CN104451396A - Seawater-corrosion-resisting high-saturation-induction-intensity magnetically soft alloy - Google Patents
Seawater-corrosion-resisting high-saturation-induction-intensity magnetically soft alloy Download PDFInfo
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Abstract
The invention relates to a seawater-corrosion-resisting high-saturation-induction-intensity magnetically soft alloy which comprises the following components in percentage by weight: 18.0-25.0 percent of Cr, 0.5-3.0 percent of Mo, 0.16-2.8 percent of micro-alloyed elements and the balance of Fe. The alloy satisfies the requirement on corrosion resistance under a severe seawater environment and is also excellent in magnetic properties, mechanical strength and seawater corrosion resistance and high in saturation induction intensity.
Description
Technical field
The present invention relates to a kind of metallic substance, particularly a kind of seawater corrosion resistance high saturated magnetic induction non-retentive alloy.
Background technology
Non-retentive alloy refers to a class alloy with low-coercivity and higher magnetic permcability, is widely used in the fields such as wireless electron industrial equipments, precision instrumentation, power equipment.The main characteristic of non-retentive alloy has " two is high ", high, the saturated magnetic strength of " two is low " i.e. magnetic permeability is high, coercive force is low, magnetic hysteresis loss is low.Non-retentive alloy can be divided into fe-Ni soft magnetic alloy, magnetic temp compensating alloy, anticorrosion soft mag, high saturated magnetic induction non-retentive alloy, high rigidity high resistance high magnetic conductance alloy etc. by its classification.
Conventional anticorrosion soft mag comprises Fe-Al system, Fe-Ni system and Fe-Cr system, for seawater corrosion resistance non-retentive alloy, can only select Fe-Cr system.Fe-Cr alloy has that resistance to corrosion is strong, magnetic temperature stability high, can be used for making the various magnetic elements worked under corrosive environmental conditions, be generally considered the desirable magnetically permeable material making various magnetic valve, therefore in nearest twenty or thirty year, receive the extensive attention of the industrial sectors such as ocean, boats and ships, oil, electronics, instrument, thus facilitate Fe-Cr anticorrosion soft mag development.Research in the past mainly to improve and to improve alloy corrosion resistance, uses under making its alloy be adapted at rugged environment.Along with the progress of industrial technology, the continuous appearance of New Instruments, the raising of the Push Technologies such as ocean, navigation, petroleum drilling, require anticorrosion soft mag existing high magnetic property (high magnetic strength, low-coercivity, the scantlings of the structure of propulsion system about part can be effectively reduced, weight reduction), there is again the characteristic of good resistant to many dielectric corrosion, particularly many instruments, equipment uses under the environment such as moist, maritime and store.
For Fe-Cr system anticorrosion soft mag, the factor affecting alloy magnetic is a lot, mainly contains chemical composition, foreign matter content, heat treating regime, stress defect etc.The magnetic of foreign matter content on non-retentive alloy has obvious impact.When there is the inclusion defects such as carbide, oxide compound, nitride in alloy, these non magnetic doping can reduce the wall energy of domain wall in a certain position, its motion of pinning effectively, suppress the movement of domain wall, cause domain wall pinning, hinder magnetic history, make coercive force increase, magnetic permeability reduction.For non-corrosive metal, the factor affecting material corrosion resistance comprises alloy species, alloying constituent, foreign matter content, internal organizational structure, condition of surface etc.Generally speaking, the beneficial element such as Cr, Ni, Mo, Nb, less foreign matter content, homogenize heterogeneous microstructure and high-quality condition of surface are conducive to improving the corrosion resistance nature of material.
Summary of the invention
The object of this invention is to provide a kind of seawater corrosion resistance high saturated magnetic induction non-retentive alloy, described alloy had both had excellent magnetic property, can also meet the corrosion resistance nature requirement under seawater severe rugged environment, have excellent mechanical property simultaneously.
Technical scheme of the present invention is:
Seawater corrosion resistance high saturated magnetic induction non-retentive alloy, its each composition weight percentage composition is: Cr 18.0 ~ 25.0%; Mo 0.5 ~ 3.0%; Micro alloying element 0.16 ~ 2.8; Fe is surplus.
The good technical scheme of the present invention is, each composition weight percentage composition of described alloy is: Cr 205. ~ 21.5%; Mo 0.8 ~ 1.8%; Micro alloying element 1.05 ~ 1.145; Fe is surplus.
Described micro alloying element is C, Si, Mn, Nb, Ni, Cu, Zr, B.
The each composition weight percentage composition of described micro alloying element is, C:0.005 ~ 0.03%; Si:0.05 ~ 0.3%; Mn:0.05 ~ 0.5%; Nb:0.05 ~ 0.5%; Ni:0 ~ 1%; Cu:0.005 ~ 0.2%; Zr:0.001 ~ 0.05%; B:0.001 ~ 0.03%.
The preparation method of seawater corrosion resistance high saturated magnetic induction non-retentive alloy, gets each component according to above-mentioned proportioning, prepares according to the following steps:
1) vacuum melting
Get Fe, Cr, Mo, start first time refining after being heated to fine melt state, it is refining temperature 1600 ~ 1650 DEG C for the first time, vacuum degree control >=10Pa, refining time 2 ~ 10kg/min; Add micro alloying element C, Si, Mn, Nb, Ni, Cu, Zr, B subsequently, fully stir, carry out second time refining, refining temperature 1550 ~ 1600 DEG C, vacuum tightness >=5Pa, refining time 3 ~ 15kg/min; Regulate molten steel temperature to 1520 ~ 1560 DEG C, with the casting of 3 ~ 18kg/min speed under argon atmosphere, obtained esr electrode bar;
2) esr
Remove step 2) the electrode obtained rod surface scale, get slag charge, each component proportion of slag charge is by weight: CaF
2: 70 parts, CaO:20 part, Al
2o
3: 10 parts, at 600 ~ 800 DEG C of temperature, toast at least 4h before slag charge heating, use the carbon dioxide process carbon electrode starting the arc during heating, after slag charge being heated to molten state, electrode bar is slowly inserted in slag bath, control voltage 40 ~ 60V, electric current 3000 ~ 9000A, esr; With the feeding of power successive subtraction method before esr terminates, the electric current lowering speed 0.007kA/s of feeding, after electroslag, by ingot casting cooling>=30min, obtains steel ingot;
3) forge
Step 3) gained steel ingot forges, and heat-up rate is 100 ~ 120 DEG C/h, holding temperature 950 ~ 1120 DEG C, soaking time 60 ~ 120min, and final forging temperature >=800 DEG C, are forged into pole;
4) thermal treatment
Step 3) gained pole carries out vacuum annealing process, air cooling, the method of vacuum annealing process is, 1000 ~ 1100 DEG C, heat-up rate 120 ~ 200 DEG C/h, soaking time is 60min ~ 240min, is cooled to 600 DEG C according to the speed of 150 ~ 200 DEG C/h, then be down to 200 DEG C according to 100 ~ 120 DEG C/h speed, obtain seawater corrosion resistance high saturated magnetic induction non-retentive alloy of the present invention.
In illustrated alloy, Cr and Mo makes alloy obtain rustless property and corrosion proof most important two kinds of elements (PREN=Cr+3.3Mo%+30N%), adding of they does not change ferritic matrix in steel, makes alloy both have outstanding solidity to corrosion and has good magnetic property.
Cr be determine alloy corrosion resistance can most fundamental element, two aspects are mainly reflected in anti-corrosion contribution, chromium element itself can improve the electropotential in steel, when chromium constituent content in alloy reaches certain amount (usually said 12.5%), electropotential will have a sudden change (1/8 rule), make alloy have rustless property; In Oxidant, chromium can make the surface of alloy form the rich chromium oxide film Cr of one deck densification very soon
2o
3, protection steel is from the oxidative attack of extraneous medium.
Mo is the important support element of corrosion resistance nature in alloy, can significantly improve the corrosion resistance of alloy in chloride ion-containing corrosive medium, and in 3.5%NaCl solution, Mo content is higher, and its solidity to corrosion is better.In addition, the magnetic property of Mo element alloy has disadvantageous effect.
C has duality in the alloy, and on the one hand, C is stable austenite element, is about 30 times of Ni, have obvious effect, but the brittle transition temperature of alloy, toughness has disadvantageous effect to raising alloy mechanical intensity; On the other hand, because the avidity of C and Cr is very large, the corrosive nature of the carbide alloy material of formation has disadvantageous effect, and the magnetic property impact of alloy material is also disadvantageous.
Si is very remarkable to the resistance of oxidation effect improving anticorrosion soft mag, simultaneously, Si can form intermetallic compound by the element such as Nb, C in material sanitary process, these compounds are separated out on crystal boundary, pinning effect is risen to crystal boundary, prevent crystal boundary from expanding, prevent crystal grain from expanding, thus affect the magnetic property of material.
Mn is austenite former, can improve the processing characteristics of stainless intensity and alloy, but adding of Mn has disadvantageous effect to stainless solidity to corrosion and magnetic property.
Nb is very strong due to the bonding force with C, contributes to the refinement of ferrite stainless crystalline grain of steel, forms stable carbide, improves the anti intercrystalline corrosion ability of alloy material.
Ni is stable austenite unit, have obvious effect, but the magnetic property of alloy has disadvantageous effect to raising alloy mechanical intensity.
Cu can improve its corrosion resistance nature in the alloy, and in general, Cu is to the stainless reducing resistance medium general corrosion of raising and resistance to containing Cl
-medium local corrosion have obvious effect.
In addition, low-alloyed cold working hardening tendency can fall in Cu, is convenient to cold working and cold-forming.
Zr and B element have the effect of purification crystal boundary, reduce the non-metallic inclusion in steel, and change its form, thus the comprehensive mechanical performance of alloy is improved a lot, in addition, Zr and B element make the resistance of domain wall drift and rotation reduce by crystal grain thinning, thus reduction coercive force, increase magnetic permeability.
Alloy of the present invention solves the high magnetic of anticorrosion soft mag, the contradictory relation of high anti-corrosion, this alloy material both had excellent magnetic property, severe rugged environment can also be met under corrosion resistance nature requirement.Compared with existing anticorrosion soft mag 1J36,1J116,1J117, magnetic property is suitable, seawater corrosion resistance ability is more excellent, and its physical strength and toughness are also more excellent.
Embodiment
One. embodiment
Embodiment 1
1) Composition Design of alloy
Alloying ingredient gross weight in the present embodiment is 90kg, and its each element proportioning (by weight percentage composition) C:0.01%, Si:0.2%, Mn:0.4%, Cr:20.5%, Mo:0.8%, Nb:0.3%, Cu:0.1%, Zr:0.02%, B:0.02%, Fe are surplus.
2) preparation of alloy
A) melting: prepare burden according to above-mentioned alloy designs proportioning, carry out vacuum melting, adopt secondary refining process, Fe, Cr, Mo are pressed bed material and load crucible, first time refining is started after power transmission to fine melt state, refining temperature 1600 ~ 1650 DEG C for the first time, controls vacuum tightness >=10Pa, refining time 20min; After first time refining completes, add micro alloying element C, Si, Mn, Nb, Cu, Zr, B, micro alloying element puts into feed compartment by small powder, abundant mechanical electromagnetic starts second time refining after stirring, refining temperature 1550 ~ 1600 DEG C during second time refining, control vacuum tightness >=5Pa, refining time 15min.Second time is after refining terminates, and after regulating molten steel temperature to 1520 ~ 1560 DEG C, under argon atmosphere, is cast into Φ 110mm ingot casting, obtained esr electrode bar with ~ 6kg/min speed.
B) esr: esr selects Φ 160mm crystallizer, slag charge counterweight 5kg, and proportioning is (kg) by weight: CaF
2: 70 parts, CaO:20 part, Al
2o
3: 10 parts.Slag charge is toasted 4h at 800 DEG C of temperature, and step a) the electrode obtained rod surface scale is removed and guarantees without silt, water mark.Use the carbon dioxide process carbon electrode starting the arc, slag charge is melted and to molten state, electrode bar is slowly inserted in slag bath, control voltage 40 ~ 48V, electric current 3000 ~ 4500A, esr.Should carry out before esr terminates vulcanizing contracting, feeding adopts power decay method, feeding electric current lowering speed 0.007kA/s, after electroslag, ingot casting indwelling should be cooled in crystallizer >=30min can the demoulding, finally obtains the ESR ingot of Φ 160mm specification.
C) forge: step b) gained ESR ingot is incubated 90min at 1080 DEG C of temperature, heat-up rate 120 DEG C/h, final forging temperature 830 DEG C.
Cogging to 80 under one ton of Single arm × 80mm square billet, and then forging is to Φ 45mm pole.
D) thermal treatment: step c) gained pole is warming up to 1050 DEG C by heat-up rate 150 DEG C/h in a vacuum furnace, and insulation 2h, is cooled to 600 DEG C by 150 DEG C/h, is then cooled to 200 DEG C according to 120 DEG C/h, air cooling of coming out of the stove.
3) alloy obtains qualified seawater corrosion resistance high-saturation-induction-density alloy for magnetic bar after car light, sampling, test.This bar is applicable to the magnetic valve in sewage treatment project.
Embodiment 2
1) design of alloy
Alloying ingredient weight in this example is 500kg, and each element proportioning (by weight percentage composition) C:0.015%, Si:0.1%, Mn:0.4%, Cr:21.5%, Mo:1.8%, Nb:0.2%, Ni:0.3%, Cu:0.1%, Zr:0.01%, B:0.02%, Fe are surplus.
2) preparation of alloy
A) melting: prepare burden according to above-mentioned alloy designs proportioning, carry out vacuum melting, adopt secondary refining process, Fe, Cr, Mo are pressed bed material and load crucible, first time refining is started after power transmission to fine melt state, refining temperature 1600 ~ 1650 DEG C for the first time, controls vacuum tightness >=10Pa, refining time 60min; After first time refining completes, add micro alloying element C, Si, Mn, Nb, Ni, Cu, Zr, B, micro alloying element puts into feed compartment by small powder, abundant mechanical electromagnetic starts second time refining after stirring, refining temperature 1550 ~ 1600 DEG C during second time refining, control vacuum tightness >=5Pa, refining time 40min; Second time is after refining terminates, after regulating molten steel temperature to 1520 ~ 1560 DEG C under argon atmosphere ~ 16kg/min speed is cast into Φ 200mm ingot casting, obtained esr electrode bar.
B) esr: the esr in this example selects Φ 320mm crystallizer, slag charge counterweight 35kg, and proportioning is (kg) by weight: CaF
2: 70 parts, CaO:20 part, Al
2o
3: 10 parts.Slag charge is toasted 8h at 800 DEG C of temperature, and step a) the electrode obtained rod surface scale is removed and guarantees without silt, water mark.Use the carbon dioxide process carbon electrode starting the arc, slag charge is melted and to molten state, electrode bar is slowly inserted in slag bath, control voltage 50 ~ 56V, electric current 7000 ~ 8500A, esr.Carry out before esr terminates vulcanizing contracting, feeding adopts power decay method, feeding electric current lowering speed 0.007kA/s, after electroslag, ingot casting indwelling should be cooled in crystallizer >=30min can the demoulding, finally obtains the ESR ingot of Φ 320mm specification.
C) forge: step b) gained ESR ingot is incubated 120min at 1120 DEG C of temperature, heat-up rate 120 DEG C/h, final forging temperature 800 DEG C.
Use cogging to 120 × 120mm square billet under 2500 tons of quick forging machines, then use 1 ton of Single arm to forge again to Φ 80mm pole.
D) thermal treatment: step c) gained pole is warming up to 1050 DEG C by heat-up rate 120 DEG C/h in a vacuum furnace, and insulation 2h, is cooled to 600 DEG C by 150 DEG C/h, is then cooled to 200 DEG C according to 100 DEG C/h, air cooling of coming out of the stove.
3) alloy obtains qualified seawater corrosion resistance high-saturation-induction-density alloy for magnetic bar after car light, sampling, test, is applicable to marine ship commercial power magnet valve.
Two. performance test
The alloy of Example 1-2 gained, does following test:
1. the mechanical property of alloy
Alloy At Room Temperature mechanical property of the present invention is as following table 1:
The room-temperature mechanical property of table 1 alloy
| Rm，MPa | R P0.2，MPa | A,% | Z,% | HB | |
| Room temperature | ≥400 | ≥300 | ≥10 | ≥25 | ≤220 |
2. the magnetic property of alloy
The magnetic property of material of the present invention meets: DC magnetic performance: Bs >=1.35T, HC≤80A/m.
3. the corrosion resistance nature of alloy
The corrosive nature of material of the present invention is as shown in table 2:
Table 2 corrosion resisting property
Conclusion: invent described material and compare with same type of material 1J36,1J116,1J117, when saturation induction density is suitable, has also had better sea water corrosion resistant and good mechanical property concurrently simultaneously.
Claims (4)
1. a seawater corrosion resistance high saturated magnetic induction non-retentive alloy, is characterized in that, each composition weight percentage composition of this alloy is:
Cr 18.0~25.0%；
Mo 0.5~3.0%；
Micro alloying element 0.16 ~ 2.8;
Fe is surplus.
2. alloy according to claim 1, is characterized in that: each composition weight percentage composition of this alloy is:
Cr 20.5~21.5%；
Mo 0.8~1.8%；
Micro alloying element 1.05 ~ 1.145;
Fe is surplus.
3. alloy according to claim 1 and 2, is characterized in that: described micro alloying element is C, Si, Mn, Nb, Ni, Cu, Zr, B.
4. alloy according to claim 3, is characterized in that: each composition weight percentage composition of described micro alloying element is, C:0.005 ~ 0.03%; Si:0.05 ~ 0.3%; Mn:0.05 ~ 0.5%; Nb:0.05 ~ 0.5%; Ni:0 ~ 1%; Cu:0.005 ~ 0.2%; Zr:0.001 ~ 0.05%; B:0.001 ~ 0.03%.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112159942A (en) * | 2020-08-18 | 2021-01-01 | 重庆材料研究院有限公司 | Constant-elasticity alloy for anti-radiation sensor and preparation method thereof |
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| CN1906714A (en) * | 2004-05-13 | 2007-01-31 | 信越化学工业株式会社 | Magnetic circuit with excellent corrosion resistance, and voice coil motor or actuator |
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