, and stainless steel is one of the best choices. However, the stainless steels are various, including austenitic stainless steels, ferritic stainless steels, duplex stainless steels, martensitic stainless steels, precipitation hardening stainless steels, etc., according to the types of the microstructure of the matrix, wherein the austenitic stainless steels are chromium-nickel type iron-based alloys developed from 18Cr-8Ni, and are the most branded, most widely used and most used stainless steels, and the typical stainless steels are 304, 309, 310, 316L, 321, etc.; according to the application, the stainless steel comprises corrosion-resistant stainless steel, heat-resistant stainless steel, super-hard stainless steel and the like. Different stainless steels are selected or different alloy designs are performed according to different application requirements. According to the experience of developed countries, the high-level radioactive liquid waste glass solidification container is mainly made of nickel-chromium type austenitic stainless steel or nickel-based alloy. Although the prior art basically meets the manufacturing requirements of the conventional austenitic stainless steel in the aspects of smelting, remelting, hot working, cold working and the like, the technical requirements of the special nuclear grade stainless steel for the high-level waste liquid glass solidification container cannot be met in the aspects of precise regulation and control of components, control of trace elements, particularly control of harmful elements.
Disclosure of Invention
The nuclear-grade stainless steel for the high-level waste glass curing container prepared by the method can ensure that rare earth elements in the nuclear-grade stainless steel are stable and controllable, harmful impurity elements are greatly reduced, the structure is uniform and compact, the processing performance of the alloy is greatly improved, the yield is improved, and the nuclear-grade stainless steel has good mechanical property, high temperature resistance, corrosion resistance, oxidation resistance and other properties, excellent hot and cold processing performance, welding performance and machining performance, and has wide popularization and application prospects in the field of nuclear waste treatment.
The technical scheme of the invention is as follows:
the preparation method of the nuclear grade stainless steel for the high-level waste glass solidification container comprises the following steps:
1) vacuum melting
Putting Fe, Cr and Ni into a crucible, heating to melt, and carrying out vacuum refining at 1550-1650 ℃ for 25-70 kg/min, wherein the vacuum degree is better than 10 Pa; then adding C, Si and Mn, fully stirring and completely melting; adding ferrochromium nitride under nitrogen atmosphere, fully stirring, and rapidly adding Ce until the Ce is completely melted; adjusting the temperature of the molten steel to 1520-1560 ℃, casting into a rod at the speed of 50-90 kg/min in the nitrogen atmosphere, and removing surface oxide skin to obtain an electrode rod;
2) electroslag remelting
Preparing an electroslag remelting slag system, wherein the electroslag remelting slag system comprises the following components in parts by weight: CaF2: 55-70 parts of CaO: 8 to 15 parts of Al2O3: 8-15 parts of MgO: 5-15 parts of SiO2: 1-5 parts of CeO2: 1-5 parts of slag, fully mixing the slag, baking, melting the slag and arcing in a crystallizer, slowly inserting the electrode rod obtained in the step 1) into molten slag liquid, regulating the voltage to 45-60V and the current to 7000-14000A until the electrode rod is stable, remelting in a nitrogen or argon protective atmosphere, performing thermal feeding before remelting is finished, keeping the electrode rod in the crystallizer after remelting is finished, cooling for more than or equal to 30min, and demolding to obtain an electroslag ingot;
3) hot working forming
Preserving the temperature of the electroslag ingot obtained in the step 2) at 1050-1180 +/-15 ℃ for 2-3 hours, and forging and hot rolling the electroslag ingot to obtain a semi-finished plate or slab; the forging or hot rolling process adopts the means of ultrasonic flaw detection, surface finishing and the like to ensure the product quality.
4) Cold working forming
Carrying out softening annealing treatment on the semi-finished plate or plate blank prepared by hot rolling at 1000-1150 +/-10 ℃ for 30-60 min, and then carrying out cold rolling to obtain a finished plate;
5) heat treatment and finishing
And carrying out solution heat treatment on the finished plate at the temperature of 1000-1150 +/-10 ℃, wherein the heat treatment time is delta mm multiplied by 3-5 min/mm according to the thickness of the plate, and carrying out machining, nondestructive inspection, physicochemical inspection and the like to obtain the finished product of the nuclear-grade stainless steel for the high-level waste glass curing container.
The nuclear grade stainless steel for the high-level waste glass curing container comprises the following components in parts by weight:
cr: 20.5-23.5%, Ni: 10.5 to 13.5%, Si: 0.5-2.5%, Mn: 0.5-2.0%, C: 0.05-0.15%, N: 0.05-0.20%, Ce: 0.04-0.08%, Co: less than or equal to 0.05 percent, B: less than or equal to 0.002%, Cu: less than or equal to 0.05 percent, V: less than or equal to 0.05%, S: less than or equal to 0.01 percent, P: less than or equal to 0.015 percent, Fe: and (4) the balance.
The vacuum degree of the vacuum refining in the step 1) is more than 10 Pa.
The vacuum refining protective atmosphere in the step 1) is nitrogen.
And 2) baking the slag at 800 ℃ for 8-12 h.
And 2) adopting nitrogen or argon for protection in the remelting process of the step 2).
And 2) feeding by adopting a power successive subtraction method, wherein the feeding initial current is the electroslag remelting finishing current, and the feeding current reduction rate is 0.006-0.008 kA/s.
And 2) the diameter of the electroslag ingot is phi 320-phi 600 mm.
Advantages and positive effects of the invention
By adopting the vacuum induction melting method, the remelting electrode rod with stable and controllable components and low impurity content can be obtained, and a solid foundation is provided for obtaining high-purity alloy steel ingots subsequently.
The slag system of the invention is adopted to obtain the high-quality electroslag remelting rod. By adopting an electroslag remelting preparation technology, the electroslag remelting electrode rod is melted into metal droplets, then the metal droplets pass through a molten slag layer and perform complex high-temperature physical and chemical reaction with the molten slag layer, the content of harmful impurity elements in the alloy is reduced, the purity of the alloy is improved, and finally the metal droplets are recrystallized at the bottom of a crystallizer to be solidified into an electroslag remelting steel ingot with compact structure, stable and uniform and controllable components and low content of the harmful impurity elements.
The steel ingot obtained by the preparation method provided by the invention has the advantages of stable and controllable chemical components, particularly rare earth elements, high purity and less impurity elements, and is greatly beneficial to the subsequent hot and cold processing of the alloy, so that the yield of the alloy is improved, and good performance is obtained.
The nuclear-grade stainless steel for the high-level waste glass curing container, which is prepared by the method, has excellent mechanical properties, high temperature resistance, corrosion resistance and oxidation resistance, and good hot and cold processing properties, welding properties and machining properties, and the mechanical properties at room temperature are Rm: 694-682 MPa; rp 0.2: 345 to 356 MPa; δ 4 d: 53-58%; HB: 187 to 192. Tensile property at high temperature of 600 ℃: rm: 462-478 MPa, Rp0.2: 178-185 MPa, delta 4 d: 50-52%, the performance meets the technical index, can be applied to the field of high-level waste treatment industry, has important significance for the development of nuclear waste treatment engineering in China, can be popularized and applied to other fields of nuclear waste treatment, and has remarkable social benefit and economic benefit.
Detailed Description
Example 1
The nuclear grade stainless steel for the high-level waste glass curing container is prepared by weighing 1000kg of ingredients according to the mass percentage: c: 0.1%, Cr: 21.5%, Ni: 11.3%, Si: 2.2%, Mn: 0.65%, N: 0.20%, Ce: 0.25%, Fe: and (4) the rest.
Taking the components according to the proportion. Putting raw materials such as Fe, Cr, Ni and the like into a crucible, electrifying, carrying out induction heating to a full-melting state, and then, starting refining, wherein the refining temperature is 1580-1620 ℃, the vacuum degree is 5-8 Pa, and the refining time is 25 kg/min; then adding micro-alloying elements C, Si and Mn, fully stirring and completely melting; then nitrogen is filled, ferrochromium nitride is added under the protection of nitrogen, the mixture is fully stirred, and the rare earth raw material Ce is rapidly added until the rare earth raw material Ce is completely melted. Sampling and analyzing the components in front of the furnace under the nitrogen protection atmosphere and adjusting the components to meet the requirements. Adjusting the temperature of the molten steel to 1520-1560 ℃, and casting into a phi 260mm round bar at the speed of 50-90 kg/min in the nitrogen protective atmosphere.
High-level waste glass curing containerThe slag system comprises the following components in parts by weight: CaF2：52kg(65％)、CaO：8.0kg(10％)、Al2O3：9.6kg(12％)、MgO：6.4kg(8％)、SiO2：2.4kg(3％)、CeO2：1.6kg(2％)。
And removing oxide skin on the surface of the cast rod, preparing slag according to a slag system with a set proportion, weighing 80kg, and baking for 8 hours at 800 ℃. Directly melting slag and arcing the slag in a copper crystallizer, slowly inserting a remelting electrode rod into a molten slag pool, adjusting the voltage to be 52V and the current to be 9000-11000A after electrifying and arcing, and remelting. The remelting process adopts a nitrogen protective atmosphere. Before remelting, thermal feeding is carried out, a power successive subtraction method is adopted for feeding, the feeding initial current is electroslag remelting ending current (is 0), and the feeding current reduction rate is 0.006 kA/s. And after remelting, the product is left in a crystallizer to be cooled for 30min, and then demoulding can be carried out. And obtaining the electroslag ingot with the diameter of phi 500mm after demoulding.
Heating and preserving heat of the obtained nuclear-grade stainless steel electroslag ingot at 1150 ℃ for 2h, forging the nuclear-grade stainless steel electroslag ingot into a delta 200X 600mm plate blank by quick forging, carrying out ultrasonic flaw detection, blanking, surface finishing and other processes on the plate blank, heating and preserving heat for 90min at 1170 ℃, carrying out hot rolling to form a delta 45X 700X Lmm thick plate, carrying out solution heat treatment on the plate at 1080 ℃ for 60min and water cooling, and carrying out surface finishing, blanking, nondestructive inspection, performance detection and other processes to obtain a finished product of the nuclear-grade stainless steel plate for the high-level waste glass curing container.
The nuclear grade austenitic stainless steel bar comprises the following components in percentage by mass: c: 0.092%, Cr: 21.0%, Ni: 11.2%, Si: 2.1%, Mn: 0.63%, N: 0.14%, Ce: 0.04%, Co: 0.01%, B: 0.0015%, Cu: 0.02%, V: 0.017%, S: 0.001%, P: 0.0078%, Fe: and (4) the rest.
Harmful impurity elements S in the nuclear-grade stainless steel plate are as follows: 0.001%, P: 0.0078%, Co: 0.01%, B: 0.0015%, Cu: 0.02%, V: 0.0017%, and the element Ce which is difficult to control: 0.04%, N: 0.14 percent, and achieves the purposes of stable and controllable elements and low content of harmful impurity elements.
The applicant verifies that the room temperature mechanical property of the nuclear grade heat-resistant stainless steel prepared by the embodiment is Rm: 682MPa, Rp0.2: 345MPa, delta 4 d: 58%, HB: 187. tensile property at high temperature of 600 ℃: rm: 462MPa, Rp0.2: 178MPa, δ 4 d: 52 percent. The performance meets the index requirement, the method is successfully applied to the field of high-level waste treatment,
example 2
2500kg of nuclear-grade stainless steel ingredients for the high-level waste glass curing container are weighed, and the ingredients in the ingredients are as follows by mass percent: c: 0.12%, Cr: 21.0%, Ni: 11.5%, Si: 2.0%, Mn: 0.65%, N: 0.18%, Ce: 0.25%, Fe: and (4) the rest.
Taking the components according to the proportion. Placing Fe, Cr, Ni and the like in a crucible, electrifying, carrying out induction heating to a full-melting state, and then, starting refining, wherein the refining temperature is 1580-1620 ℃, the vacuum degree is better than 10Pa, and the refining time is 42 kg/min; then adding micro-alloying elements C, Si and Mn, fully stirring and completely melting; then nitrogen is filled, ferrochromium nitride is added under the protection of nitrogen and is fully stirred, and then Ce is taken out and is rapidly added until the Ce is completely melted. Sampling and analyzing the components in front of the furnace under the nitrogen protection atmosphere and adjusting the components to meet the requirements. Adjusting the temperature of the molten steel to 1520-1560 ℃, and casting into a phi 400mm round bar at a speed of 80kg/min in the nitrogen protective atmosphere.
The proportioning of electroslag remelting slag of nuclear grade stainless steel for a high-level waste glass curing container is 130kg/1 furnace, and the proportioning of slag systems in parts by weight is as follows: CaF2：78kg(60％)、CaO：19.5kg(15％)、Al2O3：13kg(10％)、MgO：11.4kg(8％)、SiO2：5.2kg(4％)、CeO2：3.9kg(3％)。
And removing oxide skin on the surface of the round bar, preparing slag according to a slag system with a set proportion, weighing 130kg, and baking for 12h at 800 ℃. Directly melting and arcing the slag in a copper crystallizer, slowly inserting a remelting electrode rod into the slag in a molten state, and starting melting after regulating the voltage of 56V and the current of 12500-14000A to be stable after electrifying and arcing. The electroslag remelting adopts argon protective atmosphere, thermal feeding is carried out before remelting is finished, power successive subtraction is adopted for feeding, feeding initial current is electroslag remelting finishing current (0), and the lowering rate of feeding current is 0.007 kA/s. And after remelting, the product is left in a crystallizer to be cooled for 90min, and then demoulding can be carried out. And obtaining the electroslag ingot with the diameter of phi 600mm after demoulding.
The obtained nuclear-grade stainless steel electroslag ingot is heated and insulated for 3h at 1170 ℃, is subjected to upsetting, drawing and long forging to form a delta 200X 800mm plate blank, the plate blank is subjected to ultrasonic flaw detection, blanking, surface finishing and other procedures, is heated and insulated for 90min at 1180 ℃, is hot-rolled into a delta 8X 1200X Lmm plate, and is subjected to solution heat treatment at 1100 ℃ in a trolley furnace, and is subjected to finishing, blanking, nondestructive inspection and performance detection to prepare a finished product of the nuclear-grade stainless steel plate for the high-level waste glass curing container.
The nuclear-grade austenitic bar comprises the following components in percentage by mass: c: 0.11%, Cr: 20.7%, Ni: 11.0%, Si: 1.78%, Mn: 0.62%, N: 0.13%, Ce: 0.05%, Co: 0.01%, B: 0.0015%, Cu: 0.017%, V: 0.005%, S: 0.001%, P: 0.0086%, Fe: and (4) the rest.
Harmful impurity elements S in the nuclear-grade stainless steel plate are as follows: 0.001%, P: 0.0086%, Co: 0.01%, B: 0.0015%, Cu: 0.017%, V: 0.005%, and the element Ce which is difficult to control: 0.05%, N: 0.13 percent, thereby achieving the purposes of stable and controllable elements and low content of harmful impurity elements.
The applicant verifies that the room temperature mechanical property of the nuclear-grade austenitic heat-resistant stainless steel prepared by the embodiment is Rm: 694MPa, Rp0.2: 356MPa, δ 4 d: 53%, HB: 192. tensile property at high temperature of 600 ℃: rm: 478MPa, Rp0.2: 185MPa, delta 4 d: 50 percent. The performance meets the requirement of engineering design, and the method is successfully applied to the field of high-level waste treatment.
Claims (8)
1. A preparation method of nuclear grade stainless steel for a high-level waste glass solidification container is characterized by comprising the following steps:
1) vacuum melting
Putting Fe, Cr and Ni into a crucible, heating to melt, and carrying out vacuum refining at 1550-1650 ℃, wherein the refining time is 25-70 kg/min, and the vacuum degree is more than 10 Pa; then adding C, Si and Mn, fully stirring and completely melting; adding ferrochromium nitride under nitrogen atmosphere, fully stirring and melting, and rapidly adding Ce until the Ce is completely melted; adjusting the temperature of the molten steel to 1520-1600 ℃, casting into a rod at the speed of 50-90 kg/min in the nitrogen atmosphere, and removing surface oxide skin to obtain an electrode rod;
2) electroslag remelting
Preparing an electroslag remelting slag system, wherein the electroslag remelting slag system comprises the following components in parts by weight: CaF2: 55-70 parts of CaO: 8 to 15 parts of Al2O3: 8-15 parts of MgO: 5-15 parts of SiO2: 1-5 parts of CeO2: 1-5 parts of slag, taking slag, fully mixing, baking, melting the slag in a crystallizer, arcing, slowly inserting the electrode rod obtained in the step 1) into molten slag liquid, regulating the voltage to 45-60V and the current to 7000-14000A until the electrode rod is stable, remelting in a protective atmosphere, carrying out thermal feeding before remelting is finished, keeping the electrode rod in the crystallizer after remelting is finished, cooling for more than or equal to 30min, and demolding to obtain an electroslag ingot;
3) hot working forming
Preserving the temperature of the electroslag ingot obtained in the step 2) at 1050-1195 ℃ for 2-3 h, and forging and hot rolling the electroslag ingot to obtain a semi-finished plate or slab;
4) cold working forming
Carrying out softening annealing treatment on the semi-finished plate or plate blank prepared by hot rolling at 1000-1160 ℃ for 30-60 min, and then carrying out cold rolling to obtain a finished plate;
5) heat treatment and finishing
And carrying out solution heat treatment on the finished plate at the temperature of 1000-1160 ℃, and machining to obtain the finished product of the nuclear-grade stainless steel for the high-level waste glass curing container.
2. The method of claim 1, wherein: the nuclear grade stainless steel for the high-level waste glass curing container comprises the following components in percentage by weight:
cr: 20.5-23.5%, Ni: 10.5 to 13.5%, Si: 0.5-2.5%, Mn: 0.5-2.0%, C: 0.05-0.15%, N: 0.05-0.20%, Ce: 0.04-0.08%, Co: less than or equal to 0.05 percent, B: less than or equal to 0.002%, Cu: less than or equal to 0.05 percent, V: less than or equal to 0.05%, S: less than or equal to 0.01 percent, P: less than or equal to 0.015 percent, Fe: and (4) the balance.
3. The method of claim 1, wherein: the vacuum melting protective atmosphere in the step 1) is nitrogen.
4. The method of claim 1, wherein: and 2) baking the slag at 800 ℃ for 8-12 h.
5. The method of claim 1, wherein: and 2) adopting nitrogen or argon for protection in the remelting process of the step 2).
6. The method of claim 1, wherein: and 2) performing thermal compensation by adopting a power successive subtraction method, wherein the initial current of the thermal compensation is the current of electroslag remelting finish, and the reduction rate of the thermal compensation current is 0.006-0.008 kA/s.
7. The method of claim 1, wherein: and 2) the diameter of the electroslag ingot is phi 320-phi 600 mm.
8. The method of claim 1, wherein: and 5) the time of the solution heat treatment is delta mm multiplied by 3-5 min/mm of the thickness of the plate.
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