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

Abstract

The invention belongs to the field of metal material processing, and particularly relates to a nickel base alloy welding material for a pressure vessel and a preparation method thereof.The nickel base alloy welding material for the pressure vessel comprises, by weight, 0.01%-0.10% of C, 0.10%-0.20% of Si, 20.0%-22.0% of Cr, 17.0%-20.0% of Fe, 2.5%-4.0% of Co, 0.20%-1.00% of W, 8.0%-10.0% of Mo, 0.005%-0.050% of B, 2.0%-4.0% of the total amount of Al and Ti, 0.10%-0.50% of Zr, 0.2%-0.5% of V, 2.0%-2.5% of Nb, 0.01%-0.05% of Ta, 0.20%-0.30% of RE, smaller than 0.005% of S, smaller than 0.005% of P, 2.0%-5.0 The nickel-based alloy welding material is obtained through smelting, high and low temperature refining, annealing, forging, rolling, multi-pass drawing, annealing and solid solution-aging treatment, and the problems that in the prior art, when a nickel-based alloy welding material is used for welding, air holes or cracks are generated due to oxidation easily, and the strength is low can be effectively solved.

Description

Technical Field

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

[0002] With the progress of China's industrial technology, along with the increasingly high requirements for the performance of metal materials, whether it is the nuclear industry and aviation industry in high-tech fields or the traditional chemical industry, the demand and requirements for pressure vessels are getting higher and higher. Whether it is a storage container, such as a chemical storage tank or a hydrogen storage tank, etc.; or a reaction vessel, such as a reactor, etc., there are requirements for pressure, and at the same time, higher requirements are put forward for the materials. In the industry, according to the requirements of different media, the material selection and design of pressure vessels require sufficient strength, stiffness, service life and compatibility with the medium to meet different working conditions. It is necessary to comprehensively consider the chemical composition, mechanical properties and process performance of the pressure vessel, and at the same time, the welding performance of the pressure vessel should also be considered.

[0003] At present, pressure vessels are still mainly made of nickel-based alloys. To meet the excellent sealing performance of pressure vessels, the welding materials should also be mainly nickel (Ni). As the main element used in current welding materials, Ni is a rare alloying element that can not only improve the strength of alloy materials but also does not significantly weaken the plasticity of the materials, and has extremely excellent high-temperature resistance, oxidation resistance and corrosion resistance. However, there are obvious defects in nickel-based alloy welding: for example, pores and slag inclusions are likely to appear during the welding process due to high-temperature oxidation, affecting the welding quality and sealing performance. During the welding process, grain growth affects the toughness and the cost is too high. In addition, when used for the storage and transportation of hydrogen, there will also be a phenomenon of hydrogen embrittlement, resulting in material failure.

[0004] At present, there are two conventional methods. One is to improve the welding process, and by optimizing welding parameters, preheating temperature, etc., to alleviate the problems of pores, slag inclusions and toughness, but the effect is not good. The other is to purify alloy impurities through the design of the nickel-based alloy composition. This research and development direction will be the mainstream direction in the future. Summary of the Invention

[0005] The purpose of the present invention is to provide a new type of nickel-based alloy welding material for pressure vessels and a preparation method thereof to solve the problems of easy oxidation, generation of pores or cracks and low strength during the welding of nickel-based alloy welding materials for pressure vessels in the prior art. While solving the above problems, the new material also has the advantages of hydrogen embrittlement resistance and low cost. To achieve the above purpose, the technical solution adopted by the present invention to solve its technical problems is: The present invention provides a nickel-based alloy welding material for pressure vessels, which comprises the following powder 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%, 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 material: 2.0 - 5.0%, balance Ni.

[0006] Further, the total amount of Mo and W is not less than 9.0%.

[0007] Further, the weight ratio of Al to Ti is 0.5 - 1.5:1.

[0008] Further, the weight ratio of Al to Ti is 0.8 - 1.4:1.

[0009] Further, the RE is selected from La, Y, Ce or Sm.

[0010] Further, the nano-ceramic material is selected from alumina, zirconia, titanium carbide or silicon carbide.

[0011] Another object of the present invention is to provide a preparation method of a nickel-based alloy welding material for pressure vessels, comprising the following steps: S1: Weigh raw materials according to the formula mass percentage, and process to obtain a uniformly refined mixed powder; S2: Put the mixed powder in S1 and the nano-ceramic material into a melting furnace for melting. After high-temperature refining and low-temperature refining, remelting refining is then carried out, and it is cast into an alloy ingot; S3: After annealing the alloy ingot, it is forged and rolled to prepare an alloy wire rod; S4: After pre-treating the alloy wire rod, multi-pass drawing-annealing is carried out, S5: It is processed into alloy wires of required sizes and subjected to solution-aging treatment.

[0012] Further, the processing process in S1 is to add the raw material powder except the nano-ceramic material into ethanol for ultrasonic treatment; filter, take the insoluble matter, dry it and then carry out ball milling treatment to obtain the mixed powder.

[0013] Further, in step S3, the forging process is as follows: at 950°C, cogging is carried out to forge the alloy blank I, with a forging ratio of 3 - 4; at 1050°C, it is forged into alloy blank II, with a forging ratio of 7 - 8, and then forged into alloy blank III at the same temperature, with a forging ratio of 3 - 4; the rolling process is to keep it at 1000 - 1050°C for 0.5 - 1.5 h and hot-roll it into alloy wire rods at 950 - 1100°C.

[0014] Further, the solution treatment is as follows: in a nitrogen environment, it is heated to 950 - 1050°C and held for 2 - 3 h, then continuously heated to 1050 - 1100°C and held for 2 - 3 h, then continuously heated to 1100 - 1150°C and held for 1 - 2 h, then continuously heated to 1150 - 1170°C and held for 1 - 2 h, and then rapidly water-quenched to obtain the solution-treated alloy; the aging treatment is to heat it to 800 - 850°C and hold for 3 - 8 h, then air-cool, and then heat it to 750 - 770°C and hold for 10 - 15 h, and then air-cool.

[0015] The present invention has the following beneficial effects: (1) The present invention provides a nickel-based alloy welding material for pressure vessels. With Ni as the matrix, Cr can improve the high-temperature oxidation resistance of the alloy; Co can improve the anti-carbonization performance; 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 solution strengthening effect, enhancing its high-temperature oxidation resistance and thermal strength; at the same time, Cr, Mo, Co, and V can also form carbides with C, and hard phases such as chromium carbide and cobalt carbide are dispersed in the solution-strengthened matrix, improving the 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, effectively improving the welding strength and sealing performance; in addition, the precipitated phases of Cr, Mo, and V have stability and hydrogen trap ability, and the ionic bond formed by the carbide of V and hydrogen is the strongest, and the stably existing carbide precipitated phase is the most excellent hydrogen trap, having anti-hydrogen embrittlement performance.

[0016] (2) The present invention provides a nickel-based alloy welding material for pressure vessels. A certain proportion of Mo, Fe, and B are added to the alloy. During the high-temperature remelting process, reactions can occur to form Mo 2 FeB 2 and Mo 2 NiB 2 ternary boride hard phases, which have excellent mechanical properties such as corrosion resistance, hardness, and wear resistance.

[0017] (3) The present invention provides a nickel-based alloy welding material for pressure vessels. A certain amount of Fe, Nb, and rare earth element RE are added to the alloy. First, Fe can improve the resistance to high-temperature carburizing environment and control thermal expansion; at the same time, it can reduce the usage of precious metal Ni. Second, Nb can reduce the strain crack tendency and can form the precipitation strengthening phase γ" of Ni 3 Nb in the alloy, improving the high-temperature strength, creep resistance, corrosion resistance and other properties of the alloy. In addition, Nb has a good affinity with O and can form a stable oxide Nb 2 O 5 , which has the effect of delaying corrosion. Third, for rare earth element RE, on the one hand, RE and Nb act synergistically to improve the adhesion of the oxide film and refine the oxide grains at high temperatures; and by forming coordination with O and S at high temperatures, smaller-sized rare earth oxide nanoparticles can be preferentially formed, which can act as heterogeneous nuclei during the welding process to refine the grains and improve the mechanical strength of the weld. On the other hand, it can improve the wettability of the welding material, making the weld easier to fill and reducing defects.

[0018] (4) The present invention provides a nickel-based alloy welding material for pressure vessels. A certain amount of elements such as Al, Ti, Zr, Ta, etc. are added to the alloy, which can purify the grain boundaries and improve the properties; at the same time, it can form dispersed γ′ phases to improve the high-temperature strength of the alloy.

[0019] (5) The present invention provides a nickel-based alloy welding material for pressure vessels. A certain amount of nano-ceramic materials are 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 micro-cracks generated under stress and improve the mechanical properties. Third, it can act as a hydrogen trap (or pin the grain boundaries and reduce the diffusion of hydrogen atoms) to improve the hydrogen embrittlement resistance.

[0020] (6) The present invention provides a preparation method of a nickel-based alloy welding material for pressure vessels. First, by alcohol washing, the impurity content is reduced, effectively reducing the precipitation and segregation of harmful carbides; through ball milling treatment, the particle size of the powder is reduced to promote the compatibility between phases. Second, through forging-rolling process, the purity and plasticity of the alloy are improved. Third, under a nitrogen environment, multi-step hierarchical solution-aging treatment is adopted to refine the grain size and improve the mechanical properties; at the same time, the hydrogen embrittlement performance is improved. Specific Embodiments

[0021] The present invention will be described in detail below with reference to the embodiments. However, it should be understood that the following embodiments are only illustrative examples of the embodiments of the present invention, rather than limiting the scope of the present invention.

[0022] The object of the present invention is to develop a nickel-based alloy welding material for pressure vessels to solve the problems existing in the existing nickel-based alloy welding materials for pressure vessels. The implementation idea is as follows: mainly using Ni, adding high-temperature-resistant elements such as Cr, Co, Mo, W, and V through formula design to achieve solid solution strengthening and improve oxidation resistance; adding elements such as B and Fe to increase hardness and plasticity; and adding precipitation strengthening elements such as Al, Ti, Nb, Ta, and RE to improve high-temperature strength and purify grain boundaries; finally, compounding with 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: An embodiment of the present invention provides a nickel-based alloy welding material for pressure vessels, comprising the following powder 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%, 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 material: 2.0 - 5.0%, balance Ni.

[0023] The total amount of Mo and W is not less than 9.0%.

[0024] The weight ratio of Al to Ti is 0.5 - 1.5:1.

[0025] The weight ratio of Al to Ti is 0.8 - 1.4:1.

[0026] The RE is selected from La, Y, Ce or Sm.

[0027] The nano-ceramic material is selected from alumina, zirconia, titanium carbide or silicon carbide.

[0028] Another object of the embodiment of the present invention is to provide a preparation method of a nickel-based alloy welding material for pressure vessels, comprising the following steps: S1: Weigh the raw materials according to the mass percentage of the formula and process them to obtain a uniformly refined mixed powder.

[0029] The processing technology is to add raw material powders except nano-ceramic materials into ethanol, magnetically stir at 500 - 2000 r / min for 2 - 5 h, then place it under ultrasonic treatment at 50 KHz for 2 h to obtain an ethanol suspension; filter, take the insoluble matter, place it in a drying oven at 80°C for drying treatment for 2 h, put the above insoluble matter into a ball milling tank, add long-chain fatty acid, place the ball milling tank on a high-energy ball mill for ball milling treatment to obtain a uniformly refined mixed powder; among them, the grinding ball material is corundum ball, the ball-to-material mass ratio is 5 - 8:1, the ball milling process is 5 - 10 h, and the rotation speed of the ball milling tank is 150 - 200 r / min; The dosage ratio of the long-chain fatty acid to the total mass of the raw material powders is 2 g:100 g; The long-chain fatty acid is myristic acid or lauric acid, etc.; and preferably myristic acid.

[0030] S2: Put the mixed powder and nano-ceramic materials in S1 into a melting furnace for melting. After high-temperature refining and low-temperature refining, then adopt remelting refining and cast into an alloy ingot.

[0031] The high-temperature refining is carried out at 1750 - 1850°C for 30 - 45 min; The low-temperature refining is carried out at 1650 - 1700°C for 15 - 25 min; The remelting is electroslag remelting, and the furnace temperature is 1750 - 1850°C.

[0032] S3: After annealing the alloy ingot, carry out forging and rolling to prepare an alloy wire rod.

[0033] The annealing process is to heat to 1000 - 1050°C and keep warm for 20 - 35 h; The forging process is to perform cogging forging into alloy blank I at 950°C, with a forging ratio of 3 - 4; after tempering and heating at 950 - 1000°C for 1 - 2 h, forge into alloy blank II at 1050°C, with a forging ratio of 7 - 8, and then forge into alloy blank 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 - 1.5 h and hot roll into an alloy wire rod with a diameter of Φ4.0 - 5.0 mm at 950 - 1100°C.

[0034] S4: After pre-treating the alloy wire rod, carry out multi-pass drawing-annealing.

[0035] The pre-treatment is to heat the alloy wire rod to 950°C, keep warm for 1.5 h, perform oil quenching for softening treatment, alkali boiling, then high-pressure water washing, pickling after water washing, and then ultrasonic cleaning; For the drawing, add a lubricant before drawing and carry out multi-pass drawing processing to obtain an alloy wire; The annealing is carried out after 6 - 10 passes of drawing, and the annealing temperature is 640 - 800 °C.

[0036] S5: Process the alloy wire into the required size and carry out solution - aging treatment.

[0037] The solution is carried out in a nitrogen environment, heated to 950 - 1050 °C, held for 2 - 3 h, then heated to 1050 - 1100 °C, held for 2 - 3 h, then heated to 1100 - 1150 °C, held for 1 - 2 h, and then heated to 1150 - 1170 °C, held for 1 - 2 h, and then rapidly water - quenched to obtain the solution - state alloy; the aging is carried out by heating to 800 - 850 °C, holding for 3 - 8 h, air - cooling, then heating to 750 - 770 °C, holding for 10 - 15 h, and air - cooling.

[0038] To further understand the present invention, the nickel - based alloy welding material for pressure vessels provided by the present invention will be described in detail below in conjunction with specific embodiments. The protection scope of the present invention is not limited by the following embodiments.

[0039] Example 1 This example provides a nickel - based alloy welding material for pressure vessels, including the following powder raw materials in parts by weight: 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 material: 3.0%, balance Ni.

[0040] The weight ratio of Al to Ti is 1.2:1.

[0041] The RE is selected from Sm.

[0042] The nano - ceramic material is selected from zirconia.

[0043] This example also provides a preparation method of the nickel - based alloy welding material for pressure vessels, including the following steps: S1: Weigh the raw materials according to the mass percentage of the formula and process them to obtain a uniformly refined mixed powder.

[0044] The processing technology is to add the raw material powder except the nano-ceramic material into ethanol, stir magnetically at 1000 r / min for 3 h, then place it under ultrasonic treatment at 50 KHz for 2 h to obtain an ethanol suspension; filter, take the insoluble matter, place it in a drying oven at 80 °C for drying treatment for 2 h, put the above insoluble matter into a ball mill tank, and then add myristic acid. The ball mill tank is placed on a high-energy ball mill for ball milling treatment to obtain a uniformly refined mixed powder; among them, the grinding ball material is corundum balls, the ball-to-material mass ratio is 7:1, the ball milling process is 7 h, and the rotation speed of the ball mill tank is 180 r / min; The dosage ratio of the myristic acid to the total mass of the raw material powder is 2 g:100 g.

[0045] S2: Put the mixed powder and the nano-ceramic material in S1 into a melting furnace for melting. After high-temperature refining and low-temperature refining, electro-slag remelting is then carried out and cast into an alloy ingot.

[0046] The high-temperature refining is carried out at 1800 °C for 40 min; The low-temperature refining is carried out at 1680 °C for 20 min; The remelting is electro-slag remelting, and the furnace temperature is 1800 °C.

[0047] S3: After annealing the alloy ingot, forging and rolling are carried out to prepare an alloy wire rod.

[0048] The annealing process is to heat to 1020 °C and hold for 30 h; The forging process is to perform cogging forging into alloy blank I at 950 °C, with a forging ratio of 3.5; after tempering and heating at 980 °C for 1.5 h, forging into alloy blank II at 1050 °C, with a forging ratio of 7.5, and then forging into alloy blank III at the same temperature, with a forging ratio of 3.5; The rolling process is to hold at 1020 °C for 1 h and hot-roll into a Φ4.5 mm alloy wire rod at 1040 °C.

[0049] S4: After preprocessing the alloy wire rod, multi-pass drawing-annealing is carried out.

[0050] The preprocessing is to heat the alloy wire rod to 950 °C, hold for 1.5 h, perform softening treatment by oil cooling, alkali boiling, then high-pressure water washing, pickling after water washing, and then ultrasonic cleaning; For the drawing, a lubricant is added before drawing, and multi-pass drawing processing is carried out to obtain alloy wires; The annealing is to carry out vacuum annealing after 8 passes of drawing, and the annealing temperature is 700 °C.

[0051] S5: Process into alloy wires of the required size and carry out solution-aging treatment.

[0052] The solution treatment is carried out in a nitrogen environment. Heat to 1000 °C, hold for 2.5 h, continue to heat to 1080 °C, hold for 2.5 h, continue to heat to 1120 °C, hold for 1.5 h, continue to heat to 1160 °C, hold for 1.5 h, and then rapidly water quench to obtain the solution-treated alloy; the aging treatment is carried out by heating to 820 °C, holding for 5 h, air cooling, then heating to 760 °C, holding for 12 h, and air cooling.

[0053] Example 2 This example provides a nickel-based alloy welding material for pressure vessels, including the following powder raw materials in parts by weight: 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%, balance Ni.

[0054] The weight ratio of Al to Ti is 1.2:1.

[0055] The RE is selected from Sm.

[0056] The nano-ceramic material is selected from zirconia.

[0057] This example also provides a preparation method of a nickel-based alloy welding material for pressure vessels, including the following steps: S1: Weigh the raw materials according to the mass percentage of the formula and process them to obtain a uniformly refined mixed powder.

[0058] The processing process is to add the raw material powder except the nano-ceramic material into ethanol, magnetically stir at 500 r / min for 5 h, then place it in an ultrasonic treatment at 50 KHz for 2 h to obtain an ethanol suspension; filter, take the insoluble matter, place it in an 80 °C drying oven for drying treatment for 2 h, put the above insoluble matter into a ball milling tank, and then add myristic acid. The ball milling tank is placed on a high-energy ball mill for ball milling treatment to obtain a uniformly refined mixed powder; among them, the grinding ball material is corundum balls, the ball-to-material mass ratio is 8:1, the ball milling process is 5 h, and the rotation speed of the ball milling tank is 200 r / min; The dosage ratio of myristic acid to the total mass of the raw material powder is 2 g:100 g.

[0059] S2: Put the mixed powder in S1 and the nano-ceramic material into a melting furnace for melting. After high-temperature refining, low-temperature refining, and then remelting and refining, it is cast into an alloy ingot.

[0060] The high-temperature refining is carried out at 1750 °C for 45 min; The low-temperature refining is carried out by smelting at 1650 °C for 25 min; The remelting is electroslag remelting, and the furnace temperature is 1750 °C.

[0061] S3: After annealing the alloy ingot, forging and rolling are carried out to prepare alloy wire rods.

[0062] The annealing process is heating to 1000 °C and holding for 35 h; The forging process is at 950 °C, cogging to forge alloy blank I with a forging ratio of 3; after tempering and heating at 950 °C for 2 h, forging at 1050 °C to forge alloy blank II with a forging ratio of 8, and then forging at the same temperature to forge alloy blank III with a forging ratio of 4; The rolling process is holding at 1000 °C for 1.5 h and hot rolling at 950 °C into Φ4.0 mm alloy wire rods.

[0063] S4: After pre-treating the alloy wire rods, multi-pass drawing-annealing is carried out.

[0064] The pre-treatment is heating the alloy wire rods to 950 °C, holding for 1.5 h, oil cooling for softening treatment, alkali boiling, then high-pressure water washing, pickling after water washing, and then ultrasonic cleaning; For the drawing, a lubricant is added before drawing, and multi-pass drawing processing is carried out to obtain alloy wires; The annealing is that vacuum annealing is carried out after 10 passes of drawing, and the annealing temperature is 640 °C.

[0065] S5: Process into alloy wires of required dimensions and carry out solution-aging treatment.

[0066] The solution is carried out in a nitrogen environment, heating to 1050 °C, holding for 2 h, continuing to heat to 1100 °C, holding for 2 h, continuing to heat to 1150 °C, holding for 1 h, continuing to heat to 1170 °C, holding for 1 h, and rapid water quenching to obtain a solution-state alloy; the aging is heating to 850 °C, holding for 3 h, air cooling, then heating to 770 °C, holding for 10 h, and air cooling.

[0067] Example 3 This example provides a nickel-based alloy welding material for pressure vessels, including the following powder raw materials in parts by weight: 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%, balance Ni.

[0068] The weight ratio of Al to Ti is 1.2:1.

[0069] The RE is selected from Sm.

[0070] The nano-ceramic material is selected from zirconia.

[0071] This embodiment also provides a preparation method of a nickel-based alloy welding material for pressure vessels, comprising the following steps: S1: Raw materials are weighed according to the formula mass percentage and processed to obtain a uniformly refined mixed powder.

[0072] The processing process is to add the raw material powder except the nano-ceramic material into ethanol, magnetically stir at 2000 r / min for 2 h, then place it in an ultrasonic treatment at 50 kHz for 2 h to obtain an ethanol suspension; filter, take the insoluble matter, place it in a drying oven at 80 °C for drying treatment for 2 h, put the above insoluble matter into a ball milling tank, and then add myristic acid. The ball milling tank is placed on a high-energy ball mill for ball milling treatment to obtain a uniformly refined mixed powder; wherein the grinding ball material is corundum balls, the ball-to-material mass ratio is 5:1, the ball milling process is 10 h, and the rotation speed of the ball milling tank is 150 r / min; The dosage ratio of myristic acid to the total mass of the raw material powder is 2 g:100 g.

[0073] S2: The mixed powder in S1 and the nano-ceramic material are put into a melting furnace for melting. After high-temperature refining and low-temperature refining, electroslag remelting is then adopted, and it is cast into an alloy ingot.

[0074] The high-temperature refining is melting at 1850 °C for 30 min; The low-temperature refining is melting at 1700 °C for 15 min; The remelting is electroslag remelting, and the furnace temperature is 1850 °C.

[0075] S3: After annealing the alloy ingot, forging and rolling are carried out to prepare alloy wire rods.

[0076] The annealing process is heating to 1050 °C and holding for 20 h; The forging process is at 950 °C, cogging to forge into alloy blank I, with a forging ratio of 4; after tempering and heating at 1000 °C for 1 h, forging at 1050 °C into alloy blank II, with a forging ratio of 7, and then forging into alloy blank III at the same temperature, with a forging ratio of 3; The rolling process is holding at 1050 °C for 0.5 h and hot rolling into Φ5.0 mm alloy wire rods at 1100 °C.

[0077] S4: After pre-treating the alloy wire rods, multi-pass drawing-annealing is carried out.

[0078] The pretreatment is to heat the alloy wire rod to 950 °C, hold for 1.5 h, perform softening treatment by oil cooling, alkali boiling, followed by high-pressure water washing, pickling after water washing, and then ultrasonic cleaning; For the drawing, a lubricant is added before drawing, and multi-pass drawing processing is carried out to obtain alloy wire; The annealing is to perform vacuum annealing after 6 passes of drawing, and the annealing temperature is 800 °C.

[0079] S5: Process the alloy wire into the required size and perform solution-aging treatment.

[0080] The solution treatment is to heat to 950 °C in a nitrogen environment, hold for 3 h, continue to heat to 1050 °C, hold for 3 h, continue to heat to 1100 °C, hold for 2 h, continue to heat to 1150 °C, hold for 2 h, and perform rapid water quenching to obtain a solution-state alloy; the aging treatment is to heat to 800 °C, hold for 8 h, air cool, then heat to 750 °C, hold for 15 h, and air cool.

[0081] Example 4 Others are the same as in Example 1, the difference is that: In a nickel-based alloy welding material formula for a pressure vessel, The weight ratio of Al to Ti is 1.4:1.

[0082] Example 5 Others are the same as in Example 1, the difference is that: In a nickel-based alloy welding material formula for a pressure vessel, The weight ratio of Al to Ti is 0.8:1.

[0083] Example 6 Others are the same as in Example 1, the difference is that: In a nickel-based alloy welding material formula for a pressure vessel, The weight ratio of Al to Ti is 1.5:1.

[0084] Example 7 Others are the same as in Example 1, the difference is that: In a nickel-based alloy welding material formula for a pressure vessel, The weight ratio of Al to Ti is 0.5:1.

[0085] Example 8 Others are the same as in Example 1, the difference is that: In a nickel-based alloy welding material formula for a pressure vessel, The RE is selected from Y.

[0086] Example 9 Others are the same as Example 1, except that: In a nickel-based alloy welding material formulation for a pressure vessel, The RE is selected from Ce.

[0087] Example 10 Others are the same as Example 1, except that: In a nickel-based alloy welding material formulation for a pressure vessel, The RE is selected from La.

[0088] Example 11 Others are the same as Example 1, except that: In a nickel-based alloy welding material formulation for a pressure vessel, The nano-ceramic material is selected from alumina.

[0089] Example 12 Others are the same as Example 1, except that: In a nickel-based alloy welding material formulation for a pressure vessel, The nano-ceramic material is selected from titanium carbide.

[0090] Example 13 Others are the same as Example 1, except that: In a nickel-based alloy welding material formulation for a pressure vessel, The nano-ceramic material is selected from silicon carbide.

[0091] The following comparative examples are all compared with Example 1: Comparative Example 1 Others are the same as Example 1, except that: A nickel-based alloy welding material for a pressure vessel, comprising the following parts by weight of powder raw materials: 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 material: 3.0%, balance Ni.

[0092] Comparative Example 2 Others are the same as Example 1, except that: In a nickel-based alloy welding material formulation for a pressure vessel, The weight ratio of Al to Ti is 0:1; that is, Al is not added.

[0093] Comparative Example 3 The rest is the same as in Example 1, except that: In a nickel-based alloy welding material formula for a pressure vessel, the weight ratio of Al to Ti is 2:1.

[0094] Implement Comparative Example 4 The rest is the same as in Example 1, except that: In a nickel-based alloy welding material formula for a pressure vessel, the weight fraction of B is 0; that is, B is not added.

[0095] Implement Comparative Example 5 The rest is the same as in Example 1, except that: In a nickel-based alloy welding material formula for a pressure vessel, the weight fraction of V is 0; that is, V is not added.

[0096] Implement Comparative Example 6 The rest is the same as in Example 1, except that: In a nickel-based alloy welding material formula for a pressure vessel, the weight fraction of Nb is 0; that is, Nb is not added.

[0097] Implement Comparative Example 7 The rest is the same as in Example 1, except that: In a nickel-based alloy welding material formula for a pressure vessel, the weight fraction of RE is 0; that is, RE is not added.

[0098] Implement Comparative Example 8 The rest is the same as in Example 1, except that: In a nickel-based alloy welding material formula for a pressure vessel, the weight fraction of the nano-ceramic material is 0; that is, the nano-ceramic material is not added.

[0099] Implement Comparative Example 9 The rest is the same as in Example 1, except that: In a preparation method of a nickel-based alloy welding material for a pressure vessel, in S1, the processing technology does not perform the ball milling operation.

[0100] Implement Comparative Example 10 The rest is the same as in Example 1, except that: In a preparation method of a nickel-based alloy welding material for a pressure vessel, in S3, the forging ratio of the alloy billet II is 4.5.

[0101] Implement Comparative Example 11 Other aspects are the same as those of Example 1, except that: In a method for preparing a nickel-based alloy welding material for a pressure vessel, in S5, S5: Process the alloy wire into the required size and perform solution-aging treatment.

[0102] The solution treatment is carried out in a nitrogen environment, heated to 1000 °C, held for 2.5 h, then continuously heated to 1160 °C, held for 1.5 h, and rapidly water-quenched to obtain a solution-treated alloy; the aging treatment is carried out by heating to 760 °C, holding for 12 h, and air-cooling.

[0103] The physical properties of the nickel-based alloy welding materials for pressure vessels prepared in the examples and comparative examples of the present invention were measured respectively, and the results are shown in Table 1.

[0104] Table 1 Physical test properties of each example 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.

[0105] It can be observed from Example 1 and Comparative Examples 1-8 that the addition of appropriate amounts of Mo and W in the nickel-based alloy welding material for pressure vessels of the present invention achieves a solution strengthening effect, improving its high-temperature oxidation resistance and thermal strength; the important role of Al and Ti in forming the dispersed γ′ phase in 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 anti-hydrogen embrittlement effect; Nb has the ability to reduce the tendency of strain cracks, and can improve the high-temperature strength, creep resistance, corrosion resistance, etc. of the alloy; RE has good high-temperature oxidation resistance; at the same time, it can improve high-temperature strength, etc.; the nano-ceramic material has good mechanical properties and anti-hydrogen embrittlement properties, etc. It can be observed from Example 1 and Comparative Examples 9-11 that the ball milling process has a positive effect on reducing particle size, improving surface activity, and promoting interphase compatibility; a high forging ratio can refine grains, improve mechanical properties and anti-hydrogen embrittlement properties; the multi-step solution-aging process is beneficial to grain refinement and further improves performance. Generally speaking, a suitable preparation process has a positive effect on the performance of the nickel-based alloy welding material.

[0106] The test methods are as follows: (1) Mechanical property test: The tungsten inert gas welding was carried out on the NO8120 alloy material using the nickel alloy welding materials obtained in the examples and comparative examples. According to GB / T 2651 2008 "Test Method for Tensile Test of Welded Joints", the room-temperature mechanical properties and high-temperature mechanical properties of the welded joints were tested at room temperature and 350 °C respectively.

[0107] (2) Corrosion rate: The corrosion resistance test was carried out by the ASTM G28 A method, and the test time was 120 h.

[0108] (3) Tensile strength after hydrogen charging: The electrochemical dynamic hydrogen charging slow stretching experiment was used to study the mechanical property changes under different hydrogen charging current densities. Refer to the standard GB / T 2651-2008 "Tensile Test Method for Welded Joints". The constant current polarization method was used to synchronously charge hydrogen during the stretching process. The specimen was the cathode, the Pt sheet was the anode, and the electrolyte was 0.5 mol / L H 2 SO 4 +1.85 mmol / L Na 4 P 2 O 7 (Na 4 P 2 O 7 was used as a poison to inhibit the recombination of H into H 2 ), and the hydrogen charging current density was 40 mA / cm 2 .

[0109] Taking the ideal embodiments of the present invention described above as an inspiration, through the above description, relevant staff can completely make various changes and modifications without departing from the technical idea of this invention. The technical scope of this invention is not limited to the content in the specification, and its technical scope must be determined according to the scope of the claims.

Claims

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

8. The 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 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 blank into alloy blank I at 950°C with a forging ratio of 3-4; forge into alloy blank II at 1050°C with a forging ratio of 7-8, and then forge into alloy blank 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.

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

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