CN101935809B - High performance rare-earth duplex stainless steel alloy material and preparation method thereof - Google Patents
High performance rare-earth duplex stainless steel alloy material and preparation method thereof Download PDFInfo
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- CN101935809B CN101935809B CN2010102795096A CN201010279509A CN101935809B CN 101935809 B CN101935809 B CN 101935809B CN 2010102795096 A CN2010102795096 A CN 2010102795096A CN 201010279509 A CN201010279509 A CN 201010279509A CN 101935809 B CN101935809 B CN 101935809B
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Abstract
The invention relates to a high performance rare-earth duplex stainless steel alloy material and a preparation method thereof, belonging to the technical field of duplex stainless steels. The high performance rare-earth duplex stainless steel alloy material comprises the following components in percentages by mass: not more than 0.04 percent of C, not more than 0.020 percent of S, not more than 2.00 percent of Si, not more than 0.030 percent of P, 1.00-2.00 percent of Mn, 18.00-24.00 percent of Cr, 3.0-6.0 percent of Ni, 1.0-3.5 percent of Mo, 0.10-0.40 percent of N, 0.001-0.01 percent of B0.01-0.25 percent of mischmetal and the balance of Fe. The process comprises the following steps of smelting and casting, ingot casting or casting blank cogging, steel rolling and solution treatment. Before steel tapping, a rare earth metal is added, the molten steel casting temperature is controlled at 1,500-1,650 DEG C, the cogging starting forging temperature is controlled at 1,100-1,250 DEG C, and the final forging temperature is not less than 950 DEG C; in rolling, the rolling temperature is controlled at 1,150-1,200 DEG C and the final rolling temperature is not less than 950 DEG C; and the solution treatment temperature is 1,020-1,150 DEG C and heat is preserved for 30-60 min. The invention has the advantages of remarkably enhancing mechanical strength, improving corrosion performances, such as hot processing, high temperature resistance and hydrochloric acid resistance, and the like and having low preparation cost and high rare-earth recovery rate.
Description
Technical field
The invention belongs to the duplex stainless steel technical field, particularly relate to a kind of high-performance rare-earth diphase stainless steel alloy material and preparation method thereof.
Background technology
The duplex stainless steel of China just is in the developmental level of external s-generation duplex stainless steel at present, and the nitrogen content in the steel is below 0.2%.Nitrogenous at 0.25～0.35% super-duplex stainless steel as for what entered into the market at present abroad, China still is in the development in laboratory stage.And the use of domestic duplex stainless steel also be have necessarily circumscribed; Picture is external a large amount of use duplex stainless steels we relate to seldom such as several big fields such as pulp and paper industry, oil and gas industry, transport trade even construction industries, what have also just just begins.These fields have the excellent corrosion resisting performance except requiring steel with steel, also require to have higher intensity and toughness simultaneously, can play a key effect for the raising rare earth of over-all properties.
Recently the growth of world's stainless steel output has caused sharp rising of nickel valency.The rare development that will seriously limit China's stainless steel industry of nickel, chromium resource.And the rare earth resources rich of China, in the long term, the nickel resources that research and development rare earth duplex stainless steel can saves valuable, therefore developing the rare earth duplex stainless steel also is the selection that meets China's actual conditions.
Summary of the invention
The object of the present invention is to provide a kind of high-performance rare-earth diphase stainless steel alloy material and preparation method thereof, realized that technology is simple, rare earth yield is high, refining effect is good.
For achieving the above object, mechanism of the present invention is following: can replace the action principle of nickel in steel according to nitrogen, great deal of experimental is found, can be stablized the austenite in the duplex stainless steel with proper amount of cheap nitrogen, thereby reduce the consumption of valuable nickel; In this double phase stainless steel alloy, add an amount of rare earth simultaneously; Sulphur content in the alloy reduces greatly; Form the disperse of dystectic spherical rare-earth sulfide in matrix, avoided low-melting sulfide to be present on the phase boundary, purified crystal boundary; Thereby improved the resistance to corrosion of crystal boundary, improved the high temperature thermoplasticity of steel.
According to above-mentioned mechanism, the present invention adopts following technical scheme:
A kind of high-performance rare-earth diphase stainless steel alloy material, the composition of this alloy material and mass percent are: C≤0.045%, S≤0.020%, Si≤2.00%; P≤0.030%, Mn 1.00～2.00%,, Cr 18.00～24.00%; Ni3.0～6.0%, Mo 1.0～3.5%, and N 0.10～0.40%; B 0.001～0.01%, is main mishmetal with the cerium: 0.01～0.25%, and the Fe surplus.
Mishmetal of the present invention is main to be meant Ce >=45% with Ce, contains one or more of lanthanum, praseodymium, neodymium, promethium, samarium REE, content of rare earth＞99.5%.
Alloy material of the present invention also contains at least a among W, the Cu by percentage to the quality, and its content is 0.1～1.0% W, 0.1～1.0% Cu.
High-performance of the present invention contains the preparation method of the diphase stainless steel alloy material of rare earth, comprises following process step: smelting, casting, ingot casting or strand cogging, hot rolling and solution treatment.
(1) smelt: any technology is smelted in vacuum induction furnace, non-vacuum induction furnace, electric furnace+external refining, converter+external refining.
Requirement adds rare earth metal before the tapping casting.Pouring temperature is controlled at 1500-1650 ℃.
Need adjust suitable protection slag blanket during antivacuum smelting,, join nitrogen and adopt and add nitrided ferro-chromium alloy and/or nitrogen blowing to prevent secondary oxidation; When smelting casting, vacuum oven must cooperate and add the nitrided ferro-chromium alloy at the indoor high pure nitrogen (0.01-0.13MPa) that charges into certain pressure of casting.
The present invention is adapted to produce greatly electric furnace+external refining+continuous casting, converter+external refining+continuous casting, can adopt the continuous casting process of existing 2205 duplex stainless steels during as if the employing continuous casting.
(2) ingot casting or ingot casting cogging: ingot casting or strand can adopt hammer cogging or continuous casting and rolling, 1150-1260 ℃ of heating Wen Weidu, and initial forging temperature is controlled at 1100-1250 ℃ during cogging, final forging temperature 950-1000 ℃.
(3) hot rolling: the steel specification according to customer requirements after ingot casting or the ingot casting cogging is carried out hot rolling.During hot rolling blank heating temperature 1150-1250 ℃, start rolling temperature is controlled at 1150-1200 ℃, finishing temperature 950-1000 ℃.
(4) solution treatment: in heat treatment furnace, carry out solution treatment after the steel hot rolling, temperature is 1020-1150 ℃, is incubated 30-60 minute.The type of cooling adopts water-cooled or air cooling.Contain the rare earth duplex stainless steel through obtaining high-performance of the present invention after the solution treatment.
Compared with prior art; The technical scheme that the present invention adopted; Be in the smelting process of improving superhigh strength stainless steel, to handle molten steel, reach the purpose of desulfurization, rotten inclusion and microalloying, thereby improve the mechanical property and the corrosion resistance nature of steel with rare earth metal.This technology has not only been optimized chemical composition and mass percent; And in the composition of steel, add rotten inclusion of an amount of rare earth and microalloying: the benefit that the rotten sulfide inclusion of rare earth brings is exactly can form dystectic spherical rare-earth that distributes arbitrarily at intracrystalline to be mingled with; The sulfide that replacement distributes along crystal boundary; And the solidified structure of refinement steel reduces segregation; In addition, the microalloying effect of rare earth makes the rare earth be solid-solubilized in the steel be enriched in crystal boundary through flooding mechanism, has reduced impurity element in the gathering partially of crystal boundary, has improved grain-boundary strength, has improved the resistance to corrosion and the mechanical property of crystal boundary.This technology while, has suitably been adjusted alloying elements such as Cr, Ni, Si, Mn, Mo, and has added W, Cu element for nickel with nitrogen, has improved the intensity and the corrosion resistance nature of steel.Improved 120MPa, ballistic work A through the new alloy material tensile strength of test
KvImproved about 25J, improved the hot workability and the salt tolerant acid corrosion performance of steel, and production cost has been low, smelted simple.Test-results shows that this alloy has excellent corrosion resisting performance, and rare earth makes the erosion rate of this alloy in room temperature 5% (wt) the HCl aqueous solution that the 1.106g/m when not adding rare earth arranged
2H reduces to 0.064g/m
2H is at boiling temperature 5% (wt) H
2SO
4Solidity to corrosion in the aqueous solution obviously is superior to austenitic stainless steel 316L and OCr
18Ni
12Mo
2The Ti steel, wherein, 316L and OCr
18Ni
12Mo
2The erosion rate of Ti steel is all greater than 10g/m
2H (sees table 4) than the present invention alloy is high more than 12 times and 10 times respectively.In room temperature phenol sewage, the erosion rate of alloy of the present invention only is respectively 316L and OCr
18Ni
12Mo
21/40 and 1/150 of Ti steel.Alloy of the present invention is at 3～75%NH
4Insensitive to chloride ion corrosion in Cl+0.5～1.5%NaCl boiled water solution, its erosion rate is less than 0.1g/m
2H, and Austenitic stainless steel 1Cr
18Ni
9Ti etc. are very responsive to the cl ions spot corrosion.Have above testing data to know, the comprehensive corrosion resisting property of alloy of the present invention in different media is superior to former technological duplex stainless steel, more is superior to 316L and OCr
18Ni
12Mo
2Austenitic stainless steels such as Ti.
The thermotolerance and the hot workability of alloy of the present invention are good, and non-scale when after 1150～1250 ℃ of long-time heating, forging 850～1300 ℃ of scopes, has good ductility and plasticity, all are easy to forging rolling and are shaped.This alloy has excellent mechanical property.After vacuum induction furnace smelting, forging and solution treatment, its room-temperature mechanical property can reach: σ
s～650MPa, σ
b～850MPa, δ
5～55%, ψ～75%, A
Kv～275J, HRB～99.0, A in the time of-40 ℃
Kv～160J.Its ys is about more than 2 times of 316L, compares OCr
18Ni
12Mo
2Ti improves more than the 300MPa approximately, has good ductility, plasticity and impelling strength.
In addition, alloy of the present invention also have good smelt, cold working and welding property, be suitable for making various section bars and welding assemblys such as various foundry goods, forging and pipe, rod, line and plate.Its weldprocedure and equipment are identical with general stainless steel, and before general temperature welds down without preheating, postwelding does not need tempering.
Alloy of the present invention with nitrogen for nickel, so production cost is lower.Press the cost keeping of steely iron alloy raw material, with the 150000 yuan of calculating per ton of nickel price, the comparable OCr of its casting production cost per ton
18Ni1
2Mo
2Ti reduces about 16%, reduces expenses about 2500 yuan.In addition, because alloy corrosion resistance of the present invention is better, so if replace 316L and OCr with it
18Ni
12Mo
2Austenitic stainless steels such as Ti will cause the workpiece life-span to increase substantially, and the economic and social benefit that brings thus will be more remarkable.
The great advantage of the vacuum induction furnace smelting technology among the present invention is before tapping, to add rare earth rapidly, has reduced the rare earth scaling loss, has significantly improved rare earth yield, and has reached the purpose that desulfurization, degasification and removal are mingled with effectively.
Embodiment
The chemical ingredients scope that sets according to the present invention has been smelted 5 stove steel in vacuum induction furnace, its concrete composition is seen table 1.Tapping added mishmetal (is main with Ce, Ce >=45%, other contains REEs such as lanthanum, praseodymium, neodymium, promethium, samarium, content of rare earth＞99.5%) in preceding 2 minutes, and steel tapping casting becomes ingot then.Steel ingot forges into the slab of 20 * 50 * 200mm, 950～1250 ℃ of forging temperatures.Alloy of the present invention is forged mechanical property sample, the corrosion test of attitude and all directly from the slab of forging attitude, is laterally taken a sample test performance after the solution treatment of 1050 ℃ * 1h water-cooled with sample and industrialness lacing film.For ease of contrast, 316L and OCr also in vacuum induction furnace, have been smelted simultaneously
18Ni
12Mo
2Two kinds of austenitic stainless steels of Ti.Simultaneous test is all carried out under conditions such as identical smelting, forging, thermal treatment and corrosion test.Chemical ingredients, mechanical property and the corrosion resistance nature data of alloy of the present invention and each compared steel are listed in table 1～4 respectively.
The chemical ingredients (wt%) of table 1 alloy of the present invention and contrast grade of steel
The room-temperature mechanical property of table 2 alloy of the present invention and contrast grade of steel
The mechanical behavior under high temperature of table 3 alloy of the present invention and contrast grade of steel
Table 4 alloy of the present invention and contrast grade of steel are at boiling temperature 5% (wt.%) H
2SO
4Uniform corrosion performance in the aqueous solution
Claims (1)
1. a high-performance rare-earth diphase stainless steel alloy material is characterized in that, the composition of this alloy material and mass percent are:
C 0.030%, and S 0.0030%, and Si 1.30%, and P 0.013%, and Mn 1.35%, and Cr 21.85%, and Ni 4.58%, and Mo 3.03%, and Cu 0.55%, and N 0.17%, and B 0.0015%, is main mishmetal 0.018% with Ce, the Fe surplus;
Perhaps, C 0.025%, and S 0.0040%, and Si 1.10%, and P 0.025%, and Mn 1.30%, and Cr 23.10%, and Ni 4.33%, and Mo 3.10%, and Cu 0.44%, and N 0.20%, and B 0.0018%, is main mishmetal 0.019% with Ce, the Fe surplus;
Perhaps, C 0.045%, and S 0.0045%, and Si 1.07%, and P 0.015%, and Mn 1.22%, and Cr 22.60%, and Ni 4.44%, and Mo 2.90%, and Cu 0.48%, and N 0.28%, and B 0.0030%, is main mishmetal 0.030% with Ce, the Fe surplus;
Perhaps, C 0.043%, and S 0.0035%, and Si 1.13%, and P 0.010%, and Mn 1.25%, and Cr 23.05%, and Ni 4.60%, and Mo 2.83%, and Cu 0.27%, and N 0.25%, and B 0.0025%, is main mishmetal 0.042% with Ce, the Fe surplus;
Perhaps, C 0.040%, and S 0.0042%, and Si 1.25%, and P 0.012%, and Mn 1.18%, and Cr 21.72%, and Ni 4.45%, and Mo 3.07%, and Cu 0.32%, and N 0.35%, and B 0.0020%, is main mishmetal 0.050% with Ce, the Fe surplus;
Described mishmetal is main to be meant Ce >=45% with Ce, contains one or more of lanthanum, praseodymium, neodymium, promethium, samarium REE, content of rare earth＞99.5%.
Priority Applications (1)
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| CN2010102795096A CN101935809B (en) | 2010-09-10 | 2010-09-10 | High performance rare-earth duplex stainless steel alloy material and preparation method thereof |
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| CN2010102795096A CN101935809B (en) | 2010-09-10 | 2010-09-10 | High performance rare-earth duplex stainless steel alloy material and preparation method thereof |
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| CN101935809A CN101935809A (en) | 2011-01-05 |
| CN101935809B true CN101935809B (en) | 2012-09-05 |
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