CN104711493A - Nickel-saving rare-earth/barium-containing biphase stainless steel alloy material and preparation method thereof - Google Patents
Nickel-saving rare-earth/barium-containing biphase stainless steel alloy material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a nickel-saving rare-earth/barium-containing biphase stainless steel alloy material and a preparation method thereof. The alloy material is composed of the following components in percentage by mass: at most 0.025% of C, at most 0.005% of O, at most 0.006% of S, at most 2.00% of Si, at most 0.025% of P, 2.00-5.00% of Mn, 17.0-21.0% of Cr, 1.0-2.5% of Ni, 0.1-2.0% of W, 0.1-1.0% of Cu, 2.0-5.5% of Mo, 0.2-0.40% of N, 0.001-0.01% of B, 0.0005-0.01% of Ba, 0.01-0.2% of lanthanum-cerium mixed rare earth RE and the balance of Fe. The preparation method comprises the following steps: smelting, casting, cast ingot or casting blank cogging, hot rolling and solution treatment. The method has the advantages of nickel saving and low production cost, obviously enhances the mechanical strength, and improves the hot working properties, corrosion resistance and the like.
Description
Technical field
The invention belongs to duplex stainless steel technical field, particularly relate to a kind of nickel-saving type containing rare earth and barium diphase stainless steel alloy material and preparation method thereof.
Background technology
Duplex stainless steel is by ferritic phase and austenite phase composite, combines the advantage of single-phase ferrite and single phase austenite, has good mechanical property, good toughness and excellent corrosion resistance nature, is widely used in oil, chemical industry etc.And the use of domestic duplex stainless steel also has certain limitation at present, picture uses several large field such as such as pulp and paper industry, oil and gas industry, transport trade, even construction industry of duplex stainless steel abroad in a large number, and we relate to seldom, and what have also just just starts.
In the existing industry of China, some chemical enterprises are if phenol waste disposal plant is still using the expensive 316 type austenitic stainless steels that nickel content is higher, as austenitic stainless steels such as 0Cr18Ni12Mo2Ti and 316L.Production and the use of these alloys can consume a large amount of expensive nickel undoubtedly, not only can increase production cost, and run counter to the megatrend of " energy-saving and emission-reduction ", their application, will certainly be subject to strict restriction.
In these Chemical Manufacture corrosive environments, the alloy that nickel content is lower if select, price is relatively cheap, as modal austenitic stainless steel SUS304(Cr18Ni8) etc., be sometimes difficult to meet high temperature and corrode harsher working conditions.
The nickel resources of China is quite few, and the rare of nickel will seriously limit the development of China's stainless steel industry.And the rare earth resources of China is abundanter, in the long term, research and development can save valuable nickel resources containing the high-performance stainless steel alloy of rare earth, can ensure again the work-ing life under severe rugged environment and performance thereof simultaneously.Therefore, in order to meet the requirement of alloy under environment more severe condition, ensure or significantly improve work-ing life, again low-alloyed production cost can fall simultaneously, can substitute the austenite stainless steel grade that picture 0Cr18Ni12Mo2Ti and 316L type is nickelic, the research and development of the two-phase stainless steel containing rare earth of the nickel-saving type of good cost performance will more and more be subject to people's attention.
Summary of the invention
The object of the present invention is to provide a kind of nickel-saving type containing rare earth and barium diphase stainless steel alloy material and preparation method thereof, achieve that technique is simple, rare earth and the barium alloy rate of recovery is high, refining effect good.
For achieving the above object, the present invention can replace the action principle of nickel in steel according to nitrogen, can stablize the austenite in duplex stainless steel by appropriate cheap nitrogen, thus reduces the consumption of valuable nickel; In this double phase stainless steel alloy, add rare earth metal and Si-Ba alloy, under the prerequisite that oxygen in the alloy, sulphur content are lower, the oxide compound equal sphere forming dystectic re inclusion and barium is mingled with disperse in the base simultaneously; Rare earth and barium compound action, play combined microalloying effect, pinning crystal boundary, strengthening crystal boundary, purification crystal boundary, thus improve resistance to corrosion and the grain-boundary strength of crystal boundary, improves the high-temperature behavior of steel.
Based on above-mentioned mechanism, the present invention adopts following technical scheme:
A kind of nickel-saving type is containing rare earth and barium diphase stainless steel alloy material, and the composition of this alloy material and mass percent are: C≤0.025%, O≤0.005%, S≤0.006%, Si≤2.00%, P≤0.025%, Mn 2.00 ~ 5.00%, Cr 17.0 ~ 21.0%, Ni 1.0 ~ 2.5%, W 0.1 ~ 2.0%, Cu 0.1 ~ 1.0%, Mo 2.0 ~ 5.5%, N 0.2 ~ 0.40%, B 0.001 ~ 0.01%, Ba 0.0005 ~ 0.01%, mixed rare earth of lanthanum and cerium RE 0.01 ~ 0.2%, Fe surplus.
Above-mentioned nickel-saving type contains the preparation method of rare earth and barium diphase stainless steel alloy material, comprising: smelt, casting, ingot casting or strand cogging, hot rolling, solution treatment; Wherein:
(1) smelt: adopt any one technique in vacuum induction furnace, air induced melting, electric furnace+external refining, converter+external refining; Before tapping casting, add mixed rare earth of lanthanum and cerium RE and Si-Ba alloy, pouring temperature controls at 1500-1650 DEG C;
(2) ingot casting or ingot formation: Heating temperature 1100-1320 DEG C, during cogging, initial forging temperature controls at 1120-1300 DEG C, and final forging temperature controls at 980-1030 DEG C;
(3) hot rolling: carry out hot rolling, blank heating temperature 1150-1250 DEG C during hot rolling according to the steel specs of user's requirement after ingot casting or ingot formation, start rolling temperature controls at 1150-1200 DEG C, and finishing temperature control is at 980-1030 DEG C;
(4) solution treatment: carry out solution treatment after steel hot rolling in heat treatment furnace, temperature is 1050-1150 DEG C, and insulation 30-60 minute, the type of cooling adopts water-cooled or air cooling.
Adopt the present invention of technique scheme, compared with prior art, its beneficial effect is:
Not only optimize chemical composition and mass percent, and in the composition of steel, add appropriate rare earth and barium to go bad inclusion microalloying: the benefit that RE Modified sulfide inclusion brings is exactly can form dystectic spherical rare-earth at intracrystalline Arbitrary distribution to be mingled with, and the solidified structure of refinement steel, reduces segregation.
In addition, in the past about oxygen level all not mentioned in the patent of duplex stainless steel, and the upper range of sulphur content is all too high, cause after adding rare earth element, the form of cleaning molten steel and rotten inclusion and the effect of size are mainly played in the effect of rare earth in steel, mainly generate big and small re inclusion in steel, the rare earth be solid-solubilized in steel is almost micro-, so its Microalloying Effect played is very micro-.
And oxygen of the present invention and sulphur content require O≤0.005%, S≤0.006%, adopt aluminium final deoxygenation, make oxygen, sulphur content greatly be reduced to below 50ppm, add mishmetal and Si-Ba alloy on this basis in addition, oxygen and sulphur content will be lower, reach re-set target.So after the present invention adds rare earth element, in steel, impurity is few, rare earth Main Function is exactly Microalloying Effect, solid solution capacity increases greatly, because of features such as its activity are large, be mainly enriched in crystal boundary and intracrystalline, decrease the segregation of the impurity such as other S, P at crystal boundary, strengthening crystal boundary, improves intensity and the corrosion resistance nature of crystal boundary.
In addition, another feature of the present invention adds barium element, makes rare earth and barium compound action, play combined microalloying effect in steel.Ce(nucleidic mass 140.1), La(nucleidic mass 138.9) and Ba(nucleidic mass 137.3) atomic radius suitable, and their chemical property is active, all belong to active element, be solid-solubilized in after in steel, they can occupy the activity site on steel surface, Ce, La and Ba more effectively can occupy the null position in body-centered cubic (ferrite is body-centered cubic structure) by diffusion ratio Cr, Mo element, make the distribution of Cr, Mo element in two-phase evenly, improve the stability of rich Cr passive film, improve corrosion resistance nature; In addition, be solid-solubilized in Ce, La and Ba compound action in steel, be enriched in crystal boundary, decrease the segregation of impurity element at crystal boundary, improve grain-boundary strength, enhance crystal boundary, improve resistance to corrosion and the mechanical property of crystal boundary.The feature of this combined microalloying of Ce, La and Ba element is that the present invention is different from the maximum difference of prior art.
With nitrogen for nickel, suitably have adjusted the alloying elements such as Cr, Ni, Si, Mn, Mo, and with the addition of W, Cu element, improve intensity and the corrosion resistance nature of steel.
Alloy material new after tested has good corrosion resistance nature, at boiling temperature 5%(wt) H
2sO
4solidity to corrosion in the aqueous solution is obviously better than austenitic stainless steel 316 L, OCr
18ni
12mo
2ti steel and 2205 duplex stainless steels, wherein, 316L and OCr
18ni
12mo
2the erosion rate of Ti steel is all greater than 10g/m
2 .h, respectively 20 times and more than 12 times (as shown in Figure 5 list) higher than the present invention alloy, and the erosion rate of 2205 duplex stainless steels is also more than 3 times of this alloy.In room temperature phenol sewage, the erosion rate of alloy of the present invention is only respectively 316L and OCr
18ni
12mo
21/50 of Ti steel and 1/160.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
2 .h, and Austenitic stainless steel 1Cr
18ni
9ti etc. are very responsive to chlorion spot corrosion.Have above testing data known, the comprehensive corrosion resisting property of alloy of the present invention in different media is better than 316L and OCr
18ni
12mo
2the austenitic stainless steels such as Ti.
Well, non-scale when forging after 1150-1250 DEG C of long-time heating, 850-1300 DEG C of scope, has good ductility and plasticity for the thermotolerance of alloy of the present invention and hot workability, is all easy to forging rolling and is shaped.This alloy has excellent mechanical property.After vacuum induction furnace smelting, forging also solution treatment, its room-temperature mechanical property can reach: Rp0.2 680 MPa, Rm 910 MPa, A 58%, Z 81%, A
kv308J, A when-40 DEG C
kvits yield strength of 180J is about more than 2 times of 316L, compares OCr
18ni
12mo
2ti about improves 330 more than MPa, has good ductility, plasticity and impelling strength.
In addition, alloy of the present invention also have good to smelt, cold working and welding property, be suitable for manufacturing various section bar and the welding assemblys such as various foundry goods, forging and pipe, rod, line and plate.Its weldprocedure is identical with general stainless steel with equipment, and without preheating before welding under general temperature, postwelding does not need tempering.
Alloy of the present invention with nitrogen for nickel, so production cost is lower.By the cost keeping of steely iron alloy raw material, with the 100000 yuan of calculating per ton of nickel price, the comparable OCr of its steel production cost per ton
18ni
12mo
2ti reduces about 17%, reduces expenses about 1600 yuan.In addition, because alloy corrosion resistance of the present invention is better, if so replace 316L and OCr with it
18ni
12mo
2the Austenitic stainless steels such as Ti will cause the workpiece life-span to increase substantially, and the economic and social benefit brought thus will be more remarkable.
The great advantage of the vacuum induction furnace smelting technique in the present invention is before tapping, add mishmetal and Si-Ba alloy, decrease rare earth and Si-Ba alloy scaling loss, significantly improve the native rate of recovery of alloy, and effectively reach the combined microalloying effect of the pattern of rotten inclusion, size and rare earth and barium.
As preferably, the present invention further technical scheme is:
In described mixed rare earth of lanthanum and cerium RE, La≤51%, Ce≤42%, also containing praseodymium, neodymium, promethium, samarium rare earth element one or more, rare earth Han Liang≤99.7%.
During air induced melting, adjust suitable protection slag blanket, to prevent secondary oxidation, join nitrogen and adopt interpolation nitrided ferro-chromium alloy and/or nitrogen blowing.
When casting smelted by vacuum oven, at the high pure nitrogen of the indoor charged pressure 0.03-0.13MPa of casting, coordinate and add nitrided ferro-chromium alloy.
Accompanying drawing explanation
Fig. 1 is chemical composition (wt%) list of alloy described in the embodiment of the present invention and contrast grade of steel;
Fig. 2 is the room-temperature mechanical property list of alloy described in the embodiment of the present invention and contrast grade of steel;
Fig. 3 is the high temperature tensile properties list of alloy described in the embodiment of the present invention and contrast grade of steel;
Fig. 4 is that the alloy described in the embodiment of the present invention continues with the high temperature tensile properties list of contrast grade of steel;
Fig. 5 is alloy described in the embodiment of the present invention and contrast grade of steel at boiling temperature 5%(wt.%) H
2sO
4uniform corrosion capabilities list in the aqueous solution;
Fig. 6 is the high-temp plastic test-results schematic diagram of the embodiment of the present invention and comparative example.
Embodiment
Below in conjunction with embodiment, the present invention is further elaborated, but these embodiments do not form any restriction to the present invention.
Chemical composition ranges set by the present invention, 5 stove steel have been smelted in vacuum induction furnace, aluminium final deoxygenation is used before tapping, tap and add mixed rare earth of lanthanum and cerium RE(mixed rare earth of lanthanum and cerium in first 2 minutes, La≤51%, Ce≤42%, also containing praseodymium, neodymium, promethium, samarium rare earth element one or more, rare earth Han Liang≤99.7%) and Si-Ba alloy, then steel tapping casting becomes ingot; Steel ingot is forged into the slab of 20 × 50 × 200mm, forging temperature 980-1300 DEG C; The final chemical composition of 5 stove steel is as shown in Fig. 1 list.
The alloy forging mechanical property sample of state, corrosion test sample and industrialness lacing film are all direct from laterally sampling the slab of forging state, test performance after the solution treatment of 1080 DEG C × 40min water-cooled.For ease of contrast, also in vacuum induction furnace, 2205 duplex stainless steels, 316L and OCr have been smelted simultaneously
18ni
12mo
2ti austenitic stainless steel; Simultaneous test is all carried out under the conditions such as identical smelting, forging, thermal treatment and corrosion test.
The chemical composition of alloy described in above-described embodiment and each compared steel, mechanical property, corrosion resistance nature and high-temp plastic experimental data are shown in list shown in Fig. 1 to Fig. 5 and Fig. 6.
The foregoing is only the better feasible embodiment of the present invention, not thereby limit to interest field of the present invention, the equivalence change that all utilizations description of the present invention is done, be all contained within interest field of the present invention.
Claims (5)
1. nickel-saving type is containing rare earth and a barium diphase stainless steel alloy material, and it is characterized in that, the composition of this alloy material and mass percent are: C≤0.025%, O≤0.005%, S≤0.006%, Si≤2.00%, P≤0.025%, Mn 2.00 ~ 5.00%, Cr 17.0 ~ 21.0%, Ni 1.0 ~ 2.5%, W 0.1 ~ 2.0%, Cu 0.1 ~ 1.0%, Mo 2.0 ~ 5.5%, N 0.2 ~ 0.40%, B 0.001 ~ 0.01%, Ba 0.0005 ~ 0.01%, mixed rare earth of lanthanum and cerium RE 0.01 ~ 0.2%, Fe surplus.
2. nickel-saving type according to claim 1 is containing rare earth and barium diphase stainless steel alloy material, it is characterized in that, in described mixed rare earth of lanthanum and cerium RE, La≤51%, Ce≤42%, also containing praseodymium, neodymium, promethium, samarium rare earth element one or more, rare earth Han Liang≤99.7%.
3. nickel-saving type as claimed in claim 1 contains a preparation method for rare earth and barium diphase stainless steel alloy material, comprising: smelt, casting, ingot casting or strand cogging, hot rolling, solution treatment; It is characterized in that:
(1) smelt: adopt any one technique in vacuum induction furnace, air induced melting, electric furnace+external refining, converter+external refining; Before tapping casting, add mixed rare earth of lanthanum and cerium RE and Si-Ba alloy, pouring temperature controls at 1500-1650 DEG C;
(2) ingot casting or ingot formation: Heating temperature 1100-1320 DEG C, during cogging, initial forging temperature controls at 1120-1300 DEG C, and final forging temperature controls at 980-1030 DEG C;
(3) hot rolling: carry out hot rolling, blank heating temperature 1150-1250 DEG C during hot rolling according to the steel specs of user's requirement after ingot casting or ingot formation, start rolling temperature controls at 1150-1200 DEG C, and finishing temperature control is at 980-1030 DEG C;
(4) solution treatment: carry out solution treatment after steel hot rolling in heat treatment furnace, temperature is 1050-1150 DEG C, and insulation 30-60 minute, the type of cooling adopts water-cooled or air cooling.
4. nickel-saving type according to claim 3 contains the preparation method of rare earth and barium diphase stainless steel alloy material; it is characterized in that, during air induced melting, adjust suitable protection slag blanket; to prevent secondary oxidation, join nitrogen and adopt interpolation nitrided ferro-chromium alloy and/or nitrogen blowing.
5. nickel-saving type according to claim 3 contains the preparation method of rare earth and barium diphase stainless steel alloy material, it is characterized in that, when casting smelted by vacuum oven, at the high pure nitrogen of the indoor charged pressure 0.03-0.13MPa of casting, coordinates interpolation nitrided ferro-chromium alloy.
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| CN107541662A (en) * | 2017-09-29 | 2018-01-05 | 江苏理工学院 | A kind of corrosion resistant ferritic stainless steel alloy material and preparation method thereof |
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| CN107904522A (en) * | 2017-10-18 | 2018-04-13 | 江苏理工学院 | A kind of double phase stainless steel alloy of high intensity and preparation method thereof |
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| CN109972060A (en) * | 2019-05-07 | 2019-07-05 | 四川维珍高新材料有限公司 | A kind of low nickel high strength dual phase stainless steel material and preparation method thereof |
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