A nickel-based rolled clad plate and a method for manufacturing the same

Abstract

The application discloses a nickel-based rolling composite plate and a preparation method thereof, and relates to the technical field of alloys.The rare earth-nickel intermediate alloy is prepared by high-energy ultrasonic method through melting and mixing of pure nickel blocks and ytterbium powder; the aluminum-germanium modified nickel alloy is prepared by ball milling, pressing and sintering with nickel powder, aluminum powder and germanium powder as raw materials; the rare earth-nickel intermediate alloy and the aluminum-germanium modified nickel alloy are melted and mixed, and the modified nickel alloy is prepared by high-energy ultrasonic method; the pipeline steel plate material and the modified nickel alloy are combined by welding technology, and the nickel-based rolling composite plate is prepared by a vacuum rolling composite method.The nickel-based rolling composite plate prepared by the application has excellent mechanical properties and corrosion resistance.

Description

TECHNICAL FIELD

[0001] The present application relates to the alloy technical field, specifically to a nickel-based rolling composite plate and a preparation method thereof. BACKGROUND

[0002] In today's era, due to the continuous development of the fields of automobiles, ships and industries, the demand for materials presents a diversified trend, and higher demands for material performance, however, a single material cannot simultaneously have various excellent use performances. Therefore, in order to meet this demand, materials in the future will tend to be composite, so that materials can have different excellent performances to meet the needs; among them, the rolling composite plate is an important composite material. The nickel-based rolling composite plate is a kind of bimetallic composite material with nickel-based alloy as cladding layer and carbon steel or low alloy steel as base layer, which is widely used in high-end equipment manufacturing field; the nickel-based rolling composite plate is mainly applied in high temperature, high pressure and corrosion environment, and has the defects of insufficient strength and easy corrosion. Therefore, it is necessary to improve the existing technology to improve the strength and corrosion resistance of the nickel-based rolling composite plate. SUMMARY

[0003] The purpose of the present application is to provide a nickel-based rolling composite plate and a preparation method thereof to solve the problems in the prior art.

[0004] In order to solve the above technical problems, the present application provides the following technical scheme:

[0005] A nickel-based rolling composite plate, which is prepared by vacuum rolling of modified nickel alloy and pipeline steel plate;

[0006] The preparation method of the nickel-based rolling composite plate comprises the following preparation steps:

[0007] S1, surface treatment is performed on the 22mm-thick modified nickel alloy and the 180mm-thick pipeline steel plate, the pipeline steel plate and the modified nickel alloy are combined by using the symmetric blanking method, the pipeline steel plate is placed on the outermost side, and blanking is completed;

[0008] S2, the blanked modified nickel alloy and pipeline steel plate are welded and sealed, and vacuum treatment is performed, the vacuum degree of the vacuum treatment is not less than 10 -2 Pa, and a composite blank is prepared;

[0009] S3, the composite blank is heated to 1200~1300℃ at a heating rate of 10℃ / min, and after holding for 8~10h, rough rolling is started, and after rough rolling, the temperature of the composite blank is immediately heated to 800~1500℃ to start finish rolling, and after finish rolling, cooling is performed;

[0010] S4. After the composite billet has been cooled by precision rolling, it is first subjected to hot straightening, and then placed at a temperature of 500-1100℃ for heat treatment. After the heat treatment is completed, it is cut, separated into plates, leveled, polished and inspected, and then printed, packaged and shipped to obtain nickel-based rolled composite plates.

[0011] As an optimization, the modified nickel alloy is prepared by melting and mixing a rare earth-nickel master alloy and an aluminum-germanium modified nickel alloy, and then using a high-energy ultrasonic method; wherein, the rare earth-nickel master alloy is prepared by melting and mixing pure nickel blocks and ytterbium powder, and then using a high-energy ultrasonic method; the aluminum-germanium modified nickel alloy is prepared by using nickel powder, aluminum powder, and germanium powder as raw materials, and then by ball milling, pressing, and sintering.

[0012] As an optimization, the modified nickel alloy is prepared using the following steps:

[0013] (1) Preheat the graphite crucible to 500~520℃, put in pure nickel blocks, heat to 1400~1500℃, stir at 200~300r / min for 10~12min, add ytterbium powder at 0.06~0.08 times the mass of pure nickel blocks, continue stirring for 20~30min, preheat the ultrasonic concentrator of the ultrasonic device to 300~400℃, place the ultrasonic concentrator in the melt for ultrasonic treatment, refine and remove slag from the melt, pour it into a metal mold, cool to room temperature, and obtain rare earth-nickel master alloy;

[0014] (2) Mix the powder and polyethylene glycol at a mass ratio of 1:(0.006~0.008) evenly, place them in a mold, put the mold on a press, apply a pressure of 550~560MPa, hold for 2~3min to obtain a blank; place the blank in a sintering furnace, heat from room temperature to 350~360℃ at a heating rate of 10℃ / min, hold for 2~3h, heat to 1250~1260℃ at a heating rate of 5℃ / min, hold for 2~3h, cool to room temperature to obtain an aluminum-germanium modified nickel alloy;

[0015] (3) Preheat the graphite crucible to 380~420℃ in a pit-type resistance furnace. Place the rare earth-nickel master alloy and aluminum-germanium modified nickel alloy into the crucible at a mass ratio of 1:(2~2.2) and heat it to 1400~1500℃. Preheat the ultrasonic concentrator of the ultrasonic device to 300~400℃. Place the ultrasonic concentrator in the melt for ultrasonic treatment. Refine and remove slag from the melt. Pour it into a metal mold and cool it to room temperature to obtain the modified nickel alloy.

[0016] As optimization, the process parameters of the ultrasonic treatment in step (1) are as follows: the ultrasonic concentrator is arranged at a position 16-20 cm below the liquid surface of the melt, the ultrasonic output frequency is 1.4-1.6 kHz, the ultrasonic output power is 600-700 W, and the ultrasonic time is 10-12 min; and the mesh number of the ytterbium powder is 400 mesh.

[0017] As optimization, the preparation method of the mixed powder in step (2) is as follows: the nickel powder, the aluminum powder and the germanium powder are mixed uniformly, and are placed in a ball mill to perform ball milling under argon protection, the ball-to-material ratio is arranged as (9-10):1, the ball milling speed is 140-160 r / min, and the ball milling time is 7-9 h, so as to obtain the mixed powder.

[0018] As optimization, the mass ratio of the nickel powder, the aluminum powder and the germanium powder is 1:(0.06-0.08):(0.04-0.06).

[0019] As optimization, the mesh number of the nickel powder is 300, the mesh number of the aluminum powder is 400, and the mesh number of the germanium powder is 600.

[0020] As optimization, the type of the polyethylene glycol in step (2) is PEG2000.

[0021] As optimization, the process parameters of the ultrasonic treatment in step (3) are as follows: the ultrasonic concentrator is arranged at a position 16-20 cm below the liquid surface of the melt, the ultrasonic output frequency is 1.4-1.6 kHz, the ultrasonic output power is 600-700 W, and the ultrasonic time is 14-16 min.

[0022] Compared with the prior art, the present application has the following beneficial effects:

[0023] In the preparation of the nickel-based rolling composite plate, the pure nickel block and the ytterbium powder are melted and mixed, and a rare earth-nickel intermediate alloy is prepared by using a high-energy ultrasonic method; the nickel powder, the aluminum powder and the germanium powder are used as raw materials, and an aluminum-germanium modified nickel alloy is prepared by ball milling, pressing and sintering; the rare earth-nickel intermediate alloy and the aluminum-germanium modified nickel alloy are melted and mixed, and a modified nickel alloy is prepared by using a high-energy ultrasonic method; the pipeline steel plate material and the modified nickel alloy are combined by using a welding technology, and a nickel-based rolling composite plate is prepared by a vacuum rolling composite method.

[0024] Firstly, the pure nickel block and the ytterbium powder are melted and mixed, and a rare earth-nickel intermediate alloy is prepared by using a high-energy ultrasonic method; the addition of the ytterbium powder can refine the grains, and the ytterbium powder is uniformly dispersed in the nickel-based alloy by using a high-energy ultrasonic method, which is helpful to hinder the dislocation movement and the grain boundary sliding, and to reduce the atomic diffusion speed in the matrix, so as to realize the dispersion strengthening effect on the nickel-based alloy, inhibit the grain boundary corrosion, and endow the nickel-based rolling composite plate with excellent mechanical properties and corrosion resistance.

[0025] Secondly, taking nickel powder, aluminum powder and germanium powder as raw materials, an aluminum-germanium modified nickel alloy is prepared through ball milling, pressing and sintering; the addition of Ge element reduces the migration rate of Ni element from the substrate to the surface, Al element has a smaller atomic radius, and the migration rate is relatively fast compared with other metal elements, and it is more likely to contact with oxygen in the air, thereby forming a complete aluminum oxide film on the surface of the alloy, hindering the further oxidation of oxygen and improving the corrosion resistance of the alloy. DETAILED DESCRIPTION

[0026] The technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the embodiments of the present application. Obviously, the described embodiments are only part of the embodiments of the present application, not all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor fall within the scope of the present application.

[0027] The type of polyethylene glycol used in the following examples and comparative examples is PEG2000;

[0028] The mesh number of ytterbium powder used is 400, the mesh number of nickel powder is 300, the mesh number of aluminum powder is 400, and the mesh number of germanium powder is 600.

[0029] Example 1

[0030] A preparation method of a nickel-based rolling composite plate, the preparation method of the nickel-based rolling composite plate comprises the following preparation steps:

[0031] (1) Preheat the graphite crucible to 500℃, put in pure nickel blocks, heat to 1400℃, stir at 200r / min for 12min, add ytterbium powder with a mass of 0.06 times that of the pure nickel blocks, continue to stir for 30min, preheat the ultrasonic concentrator of the ultrasonic device to 300℃, place the ultrasonic concentrator in the melt for ultrasonic treatment, set the ultrasonic concentrator to be located 16cm below the liquid surface of the melt, the ultrasonic output frequency is 1.4KHz, the ultrasonic output power is 600W, and the ultrasonic time is 12min, refine and deslag the melt, pour in the metal mold, cool to room temperature, and obtain a rare earth-nickel intermediate alloy;

[0032] (2) mixing the nickel powder, the aluminum powder and the germanium powder uniformly according to a mass ratio of 1:0.06:0.04, placing them in a ball mill, ball milling under argon protection, setting a ball-to-material ratio of 9:1, a ball milling speed of 140 r / min, and a ball milling time of 9 h to obtain a mixed powder; mixing the mixed powder and polyethylene glycol uniformly according to a mass ratio of 1:0.006, placing them in a mold, placing the mold on a press, applying a pressure of 550 MPa, and keeping the pressure for 3 min to obtain a green body; placing the green body in a sintering furnace, heating from room temperature to 350℃ at a heating rate of 10℃ / min, keeping the temperature for 3 h, heating to 1250℃ at a heating rate of 5℃ / min, keeping the temperature for 3 h, and cooling to room temperature to obtain an aluminum-germanium modified nickel alloy;

[0033] (3) preheating a graphite crucible to 380℃ in a pit-type resistance furnace, placing the rare earth-nickel intermediate alloy and the aluminum-germanium modified nickel alloy in the crucible according to a mass ratio of 1:2, heating to 1400℃, preheating an ultrasonic concentrator of an ultrasonic device to 300℃, placing the ultrasonic concentrator in the melt for ultrasonic treatment, setting the ultrasonic concentrator at a position 16 cm below the surface of the melt, an ultrasonic output frequency of 1.4 KHz, an ultrasonic output power of 600 W, and an ultrasonic time of 16 min, refining and deslagging the melt, pouring in a metal mold, and cooling to room temperature to obtain a modified nickel alloy; performing surface treatment on a 10 mm thick modified nickel alloy and a 18 mm thick pipeline steel plate, combining the pipeline steel plate and the modified nickel alloy by using a symmetric assembly method, placing the pipeline steel plate at the outermost side, and completing the assembly; welding the edges of the assembled modified nickel alloy and the pipeline steel plate, and performing vacuum treatment, wherein the vacuum degree of the vacuum treatment is not less than 10 -2 Pa to obtain a composite blank; heating the composite blank to 1200℃ at a heating rate of 10℃ / min, keeping the temperature for 8 h, starting rough rolling, rolling the composite blank to a finished product specification of 3+24.5 mm after the temperature of the composite blank after rough rolling reaches 880℃, cooling the finished product after finishing rolling, performing hot straightening treatment on the composite blank after finishing rolling and cooling, then placing the composite blank at a temperature of 500℃ for heat treatment, performing cutting, plate dividing, flattening, surface polishing and flaw detection treatment on the composite blank after the heat treatment is completed, and then spraying, printing, packaging and delivering the composite blank to obtain a nickel-based rolled composite plate.

[0034] Example 2:

[0035] A preparation method of a nickel-based rolled composite plate, the preparation method of the nickel-based rolled composite plate comprising the following preparation steps:

[0036] (1) preheat the graphite crucible to 510℃, put the pure nickel block into the crucible, heat to 1450℃, stir at 250r / min for 11min, add Yb powder with the mass of 0.07 times of the pure nickel block, continue to stir for 25min, preheat the ultrasonic concentrator of the ultrasonic device to 350℃, put the ultrasonic concentrator into the melt for ultrasonic treatment, set the ultrasonic concentrator at 17cm below the melt surface, the ultrasonic output frequency is 1.5KHz, the ultrasonic output power is 650W, and the ultrasonic time is 11min, refine and remove slag of the melt, pour in the metal mold, cool to room temperature, and obtain the rare earth-nickel intermediate alloy;

[0037] (2) mix the nickel powder, aluminum powder and germanium powder according to the mass ratio of 1:0.07:0.05, put them into the ball mill, and ball mill under argon protection, set the ball-to-material ratio to 9.5:1, the ball milling speed to 150r / min, and the ball milling time to 8h, to obtain the mixed powder; mix the mixed powder and polyethylene glycol according to the mass ratio of 1:0.007, put them into the mold, put the mold into the pressure machine, apply a pressure of 555MPa, and keep the pressure for 2.5min, to obtain the green body; put the green body into the sintering furnace, heat from room temperature to 355℃ at a rate of 10℃ / min, keep the temperature for 2.5h, heat to 1255℃ at a rate of 5℃ / min, keep the temperature for 2.5h, and cool to room temperature, to obtain the aluminum-germanium modified nickel alloy;

[0038] (3) preheat the graphite crucible to 400℃ in the pit-type resistance furnace, put the rare earth-nickel intermediate alloy and the aluminum-germanium modified nickel alloy into the crucible according to the mass ratio of 1:2.1, heat to 1450℃, preheat the ultrasonic concentrator of the ultrasonic device to 350℃, put the ultrasonic concentrator into the melt for ultrasonic treatment, set the ultrasonic concentrator at 18cm below the melt surface, the ultrasonic output frequency is 1.5KHz, the ultrasonic output power is 650W, and the ultrasonic time is 15min, refine and remove slag of the melt, pour in the metal mold, cool to room temperature, to obtain the modified nickel alloy; perform surface treatment on the 10mm-thick modified nickel alloy and the 18mm-thick pipeline steel plate, use the symmetric assembly method to assemble the pipeline steel plate and the modified nickel alloy, put the pipeline steel plate at the outermost side, and complete the assembly; weld the edges of the assembled modified nickel alloy and the pipeline steel plate, and perform vacuum treatment, the vacuum degree of the vacuum treatment is not less than 10 -2Pa, the composite blank is heated to 1180℃ at a heating rate of 10℃ / min, and after holding for 90h, rough rolling is started, the temperature of the composite blank after rough rolling reaches 850℃, and then finish rolling is started, the product specification is 3+24.5mm, and after finish rolling, the composite blank is cooled; the composite blank after finish rolling and cooling is first subjected to hot straightening treatment, and then is subjected to heat treatment at a temperature of 600℃, after heat treatment, the composite blank is subjected to cutting, plate separating, flattening, surface polishing and flaw detection treatment, and then is sprayed, packaged and delivered, and a nickel-based rolled composite plate is prepared.

[0039] Example 3:

[0040] A preparation method of a nickel-based rolled composite plate, the preparation method of the nickel-based rolled composite plate comprises the following preparation steps:

[0041] (1) a graphite crucible is preheated to 510℃, pure nickel blocks are put in, the temperature is raised to 1500℃, stirring is carried out at 300r / min for 10min, 0.08 times the mass of the pure nickel blocks of ytterbium powder is added, and stirring is continued for 20min, an ultrasonic concentrator of an ultrasonic device is preheated to 400℃, the ultrasonic concentrator is placed in the melt for ultrasonic treatment, the ultrasonic concentrator is set to be located 20cm below the liquid surface of the melt, the ultrasonic output frequency is 1.6KHz, the ultrasonic output power is 700W, and the ultrasonic time is 10min, the melt is subjected to refining and deslagging treatment, and casting is carried out in a metal mold, and the rare earth-nickel intermediate alloy is prepared after cooling to room temperature;

[0042] (2) nickel powder, aluminum powder and germanium powder are uniformly mixed according to a mass ratio of 1:0.08:0.06, and are placed in a ball mill, ball milling is carried out under argon protection, the ball-to-material ratio is set to be 10:1, the ball milling speed is 160r / min, and the ball milling time is 7h, and the mixed powder is prepared; the mixed powder and polyethylene glycol are uniformly mixed according to a mass ratio of 1:0.008, and are placed in a mold, the mold is placed on a pressure machine, a pressure of 560MPa is applied, and the pressure holding time is 2min, and the blank is prepared; the blank is placed in a sintering furnace, and is heated from room temperature to 360℃ at a heating rate of 10℃ / min, is held for 2h, is heated to 1260℃ at a heating rate of 5℃ / min, is held for 2h, and is cooled to room temperature, and the aluminum-germanium modified nickel alloy is prepared.

[0043] (3) graphite crucible is preheated to 420℃ in the pit type resistance furnace, rare earth-nickel intermediate alloy, aluminum-germanium modified nickel alloy are put into the crucible according to the mass ratio of 1:2.2 and heated to 1500℃, the ultrasonic concentrator of the ultrasonic device is preheated to 400℃, the ultrasonic concentrator is placed in the melt for ultrasonic treatment, the ultrasonic concentrator is set to be 20cm below the liquid surface of the melt, the ultrasonic output frequency is 1.6KHz, the ultrasonic output power is 700W, the ultrasonic time is 14min, the melt is refined and deslagged, and then poured into a metal mold, cooled to room temperature to obtain the modified nickel alloy; the 10mm thick modified nickel alloy and the 18mm thick pipeline steel plate are surface treated, the pipeline steel plate and the modified nickel alloy are combined by using the symmetric blanking method, the pipeline steel plate is placed at the outermost side, and the blanking is completed; the modified nickel alloy and the pipeline steel plate are welded and sealed, and vacuum treatment is performed, the vacuum degree of the vacuum treatment is not less than 10 -2 Pa, and a composite blank is obtained; the composite blank is heated to 1250℃ at a heating rate of 10℃ / min, and after holding for 10h, rough rolling is started, the temperature of the composite blank after rough rolling reaches 880℃, and then finish rolling is started, the finished product specification is 3+24.5mm, and after finish rolling, cooling is performed; the composite blank after finish rolling and cooling is first subjected to hot straightening treatment, and then is placed at a temperature of 660℃ for heat treatment, after heat treatment, cutting, plate separation, flattening, surface polishing and flaw detection treatment are performed, and then is printed, packaged and delivered, and a nickel-based rolled composite plate is obtained.

[0044] Comparative Example 1

[0045] The preparation method of the nickel-based rolled composite plate of Comparative Example 1 is different from that of Example 2 in that step (1) is not performed, and step (3) is modified as follows: graphite crucible is preheated to 400℃ in the pit type resistance furnace, pure nickel block and aluminum-germanium modified nickel alloy are put into the crucible according to the mass ratio of 1:2.1 and heated to 1450℃, the ultrasonic concentrator of the ultrasonic device is preheated to 350℃, the ultrasonic concentrator is placed in the melt for ultrasonic treatment, the ultrasonic concentrator is set to be 18cm below the liquid surface of the melt, the ultrasonic output frequency is 1.5KHz, the ultrasonic output power is 650W, the ultrasonic time is 15min, the melt is refined and deslagged, and then poured into a metal mold, cooled to room temperature to obtain the modified nickel alloy; the 10mm thick modified nickel alloy and the 18mm thick pipeline steel plate are surface treated, the pipeline steel plate and the modified nickel alloy are combined by using the symmetric blanking method, the pipeline steel plate is placed at the outermost side, and the blanking is completed; the modified nickel alloy and the pipeline steel plate are welded and sealed, and vacuum treatment is performed, the vacuum degree of the vacuum treatment is not less than 10 -2Pa, the composite blank is prepared; the composite blank is heated to 1100°C at a heating rate of 10°C / min, and after holding for 90 h, rough rolling is started, and immediately after rough rolling, the temperature of the composite blank is heated to 1200°C, and then finish rolling is started, and after finish rolling, the composite blank is cooled; the composite blank after finish rolling and cooling is first subjected to hot straightening treatment, and then is subjected to heat treatment at a temperature of 800°C, after the heat treatment, the composite blank is cut, divided into plates, flattened, polished, and subjected to flaw detection treatment, and then is packaged and delivered, to obtain the nickel-based rolled composite plate. The other steps are the same as those in Example 2.

[0046] Comparative Example 2

[0047] The preparation method of the nickel-based rolled composite plate of Comparative Example 2 is different from that of Example 2 in that step (2) is not performed, and step (3) is modified as follows: a graphite crucible is preheated to 400°C in a pit-type resistance furnace, a rare earth-nickel intermediate alloy and pure nickel blocks are placed in the crucible at a mass ratio of 1:2.1 and heated to 1450°C, an ultrasonic energy concentrator of an ultrasonic device is preheated to 350°C, the ultrasonic energy concentrator is placed in the melt for ultrasonic treatment, the ultrasonic energy concentrator is set to be located 18 cm below the liquid surface of the melt, the ultrasonic output frequency is 1.5 kHz, the ultrasonic output power is 650 W, and the ultrasonic time is 15 min, the melt is subjected to refining and slag removal treatment, and the modified nickel alloy is prepared by pouring into a metal mold and cooling to room temperature; the 10 mm thick modified nickel alloy and the 18 mm thick pipeline steel plate are subjected to surface treatment, the pipeline steel plate and the modified nickel alloy are combined by using a symmetric assembly method, the pipeline steel plate is placed at the outermost side, and the assembly is completed; the assembled modified nickel alloy and pipeline steel plate are welded and sealed, and are subjected to vacuum treatment, the vacuum degree of the vacuum treatment is not less than 10 -2 Pa, the composite blank is prepared; the composite blank is heated to 1100°C at a heating rate of 10°C / min, and after holding for 90 h, rough rolling is started, and immediately after rough rolling, the temperature of the composite blank is heated to 1200°C, and then finish rolling is started, and after finish rolling, the composite blank is cooled; the composite blank after finish rolling and cooling is first subjected to hot straightening treatment, and then is subjected to heat treatment at a temperature of 800°C, after the heat treatment, the composite blank is cut, divided into plates, flattened, polished, and subjected to flaw detection treatment, and then is packaged and delivered, to obtain the nickel-based rolled composite plate. The other steps are the same as those in Example 2.

[0048] Test Example 1

[0049] Test of mechanical properties

[0050] Test method: the Vickers hardness of the examples and the comparative examples is tested by using a micro Vickers hardness tester, the loading pressure is 10 N, the holding time is 15 s, 20 data points are tested and the average value is calculated.

[0051] Shear samples were prepared according to GB / T6396-2008, and a universal material tensile testing machine with a model number of INSTRON5969 was used to test the mechanical properties of the shear samples, and the shear strength, yield strength and interfacial bonding strength were counted;

[0052] The intergranular corrosion rate of the coating was detected according to ASTM G28 A method;

[0053] The results are shown in Table 1.

[0054] Table 1

[0055]

[0056] As can be seen from the comparison of the experimental data of Examples 1-3 and Comparative Examples 1-2 in Table 1, the nickel-based rolled composite plate prepared by the present application has good mechanical properties.

[0057] By comparison, the hardness of Examples 1-3 is greater than that of Comparative Example 1, which shows that the rare earth-nickel intermediate alloy is prepared by melting and mixing pure nickel blocks and ytterbium powder and using high-energy ultrasonic method; the addition of ytterbium powder can refine the grain, and the uniform dispersion of ytterbium powder in the nickel-based alloy using high-energy ultrasonic method helps to hinder dislocation movement and grain boundary sliding, while reducing the atomic diffusion speed in the matrix, thereby realizing the dispersion strengthening effect on the nickel-based alloy, and endowing the nickel-based rolled composite plate with excellent mechanical properties.

[0058] Test Example 2

[0059] Test of corrosion resistance

[0060] Test method: electrochemical impedance method was used to test the corrosion resistance of the examples and comparative examples. A Gamry Interface 1000 electrochemical workstation was used, with the examples and comparative examples as working electrodes, the working area being 1cm 2 , platinum electrode as counter electrode, saturated calomel electrode as reference electrode, and the three-electrode system was used to measure the open circuit potential in 3.5% NaCl solution, the test time being 1800s, and the open circuit potential being stable, indicating that the system reached a steady state, and then the electrochemical impedance was measured, with the parameter setting being amplitude 10mV and frequency range 100kHz to 0.01Hz. The results are shown in Table 2.

[0061] Table 2

[0062]

[0063] As can be seen from the comparison of the experimental data of Examples 1-3 and Comparative Examples 1-2 in Table 2, the nickel-based rolled composite plate prepared by the present application has good corrosion resistance.

[0064] By comparison, the charge transfer resistance of examples 1~3 is greater than that of comparative example 1, which shows that the rare earth-nickel intermediate alloy is prepared by melting and mixing pure nickel block and ytterbium powder, and using high-energy ultrasonic method; the addition of ytterbium powder can refine the grain, and the use of high-energy ultrasonic method can uniformly disperse the ytterbium powder in the nickel-based alloy, which helps to hinder the dislocation movement and grain boundary sliding, and at the same time reduces the atomic diffusion speed in the matrix, so as to realize the dispersion strengthening effect of the nickel-based alloy, inhibit the grain boundary corrosion, and endow the nickel-based rolling composite plate with excellent corrosion resistance.

[0065] By comparison, the charge transfer resistance of examples 1~3 is greater than that of comparative example 2, which shows that the aluminum-germanium modified nickel alloy is prepared by ball milling, pressing and sintering with nickel powder, aluminum powder and germanium powder as raw materials; the addition of Ge element reduces the migration rate of Ni element from the matrix to the surface, and Al element has a smaller atomic radius, a relatively fast migration rate compared with other metal elements, and is more likely to contact with oxygen in the air, so as to form a complete aluminum oxide film on the surface of the alloy, hinder the further oxidation of oxygen, and improve the corrosion resistance of the alloy.

[0066] The above specific embodiments further illustrate the purpose, technical solutions and beneficial effects of the present application, and it should be understood that the above description is only a specific embodiment of the present application and is not used to limit the protection scope of the present application, and any modification, equivalent replacement, improvement, etc. within the spirit and principles of the present application should be included in the protection scope of the present application.

Claims

1. A nickel-based rolled clad plate characterized by, The nickel-based rolling composite plate is prepared by vacuum rolling composite method of modified nickel alloy and pipeline steel plate; The preparation method of the nickel-based rolling composite plate comprises the following preparation steps: S1, surface treatment is performed on the 22mm-thick modified nickel alloy and 180mm-thick pipeline steel plate, the pipeline steel plate and the modified nickel alloy are combined by using the symmetric blanking method, the pipeline steel plate is placed at the outermost side, and blanking is completed; S2, welding and sealing edges of the modified nickel alloy and pipeline steel plate materials and performing vacuum treatment, the vacuum degree of the vacuum treatment is not less than 10 -2 Pa, preparing a composite blank; S3, the composite blank is heated to 1150-1250℃ at a heating rate of 10℃ / min, and after holding for 8-10h, rough rolling is started, and after rough rolling, the temperature of the composite blank is immediately heated to 800-1500℃, and then finish rolling is started, and after finish rolling, cooling is performed; S4, after the composite blank is cooled after finish rolling, hot straightening is performed, and then the composite blank is placed at a temperature of 500-920℃ for temperature holding, and after heat treatment is completed, cutting, plate separation, flattening, surface polishing and flaw detection treatment are performed, and then the nickel-based rolling composite plate is packaged and delivered, and the nickel-based rolling composite plate is prepared; The modified nickel alloy is prepared by the following steps:

2. The nickel-based rolled clad sheet according to claim 1, characterized in that, (1) the graphite crucible is preheated to 500-520℃, the pure nickel block is put in, the temperature is increased to 1400-1500℃, and the stirring is performed at 200-300r / min for 10-12min, the ytterbium powder with a mass of 0.06-0.08 times that of the pure nickel block is added, and the stirring is continuously performed for 20-30min, the ultrasonic energy concentrator of the ultrasonic device is preheated to 300-400℃, the ultrasonic energy concentrator is placed in the melt for ultrasonic treatment, the melt is refined and deslagged, and the melt is poured in the metal mold and cooled to room temperature, and the rare earth-nickel intermediate alloy is prepared; (2) the mixed powder and polyethylene glycol are mixed uniformly according to the mass ratio of 1:(0.006-0.008), and then the mixture is placed in the mold, the mold is placed on the pressure machine, and the pressure of 550-560MPa is applied, and the pressure holding time is 2-3min, and then the blank is prepared; the blank is placed in the sintering furnace, the temperature is increased to 350-360℃ from room temperature at a heating rate of 10℃ / min, and the temperature is held for 2-3h, the temperature is increased to 1250-1260℃ at a heating rate of 5℃ / min, and the temperature is held for 2-3h, and then the aluminum-germanium modified nickel alloy is prepared by cooling to room temperature; (3) the graphite crucible is preheated to 380-420℃ in the pit-type resistance furnace, the rare earth-nickel intermediate alloy and the aluminum-germanium modified nickel alloy are put in the crucible according to the mass ratio of 1:(2-2.2), the temperature is increased to 1400-1500℃, the ultrasonic energy concentrator of the ultrasonic device is preheated to 300-400℃, the ultrasonic energy concentrator is placed in the melt for ultrasonic treatment, the melt is refined and deslagged, and the melt is poured in the metal mold and cooled to room temperature, and then the modified nickel alloy is prepared. ​ 3. The nickel-based rolled clad sheet according to claim 2, characterized in that, The process parameters of the ultrasonic treatment in step (1) are as follows: the ultrasonic concentrator is arranged at a position 16-20 cm below the liquid surface of the melt, the ultrasonic output frequency is 1.4-1.6 kHz, the ultrasonic output power is 600-700 W, and the ultrasonic time is 10-12 min; and the mesh number of the ytterbium powder is 400 mesh.

4. The nickel-based rolled clad sheet according to claim 2, characterized in that, The preparation method of the mixed powder in step (2) is as follows: the nickel powder, the aluminum powder and the germanium powder are uniformly mixed, and then are placed in a ball mill to perform ball milling under the protection of argon, the ball-to-material ratio is set to (9-10):1, the ball milling speed is 140-160 r / min, and the ball milling time is 7-9 h, so as to obtain the mixed powder.

5. The nickel-based rolled clad sheet according to claim 4, characterized in that, The mass ratio of the nickel powder, the aluminum powder and the germanium powder is 1:(0.06-0.08):(0.04-0.06).

6. The nickel-based rolled clad sheet according to claim 4, characterized in that, The mesh number of the nickel powder is 300, the mesh number of the aluminum powder is 400, and the mesh number of the germanium powder is 600.

7. The nickel-based rolled clad sheet according to claim 2, wherein The type of the polyethylene glycol in step (2) is PEG2000.

8. The nickel-based rolled clad sheet of claim 2 wherein, The process parameters of the ultrasonic treatment in step (3) are as follows: the ultrasonic concentrator is arranged at a position 16-20 cm below the liquid surface of the melt, the ultrasonic output frequency is 1.4-1.6 kHz, the ultrasonic output power is 600-700 W, and the ultrasonic time is 14-16 min.

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