CN103215415A - Method for quickly improving corrosion resistance of material surface in situ - Google Patents
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Abstract
The invention relates to a method for quickly improving corrosion resistance of a material surface in situ. The method comprises the following steps: firstly selecting suitable laser process parameters, and introducing a pre-stressing force into the material surface by utilizing laser impaction; and then carrying out laser annealing treatment on the material surface by utilizing a laser. Compared with other methods, the method for quickly improving the corrosion resistance of the material surface in situ, disclosed by the invention, has the advantages that the introduction of the pre-stressing force and a subsequent thermal treatment are finished by laser processing so that a complex surface of a workpiece can be subjected to the in-situ treatment, the crystal boundary distribution of an irregular surface can be quickly optimized, and the inter-crystal corrosion resistance of the material surface can be improved.
Description
Technical field
The invention belongs to the technology of control austenitic stainless steel top layer performance, particularly a kind of quick in situ improves the method for material surface corrosion resistance nature.
Background technology
The performance of polycrystalline material and its microstructure and crystal boundary characteristic have very closely gets in touch, because the crystal boundary place often exists bigger distortion, more defect and impurity, surfactivity is inner higher than crystal grain, with the closely-related various phenomenons of the structure of crystal boundary, as crystal boundary spread, separate out, corrosion etc., often be subjected to the influence of grain boundary structure.The intergranular carbide phenomenon that selectivity is separated out on crystal boundary mainly is because different cause different with structure of the energy that crystal boundary had.Aust and Rutter utilize first laboratory facilities to observe low energy CSL (coincident site lattice) crystal boundary to have particular performances.A large amount of low energy CSL (1≤Σ≤29) crystal boundaries that studies show that have following characteristics: 1) lower energy; 2) impurity atoms and solute segregation had lower susceptibility; 3) low diffusivity; 4) low specific resistance.Just because of having above-mentioned characteristic, low energy CSL crystal boundary (particularly Σ 3) has manifested slippage, fracture, corrosion and stress corrosion cracking, sensitization and solute segregation (balance and non-equilibrium) had strong inhibitory effects, that have or even immune fully.Low energy CSL crystal boundary is at polycrystalline material ubiquity in polycrystalline material, and the preparation process of its frequency of occurrences and material is closely related.And free crystal boundary often becomes the passage of the core and the crack propagation of crack growth, thereby causes the appearance of intergranular corrosion crackle and intergranular stress corrosion crack owing to have high energy and high movability.Based on understanding to the crystal boundary performance, Watanabe in 1984 have proposed the notion of " crystal boundary design and control " (grain boundary design and control) first, point out in overlapping position dot matrix crystal boundary model, inner some performances and the general different low Σ CSL crystal boundary of high-angle boundary (HABs) of existing of polycrystalline material, the crystal boundary inefficacy drag of this crystal boundary is more superior than general high-angle boundary, be called " special grain boundary " (SBs), can reach optimization in Properties and raising material by control to the design of crystal boundary type and distribution.Canadian subsequently material supply section scholar deduces this notion and is " crystal boundary engineering " (Grain Boundary Engineering).So-called " crystal boundary engineering " is exactly to increase the ratio of special grain boundary in the polycrystalline material by changing alloying, deformation and thermal treatment, to rationalize the crystal boundary of material characteristic distribution, make special grain boundary can interrupt the connectedness of general high-angle boundary network effectively, crystal boundary of material inefficacy drag can be significantly improved, thereby the material a certain or multiple use properties relevant with crystal boundary significantly improved.20 years in the past, the crystal boundary engineering obtained using widely in the exploitation of material and structure property control.
What can find nearly all now investigator's employing all is the hot machining process of prestress-annealing or prestress-recrystallize, its thermal treatment all is to realize by traditional chamber type electric resistance furnace heating, promptly under higher temperature, carry out anneal for a long time, greatly increased energy consumption.Prestress can be realized the control of crystal boundary characteristic distribution to block materials integral body in conjunction with traditional annealed method, thereby improves the intergranular corrosion drag of material.Yet the corrosion failure of material is normally from material surface, gradually to material internal infiltration and diffusion, therefore obtain one deck by the heat treated means of deformation mating surface and have the anti-corrosion top layer of optimizing grain boundary structure, the corrosion-resistant drag that improves material is had great importance.
Laser is the extremely strong high-energy-density thermal source of a kind of controllability, the extreme condition that it provides other conventional means to realize for the processing and the processing of material.Laser impact intensified is the laser radiation metal material surface that utilizes the close short pulse of superpower, make the plasma body of the metal gasification back formation High Temperature High Pressure of metallic surface thin layer, the plasma body blast of sharply expanding produces the shockwave impact material surface and makes it that viscous deformation take place, form residual compressive stress on the surface, the stress/strain layer thickness can reach 1mm.The stress distribution that laser-impact is introduced at material surface and traditional cold rolling a great difference that has, cold roller and deformedly only introduced normal strain at material surface, and laser-impact also produces shear strain to a certain degree when introducing normal strain, and the strain that laser-impact is introduced is complicated more.
LASER HEAT TREATMENT is a kind of laser-assisted accelerated surface heat treatment mode, LASER HEAT TREATMENT utilizes laser radiation to arrive material surface exactly, because power is high on the unit surface of laser radiation zone, workpiece can't shift this part heat rapidly, thereby the workpiece irradiated area is heated rapidly, after laser scanning finishes, because heat conducting effect, the matrix that is in cold conditions makes its quick cooling, and the self-quench hardening that carries out, thereby the annealing process procedure of realizing.LASER HEAT TREATMENT only heats workpiece surface, compares with traditional chamber type electric resistance furnace, is a kind of surface heat treatment technology.In the laser scanning process, light spot energy distributes and is the shape of a saddle, so the thermodiffusion of metallic substance is had certain compensation effect.The homogeneous temperature field in certain zone can be formed along the scanning direction, partial heat treatment can be used for part.Compare the high energy consumption of traditional chamber type electric resistance furnace tens hours even tens hours, LASER HEAT TREATMENT has that processing speed is fast, work range is wide, the characteristics of flexible operation, can significantly improve heat treatment efficiency, cut down the consumption of energy, and because the workpiece deformation amount is little after the LASER HEAT TREATMENT, the surface smoothness height can be used as finishing operation.
Laser-impact has been widely used in improving material hardness, fatigue strength and wear resisting property, LASER HEAT TREATMENT is used to the surface laser cladding of the surperficial transformation hardening of middle and high carbon steel material and iron-based, Ni-based, Co-base alloy material more, still do not have the symphyogenetic mode of the laser-impact of utilization and Laser Heat Treating in China both at home and abroad and control austenitic stainless steel top layer crystal boundary characteristic distribution, and then improve the corrosion proof report of stainless steel fast.
Summary of the invention
The object of the present invention is to provide a kind of quick in situ to improve the method for material surface corrosion resistance nature, thereby under short time and less energy-consumption, realize raising erose workpiece surface intergranular corrosion resistance performance.
The technical solution that realizes the object of the invention is as follows: a kind of quick in situ improves the method for material surface corrosion resistance nature, may further comprise the steps:
1. with shrend after the stainless steel materials solid solution;
2. the sheet material after the solid solution is placed laser-impact equipment, material surface is carried out laser-impact, according to the form below is adjusted the laser-impact processing parameter:
| Laser pulse width/ns | Spot diameter/mm | Overlapping rate | Impact energy/J |
| 10-30 | 3-5 | 30-50% | 2-10 |
；
3. the sheet material behind the laser-impact is placed laser-processing system, the plate surface behind the laser-impact is carried out laser annealing handle, according to the form below is adjusted the laser heat treatment process parameter:
| Output rating/W | Sweep velocity/mmmin -1 | Scanning times/time |
| 100-200 | 100-300 | 1-4 |
；
4. sample is carried out Water Quenching.
The present invention compared with prior art, its remarkable advantage is: (1) laser treatment is the shortening heat treatment time greatly, improves top layer crystal boundary characteristic distribution rapidly, improves the corrosion resistance on top layer; (2) laser-impact and LASER HEAT TREATMENT work range are wide, are applicable to complicated shape piece surface in-situ treatment; (4) laser-impact can cut down the consumption of energy in conjunction with Laser Heat Treating in China treatment process process, reduces discharging; (5) whole technological process easily is automated.
Below in conjunction with accompanying drawing the present invention is described in further detail.
Description of drawings
Accompanying drawing 1(a) is the crystal boundary characteristic distribution figure of undressed austenitic stainless steel.
Accompanying drawing 1(b) is the crystal boundary characteristic distribution figure of austenitic stainless steel after treatment.
Embodiment
The present invention is based on the notion of crystal boundary engineering, introduces strain by laser-impact, comes the grain boundary structure feature on control material top layer by follow-up LASER HEAT TREATMENT, thereby the corrosion resistance nature of austenitic stainless steel is improved.Concrete steps are as follows:
1. will test the shrend behind solution treatment 30min under 1050 ℃ of temperature of used stainless steel materials.
2. in laser-impact equipment, carry out laser-impact and handle, adjust the laser-impact processing parameter.
3. then the sheet material behind the laser-impact is placed laser-processing system, adjust the laser heat treatment process parameter, material surface is carried out LASER HEAT TREATMENT.
4. sample is carried out shrend.
Wherein laser-impact processing parameter such as table 1, Laser Heat Treating in China processing parameter such as table 2:
Table 1 laser-impact processing parameter
| Laser pulse width/ns | Spot diameter/mm | Overlapping rate | Impact energy/J |
| 10-30 | 2-5 | 30-50% | 2-10 |
Table 2 laser heat treatment process parameter
| Output rating/W | Sweep velocity/mmmin -1 | Scanning times/time |
| 100-200 | 100-300 | 1-4 |
In the following Examples and Comparative Examples, represent the optimization effect of material grain boundary structure feature with special grain boundary length percentage ratio (%), being worth high more explanation crystal boundary, to optimize effect good more; The corrosion resistance nature of representing material with reactivate current ratio (%) and corrosion potential (V) respectively.The reactivate current ratio is low more, and corrosion potential just is being tending towards more, and the erosion resistance of illustrative material is good more.
Embodiment 1
Utilize laser-impact equipment (YLSS-D25A type) that austenite stainless steel plate is carried out laser-impact, the laser-impact energy is selected 6J, 8J, 10J.Subsequently, in laser-processing system (YLR-200-AC type) sample is carried out LASER HEAT TREATMENT, laser output power 150W, laser scanning speed are 200mm/min, carry out Water Quenching immediately after heating finishes.The heavy site of the low energy CSL(battle array of processing sample inside) ratio of special grain boundary changes with the laser-impact energy, and concrete test result sees Table 3.
The sample of handling is inlayed with Resins, epoxy and solidifying agent, be prepared into the galvanic corrosion sample of standard.Under room temperature at 0.5M H
2SO
4In+0.01M KSCN the solution sample is carried out potentiokinetic reactivation method (EPR) experiment and polarization curve measurement, reactivate current ratio and corrosion potential change with the laser-impact energy.Sample is listed in table 3 at reactivate current ratio and corrosion potential that 650 ℃ of sensitization 2h record.
The test result of the different laser-impact power of table 3
Embodiment 2
Utilize laser-impact equipment (YLSS-D25A type) that austenite stainless steel plate is carried out laser-impact, the laser-impact energy is selected 6J.Subsequently, in laser-processing system (YLR-200-AC type) sample is carried out LASER HEAT TREATMENT, laser scanning speed is respectively 300mmmin
-1, 200mmmin
-1, 100mmmin
-1, carry out Water Quenching immediately after heating finishes.The heavy site of the low energy CSL(battle array of processing sample inside) ratio of special grain boundary changes with laser scanning speed, and concrete test result sees Table 4.
The sample of handling is inlayed with Resins, epoxy and solidifying agent, be prepared into the galvanic corrosion sample of standard.Under room temperature at 0.5M H
2SO
4In+0.01M KSCN the solution sample is carried out potentiokinetic reactivation method (EPR) experiment and polarization curve measurement, reactivate current ratio and corrosion potential change with laser scanning speed.Sample is listed in table 4 at reactivate current ratio and corrosion potential that 650 ℃ of sensitization 2h record.
The test result of the different laser scanning speeds of table 4
Annotate: V=100 mmmin
-1Once overlap the specimen surface local melting, get the molten bath lower region.
Embodiment 3
Utilize laser-impact equipment (YLSS-D25A type) that austenite stainless steel plate is carried out laser-impact, the laser-impact energy is selected 6J.Subsequently, in laser-processing system (YLR-200-AC type), sample is carried out LASER HEAT TREATMENT, the laser scanning number of times be respectively 200mm/min next time, twice, 200mm/min and 300mm/min twice (totally four times) respectively down under the 200mm/min, carry out Water Quenching immediately after heating finishes.The heavy site of the low energy CSL(battle array of processing sample inside) ratio of special grain boundary changes with the laser scanning number of times, and concrete test result sees Table 5.
The sample of handling is inlayed with Resins, epoxy and solidifying agent, be prepared into the galvanic corrosion sample of standard.In in 0.5M H2SO4+0.01M KSCN solution sample being carried out potentiokinetic reactivation method (EPR) experiment and polarization curve measurement under the room temperature, reactivate current ratio and corrosion potential change with the laser scanning number of times.Sample is listed in table 5 at reactivate current ratio and corrosion potential that 650 ℃ of sensitization 2h record.
The test result of table 5 different scanning number of times
Comparative Examples
For the difference on comparison process material and starting materials tissue and the performance, get one of starting materials at 1050 ℃ of solution treatment 30min, subsequently at 650 ℃ of sensitization 2h, 0.5M H at normal temperatures then
2SO
4Carry out electrochemical corrosion experimental in the+0.01M KSCN solution, test result is positioned at table 3-5.Can find that under identical sensitization condition, the more raw-material corrosion resistance nature of corrosion resistance nature that grain boundary structure is optimized sample is necessarily improved.
To make the standard metallographic specimen through the material that the present invention handles, and utilize EBSD technical testing crystal boundary of material characteristic distribution after polishing, polishing, the electrolytic corrosion, the ratio of special grain boundary surpasses 60% in the tissue; Under identical sensitization condition, the reactivate electric current has descended about 30% than mother metal, and the corrosion resistance nature of material is improved to a certain extent.
Fig. 1 (a) is depicted as crystal boundary characteristic distribution situation in the starting material tissue, wherein the ratio of special grain boundary (Σ≤29) is 30.08%, Fig. 1 (b) is depicted as crystal boundary characteristic distribution situation in the material structure of handling through aforesaid method, wherein the ratio of special grain boundary sees Table 5 for the 60.58%(processing condition), black lines is represented the free crystal boundary of high energy among the figure, and the grey lines are represented low energy Σ CSL crystal boundary.
Claims (4)
1. a quick in situ improves the method for material surface corrosion resistance nature, it is characterized in that may further comprise the steps:
Step 1. with the stainless steel materials solid solution after shrend;
The sheet material of step 2. after with solid solution places laser-impact equipment, adjusts the laser-impact processing parameter, and material surface is carried out laser-impact;
The sheet material of step 3. after with laser-impact places laser-processing system, adjusts the laser heat treatment process parameter, the plate surface behind the laser-impact is carried out laser annealing handle;
Step 4. is carried out Water Quenching with sample.
2. quick in situ according to claim 1 improves the method for material surface corrosion resistance nature, it is characterized in that the shrend behind solution treatment 30min under 1050 ℃ of temperature of the stainless steel materials described in the step 1.
3. quick in situ according to claim 1 improves the method for material surface corrosion resistance nature, it is characterized in that the laser-impact processing parameter according to the form below adjustment described in the step 2:
。
4. quick in situ according to claim 1 improves the method for material surface corrosion resistance nature, it is characterized in that the laser heat treatment process parameter according to the form below adjustment described in the step 3:
。
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108359780A (en) * | 2018-04-09 | 2018-08-03 | 西南交通大学 | The method for improving metastable state austenite stainless hardness of steel and anti-stress corrosion performance |
| CN108384926A (en) * | 2018-03-15 | 2018-08-10 | 温州市赢创新材料技术有限公司 | A kind of local laser process of surface treatment of austenitic stainless steel |
| CN108950144A (en) * | 2018-07-13 | 2018-12-07 | 重庆理工大学 | The method of laser surface modification austenitic stainless steel |
| CN109622615A (en) * | 2018-11-23 | 2019-04-16 | 南京理工大学 | A kind of technique obtaining controllable soft or hard layer structure sheet metal using laser heating |
| CN114985767A (en) * | 2022-06-21 | 2022-09-02 | 武汉大学 | Method for metal additive manufacturing through composite laser shock and laser annealing |
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| CN102031344A (en) * | 2010-12-17 | 2011-04-27 | 南京理工大学 | Method for controlling grain boundary characteristics of austenitic stainless steel |
| CN102965479A (en) * | 2012-12-10 | 2013-03-13 | 南京理工大学 | Method for quickly preparing high-corrosion-resistance austenitic stainless steel surface layer |
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| CN102031344A (en) * | 2010-12-17 | 2011-04-27 | 南京理工大学 | Method for controlling grain boundary characteristics of austenitic stainless steel |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108384926A (en) * | 2018-03-15 | 2018-08-10 | 温州市赢创新材料技术有限公司 | A kind of local laser process of surface treatment of austenitic stainless steel |
| CN108384926B (en) * | 2018-03-15 | 2019-11-12 | 温州市赢创新材料技术有限公司 | A kind of local laser process of surface treatment of austenitic stainless steel |
| CN108359780A (en) * | 2018-04-09 | 2018-08-03 | 西南交通大学 | The method for improving metastable state austenite stainless hardness of steel and anti-stress corrosion performance |
| CN108950144A (en) * | 2018-07-13 | 2018-12-07 | 重庆理工大学 | The method of laser surface modification austenitic stainless steel |
| CN109622615A (en) * | 2018-11-23 | 2019-04-16 | 南京理工大学 | A kind of technique obtaining controllable soft or hard layer structure sheet metal using laser heating |
| CN114985767A (en) * | 2022-06-21 | 2022-09-02 | 武汉大学 | Method for metal additive manufacturing through composite laser shock and laser annealing |
| CN114985767B (en) * | 2022-06-21 | 2024-02-02 | 武汉大学 | Method for manufacturing metal additive by combining laser impact and laser annealing |
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