Nickel-based alloy welding material for pressure vessel and preparation method thereof

Abstract

The present invention belongs to the field of metal material processing, and particularly relates to a nickel-based alloy welding material for pressure vessels and a preparation method thereof. The nickel-based alloy welding material for pressure vessels comprises the following raw materials in parts by weight: C: 0.01-0.10%, Si: 0.10-0.20%, Cr: 20.0-22.0%, Fe: 17.0-20.0%, Co: 2.5-4.0%, W: 0.20-1.00%, Mo: 8.0-10.0%, B: 0.005-0.050%, the total amount of Al and Ti: 2.0-4.0%, Z The product comprises r: 0.10-0.50%, V: 0.2-0.5%, Nb: 2.0-2.5%, Ta: 0.01-0.05%, RE: 0.20-0.30%, S: <0.005%, P: <0.005%, nano-ceramic material: 2.0-5.0%, and Ni balance. The product is obtained by melting-high and low temperature refining-annealing, forging-rolling, and multiple drawing-annealing and solution-aging treatment. The product can effectively solve the problems of easy oxidation, porosity or cracking, and low strength of nickel-based alloy welding materials during welding in the prior art.

Description

Technical Field

[0001] The present invention belongs to the field of metal materials, and in particular relates to a nickel-based alloy welding material for pressure vessels and a preparation method thereof. Background Art

[0002] With the advancement of my country's industrial technology, and the increasing demands on metal material performance, the demand and requirements for pressure vessels are increasing, whether in the high-tech fields of the nuclear and aviation industries or the traditional chemical industry. Whether it's a storage container, such as a chemical or hydrogen tank, or a reaction vessel, such as a reactor, all require pressure, which in turn places higher demands on the material. In the industry, based on the requirements of different media, the material selection and design of pressure vessels must have sufficient strength, rigidity, service life, and compatibility with the media to meet different operating conditions. The chemical composition, mechanical properties, and process performance of the pressure vessel must be comprehensively considered, and the welding performance of the pressure vessel should also be taken into consideration.

[0003] Currently, pressure vessels are still primarily made of nickel-based alloys. To ensure excellent sealing performance, welding materials should also be primarily nickel (Ni). Ni, as the primary element in current welding materials, is a rare alloying element that can both increase the strength of the alloy material and not significantly weaken its plasticity. It also possesses exceptional resistance to high temperatures, oxidation, and corrosion. However, welding nickel-based alloys also has significant drawbacks: high-temperature oxidation during welding can easily lead to pores and slag inclusions, affecting weld quality and sealing; grain growth during welding can affect toughness, and the cost is excessively high. Furthermore, hydrogen embrittlement can occur when used for hydrogen storage and transportation, leading to material failure.

[0004] Currently, there are two conventional approaches. One is to improve the welding process by optimizing welding parameters and preheating temperature to alleviate porosity, slag inclusion, and toughness issues, but the results are limited. The other is to refine the composition of nickel-based alloys to remove alloy impurities. This research direction will become the mainstream in the future. Summary of the Invention

[0005] The present invention aims to address the problems of nickel-based alloy welding materials for pressure vessels in the prior art, such as their tendency to oxidize, produce pores or cracks, and their low strength, by providing a novel nickel-based alloy welding material for pressure vessels and a method for preparing the same. This novel material not only addresses the aforementioned problems but also possesses the advantages of hydrogen embrittlement resistance and low cost. To achieve the above objectives, the present invention employs the following technical solutions to solve the technical problems:

[0006] The present invention provides a nickel-based alloy welding material for pressure vessels, comprising the following powder raw materials in parts by weight:

[0007] C: 0.01-0.10%, Si: 0.10-0.20%, Cr: 20.0-22.0%, Fe: 17.0-20.0%, Co: 2.5-4.0%, W: 0.20-1.00%, Mo: 8.0-10.0%, B: 0.005-0.050%, total amount of Al and Ti: 2.0-4.0%, Zr: 0.10-0.50%, V: 0.2-0.5%, Nb: 2.0-2.5%, Ta: 0.01-0.05%, RE: 0.20-0.30%, S: <0.005%, P: <0.005%, nano-ceramic materials: 2.0-5.0%, Ni balance.

[0008] Furthermore, the total amount of Mo and W is not less than 9.0%.

[0009] Furthermore, the weight ratio of Al to Ti is 0.5-1.5:1.

[0010] Furthermore, the weight ratio of Al to Ti is 0.8-1.4:1.

[0011] Furthermore, the RE is selected from La, Y, Ce or Sm.

[0012] Furthermore, the nano-ceramic material is selected from alumina, zirconium oxide, titanium carbide or silicon carbide.

[0013] Another object of the present invention is to provide a method for preparing a nickel-based alloy welding material for a pressure vessel, comprising the following steps:

[0014] S1: Raw materials are weighed according to the mass percentage of the formula and processed to obtain a uniform and refined mixed powder;

[0015] S2: The mixed powder and nano-ceramic material in S1 are placed in a smelting furnace for smelting, and after high-temperature refining and low-temperature refining, remelting and refining are performed, and then cast into alloy ingots;

[0016] S3: After annealing the alloy ingot, forging and rolling are performed to prepare alloy wire rods;

[0017] S4: After pre-treatment, the alloy wire rod is subjected to multiple drawing and annealing processes.

[0018] S5: Processing into alloy wire of required size and performing solution-aging treatment.

[0019] Furthermore, the processing process in S1 is to add the raw material powders except the nano-ceramic material into ethanol for ultrasonic treatment; filter, take out the insoluble matter, dry and then perform ball milling to obtain a mixed powder.

[0020] Furthermore, the forging process described in S3 is to forge the blank into alloy billet I at 950°C with a forging ratio of 3-4; forge into alloy billet II at 1050°C with a forging ratio of 7-8, and then forge into alloy billet III at the same temperature with a forging ratio of 3-4; the rolling process is to keep warm at 1000-1050°C for 0.5-1.5h, and hot-roll into alloy wire rod at 950-1100°C.

[0021] Furthermore, the solid solution is heated to 950-1050°C in a nitrogen environment, kept warm for 2-3 hours, continued to heat to 1050-1100°C, kept warm for 2-3 hours, continued to heat to 1100-1150°C, kept warm for 1-2 hours, continued to heat to 1150-1170°C, kept warm for 1-2 hours, and quickly water quenched to obtain a solid solution alloy; the aging is heated to 800-850°C, kept warm for 3-8 hours, air cooled, then heated to 750-770°C, kept warm for 10-15 hours, and air cooled.

[0022] The present invention has the following beneficial effects:

[0023] (1) The present invention provides a nickel-based alloy welding material for pressure vessels, which takes Ni as the matrix. Cr can improve the high-temperature oxidation resistance of the alloy; Co can improve the carbonization resistance; Mo can refine the grains and improve the thermal stability of the alloy; W and V can improve the strength of the alloy. The addition of Cr, Co, Mo, W, and V achieves a solid solution strengthening effect, improving its high-temperature oxidation resistance and thermal strength; at the same time, Cr, Mo, Co, and V can form carbides with C, and hard phases such as chromium carbide and cobalt carbide are dispersed in the solid solution strengthened matrix, improving high-temperature strength and plasticity; moreover, the improvement of high-temperature oxidation resistance and high-temperature strength can effectively inhibit welding pores caused by oxidation, and can effectively improve welding strength and sealing performance; in addition, the precipitated phases of Cr, Mo, and V have stability and hydrogen trapping ability, and the ionic bond formed between the carbide of V and hydrogen is the strongest, and the stably existing carbide precipitated phase is the most excellent hydrogen trap, which has hydrogen embrittlement resistance.

[0024] (2) The present invention provides a nickel-based alloy welding material for pressure vessels, wherein a certain proportion of Mo, Fe, and B are added to the alloy. During the high-temperature remelting process, a reaction occurs to form Mo2FeB2 and Mo2NiB2 ternary boride hard phases, which have excellent mechanical properties such as corrosion resistance, hardness, and wear resistance.

[0025] (3) The present invention provides a nickel-based alloy welding material for pressure vessels, wherein a certain amount of Fe, Nb and rare earth element RE are added to the alloy. First, Fe can improve resistance to high-temperature carburizing environments and control thermal expansion; at the same time, it can reduce the amount of precious metal Ni; second, Nb can reduce the tendency of strain cracking and can form Ni3Nb precipitation strengthening phase γ" in the alloy, thereby improving the alloy's high-temperature strength, creep resistance, corrosion resistance and other properties; in addition, Nb has a good affinity with O and can form a stable oxide Nb2O5, which has the effect of delaying corrosion; third, the rare earth element RE, on the one hand, RE and Nb synergistically act to improve the adhesion of the oxide film at high temperatures and refine the oxide grains; and by forming coordination with O and S at high temperatures, it can preferentially form smaller-sized rare earth oxide nanoparticles, which act as heterogeneous cores during the welding process, can refine the grains and improve the mechanical strength of the weld; on the other hand, it can improve the wettability of the welding material, make the weld easier to fill, and reduce defects.

[0026] (4) The present invention provides a nickel-based alloy welding material for pressure vessels. A certain amount of Al, Ti, Zr, Ta and other elements are added to the alloy, which can purify the grain boundaries and improve the performance; at the same time, a dispersed γ′ phase can be formed to improve the high-temperature strength of the alloy.

[0027] (5) The present invention provides a nickel-based alloy welding material for pressure vessels. A certain amount of nano-ceramic material is added to the alloy. First, it can improve the high-temperature oxidation resistance, wear resistance and other properties of the welding material; second, it can terminate the microcracks generated by stress and improve the mechanical properties; third, it can act as a hydrogen trap (or pin the grain boundaries to reduce the diffusion of hydrogen atoms) to improve the resistance to hydrogen embrittlement.

[0028] (6) The present invention provides a method for preparing nickel-based alloy welding materials for pressure vessels. First, the impurity content is reduced by alcohol washing, effectively reducing the precipitation and segregation of harmful carbides; the particle size of the powder is reduced by ball milling, promoting interphase compatibility; second, the purity and plasticity of the alloy are improved by forging-rolling process; third, a multi-step graded solid solution-aging treatment is adopted in a nitrogen environment to refine the grain size and improve the mechanical properties; at the same time, the hydrogen embrittlement performance is improved. DETAILED DESCRIPTION

[0029] The present invention will be described in detail below with reference to the following examples. However, it should be understood that the following examples are merely illustrative of the embodiments of the present invention and are not intended to limit the scope of the present invention.

[0030] The purpose of the present invention is to develop a nickel-based alloy welding material for pressure vessels to solve the problems existing in existing nickel-based alloy welding materials for pressure vessels. The idea of ​​implementation is: with Ni as the main material, the addition of high-temperature resistant elements such as Cr, Co, Mo, W, and V is added through formula design to achieve solid solution strengthening and improve antioxidant performance; add elements such as B and Fe to improve hardness and plasticity; and add precipitation strengthening elements such as Al, Ti, Nb, Ta, and RE to improve high-temperature strength and purify grain boundaries; finally, compound nano-ceramic materials to further improve hydrogen embrittlement resistance while improving mechanical properties. The above components are further improved in performance through a grain size refinement process. The embodiments of the present invention are as follows:

[0031] An embodiment of the present invention provides a nickel-based alloy welding material for a pressure vessel, comprising the following powder raw materials in parts by weight:

[0032] C: 0.01-0.10%, Si: 0.10-0.20%, Cr: 20.0-22.0%, Fe: 17.0-20.0%, Co: 2.5-4.0%, W: 0.20-1.00%, Mo: 8.0-10.0%, B: 0.005-0.050%, total amount of Al and Ti: 2.0-4.0%, Zr: 0.10-0.50%, V: 0.2-0.5%, Nb: 2.0-2.5%, Ta: 0.01-0.05%, RE: 0.20-0.30%, S: <0.005%, P: <0.005%, nano-ceramic materials: 2.0-5.0%, Ni balance.

[0033] The total amount of Mo and W is not less than 9.0%.

[0034] The weight ratio of Al to Ti is 0.5-1.5:1.

[0035] The weight ratio of Al to Ti is 0.8-1.4:1.

[0036] The RE is selected from La, Y, Ce or Sm.

[0037] The nano ceramic material is selected from alumina, zirconium oxide, titanium carbide or silicon carbide.

[0038] Another object of an embodiment of the present invention is to provide a method for preparing a nickel-based alloy welding material for a pressure vessel, comprising the following steps:

[0039] S1: The raw materials are weighed according to the mass percentage of the formula and processed to obtain a uniform and refined mixed powder.

[0040] The treatment process comprises adding raw material powders other than the nano-ceramic material into ethanol, subjecting the mixture to magnetic stirring at 500-2000 r / min for 2-5 hours, and then subjecting the mixture to ultrasonic treatment at 50 kHz for 2 hours to obtain an ethanol suspension; filtering the mixture, collecting the insoluble matter, and drying the matter in an 80° C. drying oven for 2 hours; placing the insoluble matter into a ball mill, adding long-chain fatty acids, and subjecting the ball mill to ball milling in a high-energy ball mill to obtain a uniformly refined mixed powder; wherein the grinding balls are made of corundum balls, the ball-to-material mass ratio is 5:8:1, the ball milling process lasts for 5-10 hours, and the ball milling rotation speed is 150-200 r / min;

[0041] The ratio of the long-chain fatty acid to the total mass of the raw material powder is 2g:100g;

[0042] The long-chain fatty acid is myristic acid or lauric acid, etc., and myristic acid is preferred.

[0043] S2: The mixed powder and nano-ceramic material in S1 are placed in a smelting furnace for smelting, and after high-temperature refining and low-temperature refining, they are remelted and cast into alloy ingots.

[0044] The high temperature refining is smelting at 1750-1850°C for 30-45 minutes;

[0045] The low temperature refining is smelting at 1650-1700°C for 15-25 minutes;

[0046] The remelting is electroslag remelting, and the furnace temperature is 1750-1850°C.

[0047] S3: After annealing, the alloy ingot is forged and rolled to prepare alloy wire rod.

[0048] The annealing process is to heat to 1000-1050°C and keep the temperature for 20-35h;

[0049] The forging process is as follows: at 950°C, the billet is forged into alloy billet I with a forging ratio of 3-4; after tempering at 950-1000°C for 1-2 hours, the billet is forged into alloy billet II at 1050°C with a forging ratio of 7-8; and then the billet is forged into alloy billet III at the same temperature with a forging ratio of 3-4;

[0050] The rolling process comprises the following steps: keeping the temperature at 1000-1050° C. for 0.5-1.5 hours, and hot rolling the steel bars at 950-1100° C. into Φ4.05.0 mm alloy wire rods.

[0051] S4: After pre-treatment, the alloy wire rod is subjected to multiple drawing-annealing passes.

[0052] The pretreatment comprises heating the alloy wire rod to 950° C. and keeping the temperature for 1.5 hours, oil cooling for softening, alkali boiling, high-pressure water washing, acid washing after water washing, and ultrasonic cleaning;

[0053] The drawing process includes adding a lubricant before drawing and performing multiple drawing processes to obtain the alloy wire;

[0054] The annealing is vacuum annealing after 6-10 drawing passes, and the annealing temperature is 640-800°C.

[0055] S5: Processing into alloy wire of required size and performing solution-aging treatment.

[0056] The solid solution is heated to 950-1050°C in a nitrogen environment, kept warm for 2-3 hours, continued to heat to 1050-1100°C, kept warm for 2-3 hours, continued to heat to 1100-1150°C, kept warm for 1-2 hours, continued to heat to 1150-1170°C, kept warm for 1-2 hours, and quickly water quenched to obtain a solid solution alloy; the aging is heated to 800-850°C, kept warm for 3-8 hours, air cooled, then heated to 750-770°C, kept warm for 10-15 hours, and air cooled.

[0057] In order to further understand the present invention, the nickel-based alloy welding material for pressure vessels provided by the present invention is described in detail below with reference to specific embodiments. The protection scope of the present invention is not limited by the following embodiments.

[0058] Example 1

[0059] This embodiment provides a nickel-based alloy welding material for a pressure vessel, comprising the following powder raw materials in parts by weight:

[0060] C: 0.05%, Si: 0.15%, Cr: 21.0%, Fe: 19.0%, Co: 3.5%, W: 0.7%, Mo: 9.0%, B: 0.030%, total amount of Al and Ti: 3.0%, Zr: 0.35%, V: 0.4%, Nb: 2.2%, Ta: 0.03%, RE: 0.25%, S: 0.002%, P: 0.002%, nano-ceramic materials: 3.0%, Ni balance.

[0061] The weight ratio of Al to Ti is 1.2:1.

[0062] The RE is selected from Sm.

[0063] The nano ceramic material is selected from zirconium oxide.

[0064] This embodiment also provides a method for preparing a nickel-based alloy welding material for a pressure vessel, comprising the following steps:

[0065] S1: The raw materials are weighed according to the mass percentage of the formula and processed to obtain a uniform and refined mixed powder.

[0066] The treatment process comprises adding raw material powders other than the nano-ceramic material into ethanol, magnetically stirring at 1000 rpm for 3 hours, and then subjecting the mixture to 50 kHz ultrasonic treatment for 2 hours to obtain an ethanol suspension; filtering, collecting insoluble matter, and drying the matter in an 80° C. drying oven for 2 hours; placing the insoluble matter into a ball mill, adding myristic acid, and subjecting the ball mill to ball milling in a high-energy ball mill to obtain a uniformly refined mixed powder; wherein the grinding balls are made of corundum balls, the ball-to-material mass ratio is 7:1, the ball milling process is performed for 7 hours, and the ball milling rotation speed is 180 rpm;

[0067] The usage ratio of the myristic acid to the total mass of the raw material powder is 2g:100g.

[0068] S2: The mixed powder and nano-ceramic material in S1 are placed in a smelting furnace for smelting, and after high-temperature refining and low-temperature refining, they are remelted and cast into alloy ingots.

[0069] The high temperature refining is smelting at 1800°C for 40 minutes;

[0070] The low temperature refining is smelting at 1680°C for 20 minutes;

[0071] The remelting is electroslag remelting, and the furnace temperature is 1800°C.

[0072] S3: After annealing, the alloy ingot is forged and rolled to prepare alloy wire rod.

[0073] The annealing process is heating to 1020°C and keeping the temperature for 30 hours;

[0074] The forging process is as follows: at 950°C, the billet is forged into alloy billet I with a forging ratio of 3.5; after tempering at 980°C for 1.5 hours, the billet is forged into alloy billet II at 1050°C with a forging ratio of 7.5; and then the billet is forged into alloy billet III at the same temperature with a forging ratio of 3.5;

[0075] The rolling process comprises the steps of keeping the temperature at 1020° C. for 1 hour and hot rolling the alloy wire rod at 1040° C. into a Φ4.5 mm alloy wire rod.

[0076] S4: After pre-treatment, the alloy wire rod is subjected to multiple drawing-annealing passes.

[0077] The pretreatment comprises heating the alloy wire rod to 950° C. and keeping the temperature for 1.5 hours, oil cooling for softening, alkali boiling, high-pressure water washing, acid washing after water washing, and ultrasonic cleaning;

[0078] The drawing process includes adding a lubricant before drawing and performing multiple drawing processes to obtain the alloy wire;

[0079] The annealing is vacuum annealing after 8 drawing passes, and the annealing temperature is 700°C.

[0080] S5: Processing into alloy wire of required size and performing solution-aging treatment.

[0081] The solid solution is heated to 1000°C in a nitrogen environment, kept warm for 2.5 hours, continued to heat to 1080°C, kept warm for 2.5 hours, continued to heat to 1120°C, kept warm for 1.5 hours, continued to heat to 1160°C, kept warm for 1.5 hours, and quickly water quenched to obtain a solid solution alloy; the aging is heated to 820°C, kept warm for 5 hours, air cooled, then heated to 760°C, kept warm for 12 hours, and air cooled.

[0082] Example 2

[0083] This embodiment provides a nickel-based alloy welding material for a pressure vessel, comprising the following powder raw materials in parts by weight:

[0084] C: 0.01%, Si: 0.10%, Cr: 20.0%, Fe: 17.0%, Co: 4.0%, W: 0.2%, Mo: 10.0%, B: 0.050%, total amount of Al and Ti: 4.0%, Zr: 0.1%, V: 0.5%, Nb: 2.0%, Ta: 0.05%, RE: 0.2%, S: 0.002%, P: 0.002%, nano-ceramic material: 5.0%, Ni balance.

[0085] The weight ratio of Al to Ti is 1.2:1.

[0086] The RE is selected from Sm.

[0087] The nano ceramic material is selected from zirconium oxide.

[0088] This embodiment also provides a method for preparing a nickel-based alloy welding material for a pressure vessel, comprising the following steps:

[0089] S1: The raw materials are weighed according to the mass percentage of the formula and processed to obtain a uniform and refined mixed powder.

[0090] The treatment process comprises adding raw material powders other than the nano-ceramic material into ethanol, magnetically stirring at 500 rpm for 5 hours, and then subjecting the mixture to 50 kHz ultrasonic treatment for 2 hours to obtain an ethanol suspension; filtering, collecting insoluble matter, and drying the matter in an 80° C. drying oven for 2 hours; placing the insoluble matter into a ball mill, adding myristic acid, and subjecting the ball mill to ball milling in a high-energy ball mill to obtain a uniformly refined mixed powder; wherein the grinding balls are made of corundum balls, the ball-to-material mass ratio is 8:1, the ball milling process is 5 hours, and the ball milling rotation speed is 200 rpm;

[0091] The usage ratio of the myristic acid to the total mass of the raw material powder is 2g:100g.

[0092] S2: The mixed powder and nano-ceramic material in S1 are placed in a smelting furnace for smelting, and after high-temperature refining and low-temperature refining, they are remelted and cast into alloy ingots.

[0093] The high temperature refining is smelting at 1750°C for 45 minutes;

[0094] The low temperature refining is smelting at 1650°C for 25 minutes;

[0095] The remelting is electroslag remelting, and the furnace temperature is 1750°C.

[0096] S3: After annealing, the alloy ingot is forged and rolled to prepare alloy wire rod.

[0097] The annealing process is to heat to 1000°C and keep warm for 35 hours;

[0098] The forging process is as follows: at 950°C, the billet is forged into alloy billet I with a forging ratio of 3; after tempering at 950°C for 2 hours, the billet is forged into alloy billet II at 1050°C with a forging ratio of 8; and then the billet is forged into alloy billet III at the same temperature with a forging ratio of 4;

[0099] The rolling process comprises the steps of keeping the temperature at 1000° C. for 1.5 hours and hot rolling the alloy wire rod at 950° C. into a Φ4.0 mm alloy wire rod.

[0100] S4: After pre-treatment, the alloy wire rod is subjected to multiple drawing-annealing passes.

[0101] The pretreatment comprises heating the alloy wire rod to 950° C. and keeping the temperature for 1.5 hours, oil cooling for softening, alkali boiling, high-pressure water washing, acid washing after water washing, and ultrasonic cleaning;

[0102] The drawing process includes adding a lubricant before drawing and performing multiple drawing processes to obtain the alloy wire;

[0103] The annealing is vacuum annealing after 10 drawing passes, and the annealing temperature is 640°C.

[0104] S5: Processing into alloy wire of required size and performing solution-aging treatment.

[0105] The solid solution is heated to 1050°C in a nitrogen environment, kept warm for 2 hours, continued to heat to 1100°C, kept warm for 2 hours, continued to heat to 1150°C, kept warm for 1 hour, continued to heat to 1170°C, kept warm for 1 hour, and quickly water quenched to obtain a solid solution alloy; the aging is heated to 850°C, kept warm for 3 hours, air cooled, then heated to 770°C, kept warm for 10 hours, and air cooled.

[0106] Example 3

[0107] This embodiment provides a nickel-based alloy welding material for a pressure vessel, comprising the following powder raw materials in parts by weight:

[0108] C: 0.1%, Si: 0.20%, Cr: 22.0%, Fe: 20.0%, Co: 2.5%, W: 1.0%, Mo: 8.0%, B: 0.005%, total amount of Al and Ti: 2.0%, Zr: 0.5%, V: 0.2%, Nb: 2.5%, Ta: 0.01%, RE: 0.3%, S: 0.002%, P: 0.002%, nano-ceramic material: 2.0%, Ni balance.

[0109] The weight ratio of Al to Ti is 1.2:1.

[0110] The RE is selected from Sm.

[0111] The nano ceramic material is selected from zirconium oxide.

[0112] This embodiment also provides a method for preparing a nickel-based alloy welding material for a pressure vessel, comprising the following steps:

[0113] S1: The raw materials are weighed according to the mass percentage of the formula and processed to obtain a uniform and refined mixed powder.

[0114] The treatment process comprises adding raw material powders other than the nano-ceramic material into ethanol, magnetically stirring at 2000 rpm for 2 hours, and then subjecting the mixture to 50 kHz ultrasonic treatment for 2 hours to obtain an ethanol suspension; filtering, collecting insoluble matter, and drying the matter in an 80° C. drying oven for 2 hours; placing the insoluble matter into a ball mill, adding myristic acid, and subjecting the ball mill to ball milling in a high-energy ball mill to obtain a uniformly refined mixed powder; wherein the grinding balls are made of corundum balls, the ball-to-material mass ratio is 5:1, the ball milling process is 10 hours, and the ball milling rotation speed is 150 rpm;

[0115] The usage ratio of the myristic acid to the total mass of the raw material powder is 2g:100g.

[0116] S2: The mixed powder and nano-ceramic material in S1 are placed in a smelting furnace for smelting, and after high-temperature refining and low-temperature refining, they are remelted and cast into alloy ingots.

[0117] The high temperature refining is smelting at 1850°C for 30 minutes;

[0118] The low temperature refining is smelting at 1700°C for 15 minutes;

[0119] The remelting is electroslag remelting, and the furnace temperature is 1850°C.

[0120] S3: After annealing, the alloy ingot is forged and rolled to prepare alloy wire rod.

[0121] The annealing process is heating to 1050°C and keeping the temperature for 20 hours;

[0122] The forging process is as follows: at 950°C, the billet is forged into alloy billet I with a forging ratio of 4; after tempering at 1000°C for 1 hour, the billet is forged into alloy billet II at 1050°C with a forging ratio of 7; and then the billet is forged into alloy billet III at the same temperature with a forging ratio of 3;

[0123] The rolling process comprises the steps of keeping the temperature at 1050° C. for 0.5 h and hot rolling the alloy wire rod at 1100° C. into a Φ5.0 mm alloy wire rod.

[0124] S4: After pre-treatment, the alloy wire rod is subjected to multiple drawing-annealing passes.

[0125] The pretreatment comprises heating the alloy wire rod to 950° C. and keeping the temperature for 1.5 hours, oil cooling for softening, alkali boiling, high-pressure water washing, acid washing after water washing, and ultrasonic cleaning;

[0126] The drawing process includes adding a lubricant before drawing and performing multiple drawing processes to obtain the alloy wire;

[0127] The annealing is vacuum annealing after six drawing passes, and the annealing temperature is 800°C.

[0128] S5: Processing into alloy wire of required size and performing solution-aging treatment.

[0129] The solid solution is heated to 950°C in a nitrogen environment, kept warm for 3 hours, continued to heat to 1050°C, kept warm for 3 hours, continued to heat to 1100°C, kept warm for 2 hours, continued to heat to 1150°C, kept warm for 2 hours, and quickly water quenched to obtain a solid solution alloy; the aging is heated to 800°C, kept warm for 8 hours, air cooled, then heated to 750°C, kept warm for 15 hours, and air cooled.

[0130] Example 4

[0131] The rest is the same as in Example 1, except that:

[0132] In a formula of nickel-based alloy welding material for pressure vessels,

[0133] The weight ratio of Al to Ti is 1.4:1.

[0134] Example 5

[0135] The rest is the same as in Example 1, except that:

[0136] In a formula of nickel-based alloy welding material for pressure vessels,

[0137] The weight ratio of Al to Ti is 0.8:1.

[0138] Example 6

[0139] The rest is the same as in Example 1, except that:

[0140] In a formula of nickel-based alloy welding material for pressure vessels,

[0141] The weight ratio of Al to Ti is 1.5:1.

[0142] Example 7

[0143] The rest is the same as in Example 1, except that:

[0144] In a formula of nickel-based alloy welding material for pressure vessels,

[0145] The weight ratio of Al to Ti is 0.5:1.

[0146] Example 8

[0147] The rest is the same as in Example 1, except that:

[0148] In a formula of nickel-based alloy welding material for pressure vessels,

[0149] The RE is selected from Y.

[0150] Example 9

[0151] The rest is the same as in Example 1, except that:

[0152] In a formula of nickel-based alloy welding material for pressure vessels,

[0153] The RE is selected from Ce.

[0154] Example 10

[0155] The rest is the same as in Example 1, except that:

[0156] In a formula of nickel-based alloy welding material for pressure vessels,

[0157] The RE is selected from La.

[0158] Example 11

[0159] The rest is the same as in Example 1, except that:

[0160] In a formula of nickel-based alloy welding material for pressure vessels,

[0161] The nano ceramic material is selected from alumina.

[0162] Example 12

[0163] The rest is the same as in Example 1, except that:

[0164] In a formula of nickel-based alloy welding material for pressure vessels,

[0165] The nano ceramic material is selected from titanium carbide.

[0166] Example 13

[0167] The rest is the same as in Example 1, except that:

[0168] In a formula of nickel-based alloy welding material for pressure vessels,

[0169] The nano ceramic material is selected from silicon carbide.

[0170] The following comparative examples are compared with Example 1:

[0171] Comparative Example 1

[0172] The rest is the same as in Example 1, except that:

[0173] A nickel-based alloy welding material for pressure vessels, comprising the following powder raw materials in parts by weight:

[0174] C: 0.05%, Si: 0.15%, Cr: 21.0%, Fe: 19.0%, Co: 3.5%, W: 0.7%, Mo: 8.0%, B: 0.030%, total amount of Al and Ti: 3.0%, Zr: 0.35%, V: 0.4%, Nb: 2.2%, Ta: 0.03%, RE: 0.25%, S: 0.002%, P: 0.002%, nano-ceramic materials: 3.0%, Ni balance.

[0175] Comparative Example 2

[0176] The rest is the same as in Example 1, except that:

[0177] In a formula of nickel-based alloy welding material for pressure vessels,

[0178] The weight ratio of Al to Ti is 0:1, that is, no Al is added.

[0179] Comparative Example 3

[0180] The rest is the same as in Example 1, except that:

[0181] In a formula of nickel-based alloy welding material for pressure vessels,

[0182] The weight ratio of Al to Ti is 2:1.

[0183] Comparative Example 4

[0184] The rest is the same as in Example 1, except that:

[0185] In a formula of nickel-based alloy welding material for pressure vessels,

[0186] The weight fraction of B is 0; that is, no B is added.

[0187] Comparative Example 5

[0188] The rest is the same as in Example 1, except that:

[0189] In a formula of nickel-based alloy welding material for pressure vessels,

[0190] The weight fraction of V is 0; that is, no V is added.

[0191] Comparative Example 6

[0192] The rest is the same as in Example 1, except that:

[0193] In a formula of nickel-based alloy welding material for pressure vessels,

[0194] The weight fraction of Nb is 0, that is, no Nb is added.

[0195] Comparative Example 7

[0196] The rest is the same as in Example 1, except that:

[0197] In a formula of nickel-based alloy welding material for pressure vessels,

[0198] The weight fraction of the RE is 0; that is, no RE is added.

[0199] Comparative Example 8

[0200] The rest is the same as in Example 1, except that:

[0201] In a formula of nickel-based alloy welding material for pressure vessels,

[0202] The weight fraction of the nano-ceramic material is 0, that is, no nano-ceramic material is added.

[0203] Comparative Example 9

[0204] The rest is the same as in Example 1, except that:

[0205] In a method for preparing a nickel-based alloy welding material for a pressure vessel, in S1,

[0206] The treatment process does not involve ball milling.

[0207] Comparative Example 10

[0208] The rest is the same as in Example 1, except that:

[0209] In a method for preparing a nickel-based alloy welding material for a pressure vessel, in S3,

[0210] The alloy billet II has a forging ratio of 4.5.

[0211] Comparative Example 11

[0212] The rest is the same as in Example 1, except that:

[0213] In a method for preparing a nickel-based alloy welding material for a pressure vessel, in S5,

[0214] S5: Processing into alloy wire of required size and performing solution-aging treatment.

[0215] The solid solution is heated to 1000°C in a nitrogen environment, kept warm for 2.5 hours, continued to heat to 1160°C, kept warm for 1.5 hours, and quickly water quenched to obtain a solid solution alloy; the aging is heated to 760°C, kept warm for 12 hours, and air cooled.

[0216] The physical properties of the nickel-based alloy welding materials for pressure vessels prepared in the examples of the present invention and the comparative examples were measured, and the results are shown in Table 1.

[0217] Table 1 Physical test performance of each embodiment

[0218]

[0219] It can be observed from Examples 1-13 that the nickel-based alloy welding material for pressure vessels of the present invention has excellent mechanical properties and corrosion resistance; at the same time, it has excellent anti-hydrogen embrittlement effect, etc.

[0220] From Example 1 and Comparative Examples 1-8, it can be observed that the addition of appropriate amounts of Mo and W to the nickel-based alloy welding material for pressure vessels of the present invention achieves a solid solution strengthening effect, thereby improving its high-temperature oxidation resistance and thermal strength; Al and Ti play an important role in forming a dispersed γ′ phase and improving mechanical properties; B can strengthen grain boundary stability and improve performance; V can provide high-temperature strength and the formed carbides have excellent hydrogen trapping ability, providing excellent hydrogen embrittlement resistance; Nb has a reduced tendency to strain cracking and can improve the alloy's high-temperature strength, creep resistance, corrosion resistance, and other properties; RE has good high-temperature oxidation resistance and can also improve high-temperature strength; the nano-ceramic material has good mechanical properties and hydrogen embrittlement resistance, etc.

[0221] From Example 1 and Comparative Examples 9-11, it can be observed that ball milling has a positive effect on reducing particle size, increasing surface activity, and promoting interphase compatibility; a high forging ratio can refine grains, improving mechanical properties and resistance to hydrogen embrittlement; and a multi-step solution-aging process facilitates grain refinement, further enhancing performance. In summary, a suitable preparation process has a positive effect on the performance of nickel-based alloy welding materials.

[0222] The test method is as follows:

[0223] (1) Mechanical property test: The nickel alloy welding materials obtained in the examples and comparative examples were used to perform tungsten inert gas arc welding on the NO8120 alloy material. The room temperature mechanical property and high temperature mechanical property tests of the welded joints were performed at room temperature and 350°C, respectively, in accordance with GB / T2651 2008 "Tensile test method for welded joints".

[0224] (2) Corrosion rate: The corrosion resistance test was carried out using the ASTM G28 A method, and the test time was 120 h.

[0225] (3) Tensile strength after hydrogen charging: An electrochemical dynamic hydrogen charging slow tensile test was used to study the changes in mechanical properties under different hydrogen charging current densities. The standard GB / T2651 2008 "Welded joint tensile test method" was used. A constant current polarization method was used to charge hydrogen simultaneously during the tensile process. The sample was the cathode, the Pt sheet was the anode, and the electrolyte was 0.5 mol / L H2SO4 + 1.85 mmol / L Na4P2O7 (Na4P2O7 is a poisoning agent that inhibits H from recombining into H2). The hydrogen charging current density was 40 mA / cm 2 .

[0226] With the above-described preferred embodiments of the present invention as a guide, and with reference to the above description, relevant personnel are fully capable of making various changes and modifications without departing from the technical scope of this invention. The technical scope of this invention is not limited to the contents of the specification and must be determined according to the scope of the claims.

Claims

1. A nickel-based alloy welding material for pressure vessels, characterized by: The powder raw materials include the following parts by weight: C: 0.01-0.10%, Si: 0.10-0.20%, Cr: 20.0-22.0%, Fe: 17.0-20.0%, Co: 2.5-4.0%, W: 0.20-1.00%, Mo: 8.0-10.0%, B: 0.005-0.050%, total amount of Al and Ti: 2.0-4.0%, Zr: 0.10-0.50%, V: 0.2-0.5%, Nb: 2.0-2.5%, Ta: 0.01-0.05%, RE: 0.20-0.30%, S: <0.005%, P: <0.005%, nano-ceramic materials: 2.0-5.0%, Ni balance.

2. The nickel-based alloy welding material for pressure vessels according to claim 1, characterized in that: The total amount of Mo and W is not less than 9.0%.

3. The nickel-based alloy welding material for pressure vessels according to claim 1, characterized in that: The weight ratio of Al to Ti is 0.5-1.5:

1.

4. The nickel-based alloy welding material for pressure vessels according to claim 3, characterized in that: The weight ratio of Al to Ti is 0.8-1.4:

1.

5. The nickel-based alloy welding material for pressure vessels according to claim 1, characterized in that: The RE is selected from La, Y, Ce or Sm.

6. The nickel-based alloy welding material for pressure vessels according to claim 1, characterized in that: The nano ceramic material is selected from alumina, zirconium oxide, titanium carbide or silicon carbide.

7. The method for preparing a nickel-based alloy welding material for a pressure vessel according to any one of claims 1 to 6, characterized in that: The following steps are involved: S1: Raw materials are weighed according to the mass percentage of the formula and processed to obtain a uniform and refined mixed powder; S2: The mixed powder and nano-ceramic material in S1 are placed in a smelting furnace for smelting, and after high-temperature refining and low-temperature refining, remelting and refining are performed, and then cast into alloy ingots; S3: After annealing the alloy ingot, forging and rolling are performed to prepare alloy wire rods; S4: After pre-treatment, the alloy wire rod is subjected to multiple drawing and annealing processes. S5: Processing into alloy wire of required size and performing solution-aging treatment.

8. The method for preparing a nickel-based alloy welding material for pressure vessels according to claim 7, characterized in that: The processing process in S1 is to add raw material powders except nano-ceramic materials into ethanol for ultrasonic treatment; filter, take out insoluble matter, dry and then perform ball milling to obtain mixed powder.

9. The method for preparing a nickel-based alloy welding material for pressure vessels according to claim 7, characterized in that: The forging process described in S3 is to forge the billet into alloy billet I at 950°C with a forging ratio of 3-4; forge into alloy billet II at 1050°C with a forging ratio of 7-8, and then forge into alloy billet III at the same temperature with a forging ratio of 3-4; the rolling process is to keep the billet at 1000-1050°C for 0.5-1.5h and hot-roll it into alloy wire rod at 950-1100°C.

10. The method for preparing a nickel-based alloy welding material for pressure vessels according to claim 7, characterized in that: The solid solution is heated to 950-1050°C in a nitrogen environment, kept warm for 2-3 hours, continued to heat to 1050-1100°C, kept warm for 2-3 hours, continued to heat to 1100-1150°C, kept warm for 1-2 hours, continued to heat to 1150-1170°C, kept warm for 1-2 hours, and quickly water quenched to obtain a solid solution alloy; the aging is heated to 800-850°C, kept warm for 3-8 hours, air cooled, then heated to 750-770°C, kept warm for 10-15 hours, and air cooled.

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