CN105420472A - Grain boundary engineering technique for improving corrosion resistance of 316Lmod stainless steel - Google Patents
Grain boundary engineering technique for improving corrosion resistance of 316Lmod stainless steel Download PDFInfo
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- CN105420472A CN105420472A CN201510764303.5A CN201510764303A CN105420472A CN 105420472 A CN105420472 A CN 105420472A CN 201510764303 A CN201510764303 A CN 201510764303A CN 105420472 A CN105420472 A CN 105420472A
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- 316lmod
- stainless steel
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- grain boundary
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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
- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/005—Modifying the physical properties by deformation combined with, or followed by, heat treatment of ferrous alloys
Abstract
The invention discloses a grain boundary engineering technique for improving the corrosion resistance of 316Lmod stainless steel. The grain boundary engineering technique for improving the corrosion resistance of the 316Lmod stainless steel comprises the steps that heat preservation is conducted on the 316Lmod stainless steel at the temperature of 1050-1150 DEG C for 5-60 min; machining deformation with the deformation quantity being 3%-15% is conducted at the indoor temperature after water cooling; then annealing is conducted at the temperature of 1020-1150 DEG C for 3-12 min; and finally, the 316Lmod stainless steel with high corrosion resistance can be obtained after water cooling. According to the grain boundary engineering technique for improving the corrosion resistance of the 316Lmod stainless steel, the low sigma CSL grain boundary of the 316Lmod stainless steel can be improved remarkably; the components of materials do not need to be changed, and compared with an existing similar technique, long-time annealing is not needed, repeated machining and repeated annealing are not needed either, the technique is simpler, and operation is easy; the technique can also be referred and used for other several low-stacking fault energy face-centered cubic metal materials, cost control in industrial production is facilitated, popularization is easy, and extremely remarkable economic benefits are achieved.
Description
Technical field
The present invention relates to the erosion-resisting processing method of a kind of raising alloy material, particularly relate to a kind of bounding engineering processing method of stainless material, be applied to deformation and the technical field of heat treatment technology of metallic substance.
Background technology
316Lmod stainless steel is a kind of urea class stainless steel being exclusively used in manufacture urea production equipment, it is the stainless modified form of 316L, chemical composition reduces C element content, adds the constituent contents such as Ni, Cr, Mo, object is to obtain corrosion resisting property more better than 316L stainless steel.In urea production medium and salpeter solution medium, it is that the impurity element such as phosphorus, silicon in material is at Grain Boundary Segregation that 316Lmod stainless steel produces the major cause of intergranular corrosion, crystal boundary and intracrystalline is caused to corrode the potential difference in electrolyte solution, and 316L stainless steel to produce the major cause of intergranular corrosion be C content in material is almost 2 times of the content in 316Lmod stainless steel, on crystal boundary, easily separate out the carbide of rich Cr after sensitized treatment, thus produce Cr-depleted region near crystal boundary.The high temperature such as urea first ammonium liquid, high pressure and working under having the environment of strong corrosion medium is in due to urea production equipment, equipment 316Lmod stainless steel used can be subject to very serious corrosion, and therefore etching problem becomes the problem of overriding concern in the design of 316Lmod stainless steel, manufacturing processed.How to improve from the microstructure changing 316Lmod stainless steel self concern that its intergranular corrosion resistance performance is subject to people always.
Watanabe proposed the concept of grain boundary design and control (grainboundarydesign) in 1984.Adopt suitable technique can increase the ratio of polycrystalline material coincidence site lattice (CSL, coincidencesitelattice) crystal boundary, improve the toughness and tenacity of material.There is by increasing considerably " the low ∑ of low ∑ CSL(of special construction refers to ∑≤29) " crystal boundary ratio, optimizing Grain Boundary Character distribution (GBCD, grainboundarycharacterdistribution) performance that material is relevant with crystal boundary is improved, as anti intercrystalline corrosion performance, creep-resistant property, stress-corrosion-cracking resistance etc.This viewpoint develops into bounding engineering (GBE, grainboundaryengineering) research field the nineties in last century.The research of current bounding engineering mainly concentrates on the Face-centred Cubic Metals material of low stacking fault energy, and the formation based on annealing twin improves the low Σ CSL crystal boundary ratio of this kind of material.That has reported at present mainly contains two kinds of operational paths:
1. by after 3% ~ 8% distortion, long-time (10 ~ 100h) annealing at the temperature a little less than material re-crystallizes temperature;
2. by after the distortion of 15% ~ 40%, short period of time (3 ~ 60min) annealing at the temperature higher than material re-crystallizes temperature, and repeat such technique 3 ~ 7 times.
These two kinds of techniques can significantly improve the low Σ CSL crystal boundary ratio of material, thus significantly improve the material multiple performance relevant to crystal boundary.The people such as Michiuchi utilize the first technique to impose the prestrain of 3% to 316 stainless steels, then anneal at 967 DEG C of insulation 72h, make low Σ CSL crystal boundary ratio bring up to 80%.The people such as Palumbo use the second technique to make the low Σ CSL crystal boundary ratio of Inconel600 alloy bring up to 60 ~ 70%, and erosion rate reduces by 30 ~ 60%.The advantage of these two kinds of processing methodes to change material composition, only need adjust cold deformation and heat treatment mode, just significantly can improve the low Σ CSL crystal boundary ratio of material, improve the multiple performance that material is relevant to crystal boundary.But the first technique needs long term annealing, the second technique needs cold working repeatedly and annealing, and these two kinds of techniques are all unfavorable for the cost control in industrial production.
Summary of the invention
In order to solve prior art problem, the object of the invention is to the deficiency overcoming prior art existence, a kind of bounding engineering processing method improving 316Lmod stainless steel intergranular corrosion resistance performance is provided, the stainless low Σ CSL crystal boundary ratio of 316Lmod can be significantly improved, present invention process method does not only need the composition changing material, and compared with existing similar technique, neither need long term annealing, reprocessabilty and annealing is not needed yet, technique is simpler, processing ease, also can consult and use in the Face-centred Cubic Metals material of some other low stacking fault energy, be conducive to the cost control in industrial production, easy popularization, there is fairly obvious economic benefit.
Creating object for reaching foregoing invention, adopting following technical proposals:
Improve a bounding engineering processing method for 316Lmod stainless steel corrosion resistance nature, comprise the steps:
A. 316Lmod stainless steel is incubated 5 ~ 60min, then water-cooled at 1050 ~ 1150 DEG C;
B. at room temperature carry out machining deformation again to the 316Lmod stainless steel in described step a after Overheating Treatment, controlling distortion amount is 3 ~ 15%;
C. then the 316Lmod stainless steel through deformation processing in described step b is annealed again, at 1020 ~ 1150 DEG C, be incubated 3 ~ 120min, then water-cooled during annealing, obtain the 316Lmod stainless steel with high-corrosion resistance.
The present invention compared with prior art, has following apparent outstanding substantive distinguishing features and remarkable advantage:
1. present invention process method is applied to last procedure in 316Lmod stainless steel process of manufacture, the intergranular corrosion resistance performance of material is improved be can be implemented in the prerequisite not changing alloying constituent by this technique under, the performance relevant to crystal boundary to other, as creep resistance, anti-fatigue performance are also improved;
2. present invention process method is before stainless material carries out processing deformation process, first carry out solution heat treatment, ensure there is not deformation energy storage in material, then under the state not having deformation energy storage at material, carry out in room temperature the machining deformation that deflection is 3 ~ 15%, deflection will accurately control in such scope, anneals after machining deformation, 1020 ~ 1150 DEG C of insulations, the annealing after this small deformation amount can significantly improve the Σ 3 in material
ncrystal boundary (n=1,2,3 ...) ratio, thus improve the low Σ CSL crystal boundary ratio of all materials;
3. present invention process method neither needs long annealing, does not also need cold deformation repeatedly and annealing;
4. the present invention is to 316Lmod stainless steel under the state not having deformation energy storage, carries out the processing of small deformation amount, then carries out annealing between high temperature, short time, and technique is more simple, and processing ease, has fairly obvious economic benefit.
Accompanying drawing explanation
Fig. 1 is the stainless low Σ CSL crystal boundary scale map contrast of the 316Lmod before and after preferred embodiment of the present invention art breading.
Fig. 2 is that the graph of a relation that the 316Lmod stainless steel before and after preferred embodiment of the present invention art breading obtains material surface unit surface corrosion weight loss amount and etching time by corrosion experiment contrasts.
Fig. 3 is that the 316Lmod stainless steel before and after preferred embodiment of the present invention art breading adds up through five cycles the shape appearance figure contrast that 240h corrodes rear surface again after sensitization, wherein scheming a is the pattern photo of the 316Lmod stainless steel surface after preferred embodiment of the present invention art breading, figure b be without preferred embodiment of the present invention art breading after the pattern photo of 316Lmod stainless steel surface.
Embodiment
Details are as follows for the preferred embodiments of the present invention:
In the present embodiment, adopt the modified form 316L stainless steel being exclusively used in the urea class stainless steel manufacturing urea production equipment, namely implement the bounding engineering technique of corrosion resistance nature with 316Lmod stainless steel.A kind of bounding engineering processing method improving 316Lmod stainless steel corrosion resistance nature of the present embodiment, comprises the steps:
A. 316Lmod stainless steel materials is incubated 30min at 1100 DEG C, then water-cooled;
B. at room temperature carry out machining deformation again to the 316Lmod stainless steel in described step a after Overheating Treatment, controlling distortion amount is 5%;
C. then the 316Lmod stainless steel through deformation processing in described step b is annealed again, at 1075 DEG C, be incubated 30min during annealing, then water-cooled, obtain the 316Lmod stainless steel with high-corrosion resistance.
experimental test and analysis:
Adopt the 316Lmod stainless steel after the present embodiment art breading as sample A, adopt the 316Lmod stainless steel after without the present embodiment art breading as sample B.
Adopt EBSD(electronbackscatterdiffraction, Electron Back-Scattered Diffraction) method working sample A and B, low Σ CSL crystal boundary all presses Palumbo-Aust canonical statistics.Measure through EBSD method, the low Σ CSL crystal boundary ratio in sample A is 72.4%, and the low Σ CSL crystal boundary ratio in sample B is 47.9%, see Fig. 1.Fig. 1 is the low Σ CSL crystal boundary scale map of sample A and B.The present embodiment, for 316Lmod stainless steel, determines deformation and annealing process, and obtain low Σ CSL(coincidencesitelattice, low ∑ refers to ∑≤29) crystal boundary ratio is higher than 72.4%(Palumbo-Aust standard) material.Through the material of traditional technology processing, its low Σ CSL crystal boundary ratio is 47.9%.Compared with the material that the material that low Σ CSL crystal boundary ratio is high is low with low Σ CSL crystal boundary ratio, there is higher corrosion resistance nature.
By sample A and sample B air cooling after 650 DEG C of insulation 12h, as sensitized treatment, for the preparation of the testing sample of intergranular corrosion test.Intergranular corrosion test carries out Xiu Shi experiment according to ASTMA262-2010C method, and the volume fraction adopting boiling is 65%HNO
3as etchant solution, test according to 48h × 5 cycle.After polishing is carried out to testing sample surface, surface measurements area, and weigh.Be immersed in etchant solution by sample after having weighed, in experiment, nitric acid keeps micro-boiling state.Each cycle is 48h, and each cycle, by brushing off the oxide compound on surface after sample taking-up in flowing water with soft brush, then soaks 10min in alcohol, dries, then weigh after taking-up with hair dryer, obtains the corrosion weight loss situation through all after dates of current corrosion experiment.5 cycles have been carried out in such immersion corrosion experiment altogether, carry out altogether the corrosion experiment of 240h.Sample surfaces scanning electron microscopic observation after corrosion, see Fig. 2.The relation of Fig. 2 unit surface corrosion weight loss amount that to be 316Lmod stainless steel sample A and B containing different low Σ CSL crystal boundary ratio obtain through intergranular corrosion test after 12 hours 650 DEG C of sensitizations and etching time, as can be seen from Figure, low Σ CSL crystal boundary ratio be 47.9% sample B corrosion weight loss amount obviously than low Σ CSL crystal boundary ratio be 72.4% sample A large.
The major cause that metallic substance produces intergranular corrosion weightlessness causes crystal grain to come off after material surface grain boundary corrosion, as shown in Figure 3, through the corrosion in 5 cycles, obtains the pattern photo of 316Lmod stainless steel surface.Wherein scheming a is the pattern photo of the 316Lmod stainless steel surface after preferred embodiment of the present invention art breading, figure b be without preferred embodiment of the present invention art breading after the pattern photo of 316Lmod stainless steel surface.As can be seen from Fig. 3, sample A surface crystal boundary is obviously etched, and have a small amount of crystal grain to come off, and the crystal grain on sample B surface comes off in a large number, and internal layer crystal grain also drops many.This illustrates that low Σ CSL crystal boundary ratio has very large impact to corrosion among crystalline grains, the sample more intergranular corrosion resistance that the sample that low Σ CSL crystal boundary ratio is high is obviously low than low Σ CSL crystal boundary ratio.
The present embodiment processing method does not only need the composition changing material, and compared with existing similar technique, neither needs long term annealing, does not need reprocessabilty and annealing yet, and technique is more simple, and processing ease, has fairly obvious economic benefit.
By reference to the accompanying drawings the embodiment of the present invention is illustrated above; but the invention is not restricted to above-described embodiment; content according to the present invention can also make multiple change; change, the modification made under all spirit according to technical solution of the present invention and principle, substitute, combination or simplify; all should be the substitute mode of equivalence; as long as goal of the invention according to the invention; only otherwise deviate from know-why and the inventive concept that the present invention improves the bounding engineering processing method of 316Lmod stainless steel corrosion resistance nature, all protection scope of the present invention is belonged to.
Claims (1)
1. improve a bounding engineering processing method for 316Lmod stainless steel corrosion resistance nature, it is characterized in that, comprise the steps:
A. 316Lmod stainless steel is incubated 5 ~ 60min, then water-cooled at 1050 ~ 1150 DEG C;
B. at room temperature carry out machining deformation again to the 316Lmod stainless steel in described step a after Overheating Treatment, controlling distortion amount is 3 ~ 15%;
C. then the 316Lmod stainless steel through deformation processing in described step b is annealed again, at 1020 ~ 1150 DEG C, be incubated 3 ~ 120min, then water-cooled during annealing, obtain the 316Lmod stainless steel with high-corrosion resistance.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105842308A (en) * | 2016-03-25 | 2016-08-10 | 华南理工大学 | Method for eliminating super 304H steel inter-granular corrosion sensitivity |
| CN106868280A (en) * | 2017-01-13 | 2017-06-20 | 南京理工大学 | The preparation method of the Fe Ni Cr based austenite alloys of low intercrystalline corrosion tendency |
| CN108193036A (en) * | 2017-12-18 | 2018-06-22 | 南昌大学 | A kind of method for optimizing the distribution of 316L austenitic stainless steels Grain Boundary Character |
| CN108193024A (en) * | 2017-12-18 | 2018-06-22 | 南昌大学 | A kind of method for improving 316LN austenitic stainless steel special grain boundary ratios |
| CN110607428A (en) * | 2019-10-08 | 2019-12-24 | 南通理工学院 | Corrosion-resistant treatment method for face-centered cubic structure metal |
| CN111155020A (en) * | 2020-01-20 | 2020-05-15 | 东南大学 | Method for regulating and controlling corrosion resistance of CoNiFe intermediate entropy alloy |
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| JP2006233292A (en) * | 2005-02-25 | 2006-09-07 | Toshiba Corp | Corrosion resistant steel and producing method therefor |
| CN103993145A (en) * | 2014-05-06 | 2014-08-20 | 上海大学 | Method for improving special structure grain-boundary proportion of austenitic stainless steel |
| CN104593571A (en) * | 2015-01-16 | 2015-05-06 | 上海大学 | Grain boundary engineering process method for improving corrosion resistance of stainless steel 316 |
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| EP0674721B1 (en) * | 1992-12-21 | 1998-05-13 | Ontario Hydro | Thermomechanical processing of metallic materials |
| JP2006233292A (en) * | 2005-02-25 | 2006-09-07 | Toshiba Corp | Corrosion resistant steel and producing method therefor |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105842308A (en) * | 2016-03-25 | 2016-08-10 | 华南理工大学 | Method for eliminating super 304H steel inter-granular corrosion sensitivity |
| CN106868280A (en) * | 2017-01-13 | 2017-06-20 | 南京理工大学 | The preparation method of the Fe Ni Cr based austenite alloys of low intercrystalline corrosion tendency |
| CN108193036A (en) * | 2017-12-18 | 2018-06-22 | 南昌大学 | A kind of method for optimizing the distribution of 316L austenitic stainless steels Grain Boundary Character |
| CN108193024A (en) * | 2017-12-18 | 2018-06-22 | 南昌大学 | A kind of method for improving 316LN austenitic stainless steel special grain boundary ratios |
| CN110607428A (en) * | 2019-10-08 | 2019-12-24 | 南通理工学院 | Corrosion-resistant treatment method for face-centered cubic structure metal |
| CN111155020A (en) * | 2020-01-20 | 2020-05-15 | 东南大学 | Method for regulating and controlling corrosion resistance of CoNiFe intermediate entropy alloy |
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Application publication date: 20160323 |