CN110983164A - Microalloy element Nb-reinforced duplex stainless steel and preparation method thereof - Google Patents
Microalloy element Nb-reinforced duplex stainless steel and preparation method thereof Download PDFInfo
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- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C33/00—Making ferrous alloys
- C22C33/04—Making ferrous alloys by melting
- C22C33/06—Making ferrous alloys by melting using master alloys
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
- C21D1/18—Hardening; Quenching with or without subsequent tempering
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D6/00—Heat treatment of ferrous alloys
- C21D6/004—Heat treatment of ferrous alloys containing Cr and Ni
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- C21D6/00—Heat treatment of ferrous alloys
- C21D6/008—Heat treatment of ferrous alloys containing Si
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Abstract
The invention belongs to the field of stainless steel metal materials, and particularly relates to microalloy element Nb-reinforced duplex stainless steel and a preparation method thereof. The duplex stainless steel comprises the following components in percentage by mass: c is less than or equal to 0.03 percent; si is less than or equal to 1.0 percent; mn is less than or equal to 2.0 percent; s is less than or equal to 0.02 percent; p is less than or equal to 0.03 percent; cr: 21% -23%; ni: 4.5% -6.5%; mo: 2.5% -3.5%; nb: 0.03% -0.05%; n: 0.08% -0.20%, and the balance of Fe and inevitable impurities. According to the duplex stainless steel, trace Nb element is added into 2205 duplex stainless steel, so that the 2205 duplex stainless steel has more excellent mechanical property, meanwhile, the corrosion resistance of the duplex stainless steel is not reduced, the cost of the duplex stainless steel can be effectively reduced, the application range of the duplex stainless steel is expanded, the preparation method is simple, and the duplex stainless steel has important engineering application value and remarkable economic benefit.
Description
Technical Field
The invention belongs to the field of stainless steel metal materials, and particularly relates to microalloy element Nb-reinforced duplex stainless steel and a preparation method thereof.
Background
With the development of the economy and Stainless Steel industry in China and the increase of the demand of Stainless Steel materials in various fields, China has become a genuine large country and a consuming country in the world, in recent years, the total consumption of Stainless Steel in China is still increasing year by year, and the requirements of various fields on the quality of Steel are higher and higher due to the importance of people on life and property safety.
The addition of about 0.1 mass percent (unless otherwise stated, mass percent is referred to below) of related elements in the steel can have a significant or special influence on the microstructure and properties of the steel, i.e., microalloying. The alloy elements comprise Nb, V, Ti, Al, B, rare earth elements and the like, wherein among the elements, the three elements of Nb, V and Ti can be combined with C, N and the like in steel to precipitate to generate second phase particles which are dispersed and distributed, and the second phase particles can block the growth of grains and tissues, so that the effects of refining the grains and the tissues are achieved; or solid solution in the matrix, which hinders the growth of crystal grains due to the solid solution dragging effect.
The patent technology of 'ferritic stainless steel with excellent sound absorption performance for an exhaust system heat exchanger and a manufacturing method thereof' (CN 109790603A) adds 0.3% -0.6% of Nb in the steel, effectively utilizes the combination of Nb and carbon to separate out NbC, reduces the dissolving amount of the carbon in the steel, and improves the corrosion resistance and high-temperature strength of the ferritic steel. The invention relates to a ferritic stainless steel and a manufacturing method thereof (CN 101812641A), which is a technology for adding 0-0.06% of Nb and 0.05-0.25% of Ti into the steel, wherein Ti is more than or equal to 4 multiplied by Nb, the invention effectively utilizes the properties of strong ferrite forming elements and stabilizing elements of Nb, Nb and Ti are added into the ferritic stainless steel, and Nb and Ti can be combined with C, N in the ferritic stainless steel to form carbonitride of Nb and Ti, thereby inhibiting the precipitation of carbonitride of chromium in the ferritic steel and being beneficial to improving the intergranular corrosion resistance of the stainless steel; the method has the advantages that trace Nb is added to play a role in refining grains and improving the equiaxial proportion, so that the formability of the ferritic steel is improved; the component range of the invention is Nb: 0 to 0.06%, preferably 0 to 0.05%, Ti: 0.05-0.25% and Ti is more than or equal to 4 multiplied by Nb. The patent technology of the super austenitic stainless steel rolling composite steel plate and the manufacturing method thereof (CN 108116006A) adds 0.005-0.018% of Ti and 0.010-0.030% of Nb into the steel. The Nb is added into the base layer mainly for improving the recrystallization temperature of the stainless steel, so that crystal grains of the base layer can not grow rapidly after austenite recrystallization rolling is finished, and the improvement of the low-temperature impact toughness of the base layer steel is facilitated. Therefore, the mass percent of Nb in the base layer of the super austenitic stainless steel rolled composite steel plate is controlled to be 0.010-0.030%.
Nb microalloyed ferritic steel and austenitic steel products and application are more, but Nb microalloyed cast duplex stainless steel products and application are few, and the action mechanism of Nb on the duplex stainless steel is relatively immature. According to the invention, by adding a trace amount (0.03-0.05%) of Nb, the tensile strength is effectively improved on the premise of not reducing the corrosion resistance of the duplex stainless steel, the relationship between the Nb content and the structure, tensile strength and corrosion resistance of the duplex stainless steel under a certain solution treatment condition is determined, and the reasonable range of the Nb content in the duplex stainless steel is determined. Therefore, the microalloy element Nb-reinforced duplex stainless steel and the preparation method thereof have important significance for further improving the strength of the duplex stainless steel, improving the quality of the duplex stainless steel and saving the cost.
Disclosure of Invention
The invention provides a microalloy element Nb reinforced duplex stainless steel and a preparation method thereof. Finally, the reasonable Nb content range in the duplex stainless steel is determined, compared with the duplex stainless steel of the corresponding standard grade, the Nb-containing duplex stainless steel has better mechanical property and equivalent corrosion resistance, the quality of the duplex stainless steel is improved, the reduction manufacturing is facilitated, the cost is saved, and the application of the Nb-containing duplex stainless steel can be further promoted.
In order to achieve the purpose, the invention adopts the following technical scheme:
the microalloy element Nb reinforced duplex stainless steel comprises the following components in percentage by mass: c is less than or equal to 0.03 percent; si is less than or equal to 1.0 percent; mn is less than or equal to 2.0 percent; s is less than or equal to 0.02 percent; p is less than or equal to 0.03 percent; cr: 21% -23%; ni: 4.5% -6.5%; mo: 2.5% -3.5%; nb: 0.03% -0.05%; n: 0.08% -0.20%, and the balance of Fe and inevitable impurities.
The preparation method of the microalloy element Nb reinforced duplex stainless steel comprises the following steps:
(1) smelting in a medium-frequency induction furnace: all raw materials required by smelting need to be subjected to oil removal, degassing, rust removal and drying treatment before entering a furnace for smelting;
the materials used for smelting and the mass fractions thereof are respectively as follows:
23-25% of 316L stainless steel leftover materials, 4.5-4.7% of ferromolybdenum with the molybdenum content not less than 60%, 17.8-18.1% of metal chromium with the chromium content not less than 99%, 0.04-0.31% of Nb iron with the Nb content not less than 65%, 3.0-3.2% of metal nickel with the nickel content not less than 99%, 0.5-0.7% of metal manganese with the manganese content not less than 99%, and the balance furnace burden is industrial pure iron, wherein the sum of the mass percentages of the materials is 100%;
(2) firstly, adding cleaned and dried 316L stainless steel scraps into a crucible of a medium-frequency induction furnace for melting, and then sequentially adding ferromolybdenum, industrial pure iron, metal chromium, metal manganese, metal nickel and Nb iron; when the temperature of the stainless steel reaches 1600-1610 ℃, the stainless steel solution is deoxidized, and the amount of added deoxidizer silicon, calcium and manganese is 0.3 percent of the total smelting mass; then carrying out slag removal treatment on the stainless steel solution, measuring the temperature of the stainless steel solution before pouring, wherein the pouring temperature is not higher than 1620 ℃; proper degassing and dewatering treatment is carried out on an investment mould shell used for casting before casting;
(3) and (3) air-cooling the prepared duplex stainless steel with different Nb contents to room temperature, preserving the temperature at 1050 ℃ for 2h, and then performing water quenching.
The invention has the beneficial effects that: the microalloy element Nb-reinforced duplex stainless steel is prepared by adding trace Nb (0.03-0.05% of Nb) into 2205 duplex stainless steel, wherein the trace Nb is dissolved in a matrix, solid solution dragging of the dissolved Nb can also block the growth of grains so as to refine the grains, and the solid solution strengthening and fine grain strengthening effects are achieved, so that the 2205 duplex stainless steel has more excellent mechanical properties, the corrosion resistance of the duplex stainless steel is not reduced, the cost of the duplex stainless steel can be effectively reduced, the application range of the duplex stainless steel is expanded, the preparation method is simple, and the microalloy element Nb-reinforced duplex stainless steel has important engineering application value and remarkable economic benefit.
Drawings
FIG. 1 is a scanning electron microscope metallographic image of 0.03% Nb duplex stainless steel before corrosion;
FIG. 2 is a scanning electron microscope image of metallographic phase and NbMo phase of 0.05% Nb duplex stainless steel before corrosion;
FIG. 3 is a scanning electron microscope image of metallographic phase and NbMo phase of 0.10% Nb duplex stainless steel before corrosion;
FIG. 4 is a scanning electron microscope image of metallographic phase and NbMo phase of 0.15% Nb duplex stainless steel before corrosion;
FIG. 5 is a scanning electron microscope image of metallographic phase and NbMo phase of 0.20% Nb duplex stainless steel before corrosion;
FIG. 6 is an in situ scanning electron micrograph of the structure shown in FIG. 5 after etching;
FIG. 7 is a pitting corrosion morphology map of a 0.00% Nb duplex stainless steel;
FIG. 8 is a pitting corrosion morphology diagram of a 0.03% Nb duplex stainless steel;
FIG. 9 is a pitting corrosion morphology diagram of a 0.05% Nb duplex stainless steel;
FIG. 10 is a pitting topography of a 0.10% Nb duplex stainless steel;
FIG. 11 is a pitting corrosion morphology map of a 0.15% Nb duplex stainless steel;
FIG. 12 is a pitting corrosion morphology map of 0.20% Nb duplex stainless steel.
Detailed Description
The present invention will be described in more detail with reference to examples. These examples are merely illustrative of the best mode of carrying out the invention and do not limit the scope of the invention in any way.
Example (b): smelting biphase stainless steel liquid by using a medium-frequency induction furnace, pouring the biphase stainless steel liquid into an investment mould shell to be solidified into a test bar, after a casting is cooled, carrying out sand cleaning treatment, cutting off a casting cap opening, cutting out the test bar, and then carrying out machining to obtain the test bar with the thickness of ∅ 22mm multiplied by 220 mm.
The chemical composition of the microalloy element Nb-reinforced duplex stainless steel of the invention is shown in Table 1, and the heat treatment mode thereof is shown in Table 2. (examples 1, 2, 3, 4, 5 are duplex stainless steels of different Nb contents prepared by adding Nb iron, comparative example 1 is a duplex stainless steel without Nb addition.)
TABLE 1 chemical composition of different materials
Note: the balance being Fe.
The solution treatment method of the examples and comparative examples is shown in table 2.
TABLE 2 solution treatment mode of materials
Processing the test bar into a standard tensile sample according to the national standard GB/T228.1-2010, and testing the tensile strength of the standard tensile sample by adopting a universal tensile testing machine; and testing Tafel curves of different materials in a simulated oil field by adopting a German Princeton electrochemical workstation to obtain corrosion current densities of the different materials. Tensile strength, elongation and corrosion current density are shown in table 3;
TABLE 3 comparison table of tensile strength, elongation and corrosion current density
As can be seen from the above examples, the microalloy element Nb-reinforced duplex stainless steel of the present invention has more excellent tensile strength, elongation and corrosion resistance, and the tensile strength, elongation and corrosion resistance of example 1 are superior to those of comparative example 1; the corrosion resistance of example 2 is equivalent to that of comparative example 1, and the corrosion resistance of example 3 is inferior to that of comparative example 1, but the tensile strength and elongation are superior to those of comparative example 1. Therefore, the Nb content of this duplex stainless steel should not exceed 0.10%.
The tensile strength of the microalloy element Nb reinforced duplex stainless steel is improved compared with that of standard duplex stainless steel. As the amount of Nb increased, a precipitate phase formed in the duplex stainless steel, as determined by scanning electron mirror scanning, was NbMo phase and was bright white under backscattered electron imaging conditions, as shown in fig. 1 to 5.
As can be seen from fig. 1 to 5, in example 1, under a certain solution treatment condition, NbMo phase precipitation was not observed, and then, as the amount of Nb increased, the number of NbMo phases in the duplex stainless steel increased, the size increased, and the shape also changed from the granular form at the time of initial precipitation to a spindle-like form having sharp edges, which was disadvantageous in both mechanical properties and corrosion resistance of the duplex stainless steel. When the addition amount of Nb is too high, the tensile strength is reduced because the sharp NbMo phase splits the matrix, so that the surrounding stress is concentrated to form a crack source, and the tensile strength of the duplex stainless steel is reduced. In addition, the material with too high Nb addition has reduced corrosion resistance because the NbMo phase preferentially falls off during corrosion, leaving defects corresponding to the outline of the NbMo phase on the duplex stainless steel substrate, forming a corrosion source, and reducing the corrosion resistance of the material, and the comparison between before and after NbMo falls off before and after corrosion is shown in fig. 5 and 6, respectively. The Tafel curves of different Nb-containing duplex stainless steels are tested by taking a simulated oil field as a corrosion solution, and formed pitting pits are respectively shown in FIGS. 7 to 12, and as can be seen from FIGS. 7 to 12, the shapes of the pits in the materials are all round, the number of the pits in example 1 is less than that of the comparative example, the pitting resistance is better, the number of the pits in example 2 is equivalent to that of the comparative example, and the pitting resistance is not greatly different; the number of pits and the size of pits in examples 3 to 5 were larger than those in the comparative example, and the pitting resistance was inferior to that in the comparative example. Therefore, the microalloy element Nb reinforced duplex stainless steel should control the addition amount of Nb, and should avoid the precipitation of coarse or sharp-edged second phase while ensuring the precipitation of second phase particles so as to avoid reducing the mechanical property and the corrosion resistance.
The above description is only a preferred embodiment of the present invention, and all equivalent changes and modifications made in accordance with the claims of the present invention should be covered by the present invention.
Claims (6)
1. A microalloy element Nb reinforced duplex stainless steel is characterized in that: the duplex stainless steel comprises the following components in percentage by mass: c is less than or equal to 0.03 percent; si is less than or equal to 1.0 percent; mn is less than or equal to 2.0 percent; s is less than or equal to 0.02 percent; p is less than or equal to 0.03 percent; cr: 21% -23%; ni: 4.5% -6.5%; mo: 2.5% -3.5%; nb: 0.03% -0.05%; n: 0.08% -0.20%, and the balance of Fe and inevitable impurities.
2. A method of making a micro-alloyed element Nb reinforced duplex stainless steel according to claim 1, characterized in that: the method comprises the following steps:
(1) smelting in a medium-frequency induction furnace: all raw materials required by smelting need to be subjected to oil removal, degassing, rust removal and drying treatment before entering a furnace for smelting;
(2) firstly, adding cleaned and dried 316L stainless steel scraps into a crucible of a medium-frequency induction furnace for melting, and then sequentially adding ferromolybdenum, industrial pure iron, metal chromium, metal manganese, metal nickel and Nb iron; when the temperature of the stainless steel reaches 1600-1610 ℃, performing deoxidation treatment on the stainless steel solution; then deslagging the stainless steel solution, measuring the temperature of the stainless steel solution before pouring, and carrying out proper degassing and dewatering treatment on an investment mold shell used for pouring before pouring;
(3) and (3) air-cooling the prepared duplex stainless steel with different Nb contents to room temperature, and then carrying out water quenching after heat preservation.
3. The method of claim 2, wherein: the smelting materials in the step (1) and the mass fractions thereof are respectively as follows:
23-25% of 316L stainless steel leftover materials, 4.5-4.7% of ferromolybdenum with the molybdenum content of not less than 60%, 17.8-18.1% of metal chromium with the chromium content of not less than 99%, 0.04-0.31% of Nb iron with the Nb content of not less than 65%, 3.0-3.2% of metal nickel with the nickel content of not less than 99%, 0.5-0.7% of metal manganese with the manganese content of not less than 99%, and the balance furnace burden is industrial pure iron, wherein the sum of the mass percentages of the materials is 100%.
4. The method of claim 2, wherein: the addition amount of the deoxidizer silicon calcium manganese in the deoxidation treatment in the step (2) is 0.3 percent of the total smelting mass.
5. The method of claim 2, wherein: the temperature of the pouring in the step (2) is not higher than 1620 ℃.
6. The method of claim 2, wherein: and (3) specifically, the heat preservation in the step (3) is carried out at 1050 ℃ for 2 h.
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Application publication date: 20200410 |