CN109706400B - Hastelloy and carbon steel composite plate and manufacturing method thereof - Google Patents
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- 229910000856 hastalloy Inorganic materials 0.000 title claims abstract description 83
- 229910000975 Carbon steel Inorganic materials 0.000 title claims abstract description 63
- 239000010962 carbon steel Substances 0.000 title claims abstract description 63
- 239000002131 composite material Substances 0.000 title claims abstract description 57
- 238000004519 manufacturing process Methods 0.000 title abstract description 13
- 238000005096 rolling process Methods 0.000 claims abstract description 54
- 238000010438 heat treatment Methods 0.000 claims abstract description 15
- 229910000831 Steel Inorganic materials 0.000 claims description 27
- 239000010959 steel Substances 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 17
- 238000004321 preservation Methods 0.000 claims description 12
- 238000005098 hot rolling Methods 0.000 claims description 11
- 238000003466 welding Methods 0.000 claims description 11
- 239000012535 impurity Substances 0.000 claims description 10
- 238000002360 preparation method Methods 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 6
- 229910052804 chromium Inorganic materials 0.000 claims description 5
- 239000011248 coating agent Substances 0.000 claims description 5
- 238000000576 coating method Methods 0.000 claims description 5
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 229910000765 intermetallic Inorganic materials 0.000 claims description 3
- 230000001680 brushing effect Effects 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims description 2
- 238000002955 isolation Methods 0.000 claims description 2
- 238000007789 sealing Methods 0.000 claims description 2
- 238000005728 strengthening Methods 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims 2
- 229910052742 iron Inorganic materials 0.000 claims 1
- 229910052748 manganese Inorganic materials 0.000 claims 1
- 229910052721 tungsten Inorganic materials 0.000 claims 1
- 238000010008 shearing Methods 0.000 abstract description 3
- 238000013329 compounding Methods 0.000 abstract description 2
- 230000007797 corrosion Effects 0.000 description 22
- 238000005260 corrosion Methods 0.000 description 22
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 239000011651 chromium Substances 0.000 description 5
- 239000000956 alloy Substances 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 238000010894 electron beam technology Methods 0.000 description 3
- 150000002736 metal compounds Chemical class 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000002360 explosive Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910000851 Alloy steel Inorganic materials 0.000 description 1
- 229910001209 Low-carbon steel Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- BIJOYKCOMBZXAE-UHFFFAOYSA-N chromium iron nickel Chemical compound [Cr].[Fe].[Ni] BIJOYKCOMBZXAE-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 229910000623 nickel–chromium alloy Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000009489 vacuum treatment Methods 0.000 description 1
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Abstract
The invention discloses a Hastelloy and carbon steel composite plate and a manufacturing method thereof, wherein the Hastelloy and carbon steel composite plate comprises a Hastelloy layer, an intermediate layer interface adjacent to the Hastelloy, an intermediate layer interface adjacent to the carbon steel and a carbon steel layer, wherein the intermediate layer is positioned between the intermediate layer interface adjacent to the Hastelloy and the intermediate layer interface adjacent to the carbon steel and is connected with the intermediate layer interface adjacent to the Hastelloy and the intermediate layer interface adjacent to the carbon steel. The manufacturing method of the hastelloy and carbon steel composite plate adopts vacuum rolling compounding, the blank is kept warm when being heated, the temperature difference between the rolling temperature and the heating temperature is controlled within a certain range, and multi-pass rolling is carried out, so that the hastelloy and carbon steel composite plate with higher shearing strength is finally obtained.
Description
Technical Field
The invention belongs to the technical field of metal composite materials and engineering, and particularly relates to a hastelloy and carbon steel composite plate and a manufacturing method thereof.
Background
Because steel and general metal materials are easy to react with substances such as oxygen, water and the like in the air to cause corrosion, the corrosion is more serious in an acid-base environment, and the engineering integrity is damaged due to the corrosion phenomenon, so that economic loss is caused. The single steel does not meet the requirements for a highly corrosion-resistant working environment. Hastelloy is a corrosion-resistant alloy with a plurality of excellent performances, has good resistance to oxidative corrosion and medium reductive corrosion, has excellent stress corrosion cracking resistance and good local corrosion resistance, and is a widely applied corrosion-resistant alloy material.
The hastelloy and carbon steel composite plate has excellent high-temperature resistance and corrosion resistance of the hastelloy and mechanical properties and cost advantages of carbon steel, has excellent new performances of resisting pitting corrosion, crevice corrosion and stress corrosion cracking in the state of simultaneous existence of an oxidation environment and a reduction environment, can be used for manufacturing pipelines or containers for conveying or containing corrosive liquid or gas, and has wide application prospects in the fields of paper making industry, chemical industry, petroleum industry and the like.
In view of the above advantages of hastelloy and carbon steel composite plates, the development of high-performance nickel-based composite plates is an important trend in the development of composite plates. In view of the above, a great deal of research is conducted at home and abroad, and for example, patent documents of patent No. cn2017222.u provide a method for preparing a C276 hastelloy and steel composite plate by an explosive welding process. However, the explosive welding process is complex, has high requirements on test sites and test environments, is complex to operate, has high risk, has larger environmental and noise pollution, and is difficult to be applied on a large scale. Patent CN104525611 discloses a method for preparing a nickel-chromium alloy and carbon steel composite plate for a pipeline by adopting continuous rolling water cooling, which is easy to realize automation, the thickness of the material and the components of a bonding layer can be controlled by adjusting the rolling process parameters, the bonding strength is high, the corrosion resistance is good, and compared with the preparation process of an explosion welding composite plate, the method is easier to industrialize. But the selected nickel-chromium-iron-based alloy can only resist the corrosion of the reduction environment. The Hastelloy and steel composite plate material which is prepared by adopting a rolling process and can resist the corrosion of two comprehensive environments of oxidation and reduction is still blank at present, and becomes an important trend for developing high-performance composite plates.
Disclosure of Invention
The purpose of the invention is as follows: the invention discloses a Hastelloy and carbon steel composite plate and a manufacturing method thereof. The manufacturing method of the hastelloy and carbon steel composite plate adopts vacuum rolling, does not pollute the environment, and the composite plate manufactured by adopting the process can resist the corrosion of two comprehensive environments of oxidation and reduction.
The technical scheme is as follows: a Hastelloy and carbon steel composite plate comprises a Hastelloy layer, an intermediate layer interface adjacent to the Hastelloy, an intermediate layer interface adjacent to the carbon steel and a carbon steel layer, wherein the intermediate layer is positioned between the intermediate layer interface adjacent to the Hastelloy and the intermediate layer interface adjacent to the carbon steel and is connected with the intermediate layer interface adjacent to the Hastelloy and the intermediate layer interface adjacent to the carbon steel.
Intermetallic compounds are precipitated from the interface of the intermediate layer adjacent to the hastelloy, and mainly comprise three elements of Ni, Cr and Mo.
The mass percentage content of the carbon steel layer is that C is less than or equal to 0.22 percent, Mn is less than or equal to 1.8 percent, Si is less than or equal to 0.6 percent, S is less than or equal to 0.050P and less than or equal to 0.045, and the balance is Fe and inevitable impurity elements, or microalloy strengthening element V with the mass fraction not more than 0.12 percent is added.
The hastelloy layer comprises, by mass, not more than 0.02% of C, not less than 21% of Cr within a range of 10%, not less than 20% of Mo within a range of 13%, not less than 9% of Fe within a range of 3%, not less than 6% of W within a range of 3%, not more than 0.10% of Si, not more than 3.5% of Co, and the balance of Ni and inevitable impurity elements.
The invention also discloses a preparation method of the hastelloy and carbon steel composite plate, which comprises the following steps:
1) rolling a base material steel plate or a steel billet and a composite hastelloy to a designed size, cleaning the surfaces of the hastelloy and carbon steel, and brushing a high-temperature resistant isolation coating on one surface of the hastelloy; combining carbon steel or steel blanks with hastelloy by adopting a symmetrical assembly method, and placing the steel plate or steel blank on the outermost side to complete the combination of the steel plate or steel blank;
2) welding and sealing edges of the combined steel plate and the Hastelloy plate, and vacuumizing to obtain a combined blank;
3) placing the combined blank at the temperature of 800-1500 ℃ for heat preservation, then starting hot rolling, immediately heating the composite plate to reach the temperature of 800-1500 ℃ after rolling, then taking out the composite plate for rolling, and forming the composite plate after multi-pass heat preservation-rolling procedures, wherein the single-pass reduction rate is 10-40%;
4) and (3) placing the composite plate formed after hot rolling at the temperature of 500-1100 ℃ for heat treatment.
Specifically, the combined blank in the step 3) is placed at the temperature of 1100 ℃ for heat preservation and then hot rolling is started, and the shear strength of the obtained composite plate is the highest.
Specifically, the heat treatment temperature in the step 4) is 1000 ℃. In the step 3), the difference between the initial rolling temperature and the heat preservation temperature is controlled within 50 ℃, and the difference between the final rolling temperature and the heat preservation temperature is controlled within 100 ℃. Step 2) vacuum treatment with vacuum degree not less than 10-2Pa。
Has the advantages that: the hastelloy in the hastelloy and carbon steel composite plate contains high-content Mo element, and the addition of the Mo element greatly improves the corrosion resistance of the material in strong reduction and strong oxidation environments, and improves the two performances of the material, namely the resistance to crevice corrosion and the resistance to stress corrosion. Meanwhile, because the content of Mo in the selected Hastelloy is high, the Mo-rich compound can be formed with other elements in a high-temperature environment, and the corrosion resistance of the Hastelloy can be reduced along with the growth of a metal compound. Therefore, it is a critical requirement for the process design of this patent to effectively control the formation of Mo-rich metal compounds. The manufacturing method of the hastelloy and carbon steel composite plate strictly controls the vacuum degree, prevents the contact of a bonding interface and oxygen, and avoids the generation of brittle oxides at the bonding interface. And a unique rolling process is designed, and the internal stress generated at the interface due to the thermal expansion difference is released by controlling the rolling temperature, so that the generation of defects of the bonding surface in the rolling process is avoided. Meanwhile, the diffusion distance of the interface elements is effectively controlled to be 2-3 mu m, and the composite board is formed by metal compounds, so that high-quality combination of the composite board is realized.
Drawings
Fig. 1 is a schematic view of the assembly of the composite slab of the present invention before rolling.
FIG. 2 is a secondary electron micrograph of a SEM of a Hastelloy alloy and carbon steel composite plate according to the present invention.
FIG. 3 is a shear strength curve of the Hastelloy prepared by the invention and a carbon steel composite plate.
FIG. 4 is a comparison curve of the shearing strength of the hastelloy prepared at the rolling temperature of 1000 ℃, 1100 ℃ and 1200 ℃ in the invention and the carbon steel composite plate.
Detailed Description
Example 1
A manufacturing method of a hastelloy and carbon steel composite plate comprises the following steps:
1) c-276 hastelloy with the size of 100mm multiplied by 120mm multiplied by 4mm and carbon steel with the size of 100mm multiplied by 120mm multiplied by 8m are polished to be bright, and surface impurities are washed away by acid; wherein, the mass percentage content of the carbon steel is that C is less than or equal to 0.22 percent, Mn is less than or equal to 1.8 percent, Si is less than or equal to 0.6 percent, S is less than or equal to 0.050P is less than or equal to 0.045, and the balance is Fe and inevitable impurity elements; the hastelloy comprises, by mass, not more than 0.02% of C, not less than 21% of Cr which is not less than 10%, not less than 20% of Mo which is not less than 13%, not less than 9% of Fe which is not less than 3%, not less than 6% of W which is not less than 3%, not more than 0.10% of Si, not more than 3.5% of Co, and the balance of Ni and inevitable impurity elements.
2) Coating a release agent between the contact surfaces of the two layers of hastelloy to prepare a symmetrical combined butt-joint billet, and placing a steel plate or a steel billet on the outermost side.
3) Adding edge strips to the combined Hastelloy and carbon steel billet, adopting a vacuum electron beam welding method to vacuumize the combined billet by using a mechanical pump, wherein the vacuum degree reaches 10-2And welding after Pa to obtain a blank with the total thickness of 24 mm.
4) And (2) placing the combined blank at 1100 ℃ for heat preservation for 10min, then starting hot rolling, wherein the rolling speed is 40m/min, the rolling amount of the first rolling is 5mm, immediately heating the composite plate to 1100 ℃ after rolling, then taking out the plate, rolling at the same rolling speed, and rolling at the second rolling amount of 4mm, repeating the processes, wherein the rolling amount of the third rolling is 5mm, the rolling amount of the fourth rolling is 4mm, finally rolling to the thickness of 6mm, cutting off four sides of the rolled plate, so as to obtain two hastelloy and carbon steel composite plates with the thickness of 3mm, the interface bonding of the hastelloy and carbon steel is good, the microstructure is shown in figure 2, the performance is excellent, the shear strength is 422MPa, and the shear curve is shown in figure 3.
5) And (3) respectively placing the hastelloy and the carbon steel composite plate which are subjected to hot rolling compounding at the temperature of 1100 ℃ at the temperature of 500-1100 ℃ and preserving heat for 1h with the temperature gradient of 100 ℃, and then air-cooling. The shear strength of the composite panel after heat treatment is as follows:
TABLE 1
As shown by the comparison of the shear strength data in Table 1, the shear strength at 600 ℃, 900 ℃ and 1000 ℃ is over 300MPa, the performance is the best at 1000 ℃, the shear strength can reach 480MPa, and the strength is increased by 15 percent. However, the interface strength is increased in the 1000 ℃ heat treatment alone compared to the 1100 ℃ hot rolled state, as compared to the interface shear strength of the non-heat treatment process. The interface bonding strength of the 1100 ℃ hot rolling state is 422MPa, and the interface bonding strength of the other temperature heat treatment is lower than that of the 1100 ℃ hot rolling state. The diffusion between molecules is enhanced mainly due to the heat treatment, and the reaction diffusion between atoms is promoted by the increase of the temperature. Elements between interfaces react with each other to generate intermetallic oxide and brittle phase hard particles, cracks are generated when the shearing stress reaches a critical value, the brittle phase hard oxide and the brittle phase hard particles cannot consume the energy of crack propagation, namely cannot block the crack propagation, and finally the interfaces break and debond.
Example 2
A manufacturing method of a hastelloy and carbon steel composite plate comprises the following steps:
1) c-276 hastelloy with the size of 150mm multiplied by 3mm and carbon steel with the size of 150mm multiplied by 9m are polished to be bright, and surface impurities are washed away by acid; wherein the mass percentage content of the carbon steel is that C is less than or equal to 0.22 percent, Mn is less than or equal to 1.8 percent, Si is less than or equal to 0.6 percent, S is less than or equal to 0.050P is less than or equal to 0.045, and the balance is Fe and inevitable impurity elements; the hastelloy comprises, by mass, not more than 0.02% of C, not less than 21% of Cr which is not less than 10%, not less than 20% of Mo which is not less than 13%, not less than 9% of Fe which is not less than 3%, not less than 6% of W which is not less than 3%, not more than 0.10% of Si, not more than 3.5% of Co, and the balance of Ni and inevitable impurity elements.
2) Coating a release agent between the contact surfaces of the two layers of hastelloy to prepare a symmetrical combined butt-joint billet, and placing a steel plate or a steel billet on the outermost side.
3) Adding edge strips to the combined Hastelloy and carbon steel billet, adopting a vacuum electron beam welding method to vacuumize the combined billet by using a mechanical pump, wherein the vacuum degree reaches 10-2And Pa later, welding to obtain a blank with the total thickness of 30 mm.
4) And (2) placing the combined blank at the temperature of 1000 ℃ for heat preservation for 10min, starting hot rolling, wherein the rolling speed is 30m/min, the rolling amount of the first rolling is 4mm, immediately heating the composite plate to 1000 ℃ after rolling, then taking out the plate, rolling at the same rolling speed, wherein the rolling amount of each rolling is 4mm, finally rolling to the thickness of 6mm after 6 times of rolling, cutting off four edges of the rolled plate to obtain two hastelloy and carbon steel composite plates with the thickness of 3mm, and the interface bonding strength of the hastelloy and the carbon steel reaches 270 MPa.
Example 3
The invention also sets a contrast experiment aiming at the influence of the rolling temperature on the bonding strength of the manufacturing method of the hastelloy and carbon steel composite plate, and the specific experiment steps are as follows:
1) c-276 Hastelloy with the size of 150mm 125mm 4mm and low-carbon steel with the size of 150mm 125mm 8mm Q235 are polished to be bright and cleaned with acid to remove surface impurities. Hastelloy compositions are as follows in table 2:
TABLE 2 Hastelloy composition (wt%)
2) Coating a release agent between the contact surfaces of the two layers of hastelloy to prepare a symmetrical combined butt-joint billet, and placing a steel plate or a steel billet on the outermost side.
3) Adding edge strips to the combined Hastelloy and carbon steel billet, adopting a vacuum electron beam welding method to vacuumize the combined billet by using a mechanical pump, wherein the vacuum degree reaches 10-2And (6) welding after Pa to obtain the vacuum combined butt-joint blank.
4) Heating the vacuum combined blank at 1000 deg.C, 1100 deg.C, 1200 deg.C respectively, and setting the initial heat preservation time to 20 min. In order to ensure that the temperature in the whole rolling process is as close to the initial temperature as possible, the on-line furnace returning and heat preservation are carried out for 5min between each pass of rolling, and the rolling speed is 40 m/min. And (3) preserving the heat of the combined plate blank at different temperatures, and researching the influence of different temperatures on the rolling bonding strength. The shear strength versus curve is shown in FIG. 4. As shown in Table 3, the hastelloy and the carbon steel composite plate manufactured at three different rolling temperatures can be well combined, but the mechanical property is relatively best at 1100 ℃, and the shear strength reaches 422 MPa. The interfacial fracture mode is brittle fracture at a rolling temperature of 1000 ℃, ductile fracture at 1200 ℃ and both fracture modes at 1100 ℃.
Table 31000 ℃, 1100 ℃, 1200 ℃ shear strength
The hastelloy and carbon steel composite plate manufactured by the manufacturing method of the hastelloy and carbon steel composite plate disclosed by the three embodiments comprises a hastelloy layer, an intermediate layer interface adjacent to the hastelloy, an intermediate layer interface adjacent to the carbon steel and a carbon steel layer, wherein the intermediate layer is positioned between the intermediate layer interface adjacent to the hastelloy and the intermediate layer interface adjacent to the carbon steel and is connected with the intermediate layer interface adjacent to the hastelloy and the intermediate layer interface adjacent to the carbon steel. Intermetallic compounds are separated out from the interface of the adjacent intermediate layers of the hastelloy, and mainly comprise three elements of Ni, Cr and Mo.
Claims (5)
1. The hastelloy and carbon steel composite plate is characterized in that: the high-strength steel plate comprises a Hastelloy layer, an intermediate layer interface adjacent to the Hastelloy, an intermediate layer interface adjacent to carbon steel and a carbon steel layer, wherein the mass percent of the carbon steel layer is less than or equal to 0.22 percent of C, less than or equal to 1.8 percent of Mn, less than or equal to 0.6 percent of Si, less than or equal to 0.050 percent of S, less than or equal to 0.045 percent of P, and the balance of Fe and inevitable impurity elements, or microalloy strengthening elements V with the mass fraction of no more than 0.12 percent is added, the mass percent of the Hastelloy layer is less than or equal to 0.02 percent of C, less than or equal to 10 percent of Cr and less than or equal to 21 percent of Cr, less than or equal to 13 percent of Mo and less than or equal to 20 percent of Fe, less than or equal to 9 percent of 3 percent, less than or equal to 6 percent of W, less than or equal to 0.10 percent of Si, less than or equal to 3.5 percent of Co, intermetallic compounds are precipitated from the interface of the adjacent intermediate layers of the hastelloy, and mainly comprise three elements of Ni, Cr and Mo.
2. The preparation method of the hastelloy and carbon steel composite plate according to claim 1, wherein the preparation method comprises the following steps: the method comprises the following steps:
1) rolling a base material steel plate or a steel billet and a composite hastelloy to a designed size, cleaning the surfaces of the hastelloy and carbon steel, and brushing a high-temperature resistant isolation coating on one surface of the hastelloy; combining carbon steel or steel blanks with hastelloy by adopting a symmetrical assembly method, and placing the steel plate or steel blank on the outermost side to complete the combination of the steel plate or steel blank;
2) welding, edge sealing and vacuumizing the combined steel plate and Hastelloy plate, wherein the vacuum degree of the vacuumizing treatment is not lower than 10-2Pa, obtaining a combined blank;
3) placing the combined blank at the temperature of 800-1500 ℃ for heat preservation, then starting hot rolling, immediately heating the composite plate to reach the temperature of 800-1500 ℃ after rolling, then taking out the composite plate for rolling, and forming the composite plate after multi-pass heat preservation-rolling procedures;
4) and (3) preserving heat of the composite plate formed by hot rolling at the temperature of 500-1100 ℃ for heat treatment, wherein the difference between the initial rolling temperature and the heat preservation temperature is controlled within 50 ℃, and the difference between the final rolling temperature and the heat preservation temperature is controlled within 100 ℃.
3. The preparation method of the hastelloy and carbon steel composite plate according to claim 2, wherein the preparation method comprises the following steps: and in the step 3), the combined blank is subjected to heat preservation at 1100 ℃ and then hot rolling is started.
4. The preparation method of the hastelloy and carbon steel composite plate according to claim 2, wherein the preparation method comprises the following steps: the heat treatment temperature in the step 4) is specifically 1000 ℃.
5. The preparation method of the hastelloy and carbon steel composite plate according to claim 2, wherein the preparation method comprises the following steps: the single-pass reduction rate in the step 3) is 10-40%.
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