CN104451396B - 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 metal material, close particularly to a kind of seawater corrosion resistance high saturated magnetic induction soft magnetism
Gold.
Background technology
Magnetically soft alloy refers to a class alloy with low-coercivity and higher magnetic permcability, is widely used in wireless electron industry
The fields such as equipment, precision instrumentation, power equipment.The key property of magnetically soft alloy have " two high ", " two is low " i.e. pcrmeability height,
Saturated magnetic strength is high, coercivity is low, magnetic hystersis loss is low.Magnetically soft alloy can be divided into fe-Ni soft magnetic alloy, magnetic temp compensating by its classification
Alloy, anticorrosion soft mag, high saturated magnetic induction magnetically soft alloy, high rigidity high resistance high magnetic conductance alloy etc..
Conventional anticorrosion soft mag includes Fe-Al system, Fe-Ni system and Fe-Cr system, for seawater corrosion resistance magnetically soft alloy
For, Fe-Cr system can only be selected.Fe-Cr alloy has that resistance to corrosion is strong, magnetic temperature stability high, can be used for making
Make the various magnetic elements worked under corrosive environmental conditions, be generally considered the preferable magnetic conduction making various electromagnetic valves
Material, therefore receives the extensive weight of the industrial departments such as ocean, boats and ships, oil, electronics, instrument and meter in nearest twenty or thirty year
Depending on, thus promote Fe-Cr anticorrosion soft mag development.Conventional research is mainly to improve and to improve alloy corrosion-resistant
Ability is main so that it is alloy is suitable under rugged environment using.Along with the progress of industrial technology, New Instruments continuous
Occur, the raising of the Push Technologies such as ocean, navigation, oil drilling, it is desirable to existing high magnetic property (the high magnetic of anticorrosion soft mag
Sense, low-coercivity, can effectively reduce the propulsion system physical dimension about part, alleviate weight), have again good resistance to many
The characteristic of kind of dielectric corrosion, particularly many instruments, equipment are to use 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 has chemical composition, miscellaneous
Matter content, heat treating regime, stress defect etc..Impurity content has significantly impact to the magnetic of magnetically soft alloy.When alloy is deposited
When inclusion defects such as carbide, oxide, nitride, these non magnetic doping can reduce the domain wall domain wall in a certain position
Can, its motion of pinning effectively, the movement of suppression domain wall, causes domain wall pinning, hinders magnetic history so that coercivity increases
Add, pcrmeability reduces.For corrosion resistant alloy, affect the factor of material corrosion resistance include alloy species, alloying component,
Impurity content, internal organizational structure, apparent condition etc..It is said that in general, the beneficial elements such as Cr, Ni, Mo, Nb, less impurity contain
Measure, homogenize heterogeneous microstructure and the decay resistance of high-quality apparent condition beneficially raising material.
Summary of the invention
It is an object of the invention to provide a kind of seawater corrosion resistance high saturated magnetic induction magnetically soft alloy, described alloy was both
There is the magnetic property of excellence, moreover it is possible to meet the decay resistance requirement under sea water severe rugged environment, there is excellent mechanicalness simultaneously
Energy.
The technical scheme is that
Seawater corrosion resistance high saturated magnetic induction magnetically soft 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 preferable 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.
Described micro alloying element each composition weight percentage composition 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 magnetically soft alloy, takes each component according to above-mentioned proportioning,
Prepare according to the following steps:
1) vacuum melting
Take Fe, Cr, Mo, after being heated to fine melt state, start refine for the first time, its first time refining temperature 1600～1650
DEG C, vacuum degree control >=10Pa, refining time 2～10kg/min；Be subsequently added micro alloying element C, Si, Mn, Nb, Ni, Cu,
Zr, B, be sufficiently stirred for, carry out second time refine, refining temperature 1550～1600 DEG C, vacuum >=5Pa, refining time 3～
15kg/min；Regulation molten steel temperature is to 1520～1560 DEG C, with 3～18kg/min speed casting, system under argon atmosphere
Obtain electroslag remelting electrode bar；
2) electroslag remelting
Remove step 2) the electrode obtained rod surface scale, take slag charge, each component proportion of slag charge is by weight: CaF2:
70 parts, CaO:20 part, Al2O3: 10 parts, before slag charge heating, at a temperature of 600～800 DEG C, toast at least 4h, during heating, use carbon electricity
The pole starting the arc, slowly inserts electrode bar in slag bath after slag charge is heated to molten condition, controls voltage 40～60V, electric current 3000
～9000A, electroslag remelting；Electroslag remelting terminate before with power diminishing method feeding, electric current decrease speed 0.007kA/s of feeding,
After electroslag, by ingot casting cooling >=30min, obtain steel ingot；
3) forging
Step 3) gained steel ingot forges, and programming rate is 100～120 DEG C/h, holding temperature 950～1120 DEG C, protects
The temperature time 60～120min, final forging temperature >=800 DEG C, it is forged into pole；
4) heat treatment
Step 3) gained pole carries out vacuum annealing process, air cooling, and the method that vacuum annealing processes is, 1000～1100
DEG C, programming rate 120～200 DEG C/h, temperature retention time is 60min～240min, is cooled to according to the speed of 150～200 DEG C/h
600 DEG C, then according to 100～120 DEG C/h speed is down to 200 DEG C, obtain seawater corrosion resistance high-saturation magnetic induction of the present invention
Intensity magnetically soft alloy.
In alloy shown in the present invention, Cr and Mo is to make alloy obtain rustless property and corrosion proof most important in rustless steel
Two kinds of elements (PREN=Cr+3.3Mo%+30N%), their addition does not change ferritic matrix in steel, makes alloy both
There is outstanding corrosion resistance and there is preferable magnetic property.
Cr is the most basic element determining alloy corrosion resistance energy, and anti-corrosion contribution is mainly reflected in two aspects, chromium
Element itself can improve the electrode potential in steel, when in alloy chromium constituent content when reaching a certain amount (usually said
12.5%), electrode potential will have a sudden change (1/8 rule), make alloy have rustless property；In Oxidant, chromium can make conjunction
The surface of gold quickly forms one layer of fine and close chromium-rich oxide-film Cr2O3, protect steel from the oxidative attack of extraneous medium.
Mo is the important support element of decay resistance in alloy, can significantly improve alloy at chloride ion-containing corrosive medium
In corrosion resistance, in 3.5%NaCl solution, Mo content is the highest, and its corrosion resistance is the best.Additionally, the magnetic that Mo element is to alloy
Performance adversely affects.
C has duality in the alloy, on the one hand, C is 30 times of stable austenite element, about Ni, to improving alloy
Mechanical strength has obvious effect, but adversely affects brittle transition temperature, the toughness of alloy；On the other hand, due to C and Cr
Affinity very big, the corrosive nature of alloy material is adversely affected by the carbide of formation, the magnetic property shadow to alloy material
Sound is also disadvantageous.
Si is very notable to the oxidation resistance effect improving anticorrosion soft mag, and meanwhile, Si can in material sanitary process
Forming intermetallic compound with elements such as Nb, C, these compounds separate out on crystal boundary, and crystal boundary rises pinning effect, prevent crystal boundary
Expansion, prevents crystal grain from expanding, thus affects the magnetic property of material.
Mn is austenite former, it is possible to increase stainless intensity and the processing characteristics of alloy, but the addition of Mn
Stainless corrosion resistance and magnetic property are all adversely affected.
Nb is very strong due to the adhesion with C, contributes to the refinement of ferrite stainless crystalline grain of steel, forms stable carbide,
Improve the anti intercrystalline corrosion ability of alloy material.
Ni is stable austenite unit, has obvious effect to improving alloy mechanical intensity, but has the magnetic property of alloy
Adverse effect.
Cu can improve its decay resistance in the alloy, and in general, Cu is to improving stainless reducing resistance medium
General corrosion and resistance to containing Cl—Medium local corrosion have obvious effect.
Additionally, low-alloyed flow harden tendency can drop in Cu, it is simple to cold working and cold forming.
Zr and B element have the effect purifying crystal boundary, reduce the non-metallic inclusion in steel, and change its form, thus
The comprehensive mechanical performance making alloy improves a lot, additionally, Zr and B element make the resistance of domain wall drift and rotation by crystal grain thinning
Power reduces, thus reduces coercivity, increases pcrmeability.
Alloy of the present invention solves the high magnetic of anticorrosion soft mag, the contradictory relation of high corrosion-resistant, this alloy material
Expect the magnetic property both with excellence, the decay resistance requirement that can also meet under severe rugged environment.With existing anticorrosion soft mag
1J36,1J116,1J117 compare, and magnetic property is suitable, seawater corrosion resistance ability is the most excellent, and its mechanical strength and toughness also will be more
For excellent.
Detailed description of the invention
One. embodiment
Embodiment 1
1) the composition design of alloy
Alloying ingredient gross weight in the present embodiment is 90kg, its each element proportioning (percentage composition by weight) 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: carry out dispensing according to above-mentioned alloy design proportioning, carry out vacuum melting, use secondary refining process, will
Fe, Cr, Mo press bed material and load crucible, start for the first time refine after power transmission to fine melt state, for the first time refining temperature 1600～
1650 DEG C, control vacuum >=10Pa, refining time 20min；After refine completes for the first time, add micro alloying element C, Si,
Mn, Nb, Cu, Zr, B, micro alloying element puts into feed compartment by small powder, starts second time refine after the stirring of abundant mechanical electromagnetic,
Refining temperature 1550～1600 DEG C during refine for the second time, control vacuum >=5Pa, refining time 15min.Refine for the second time terminates
After, regulation molten steel temperature to after 1520～1560 DEG C, under argon atmosphere with～6kg/min speed be cast into Φ 110mm
Ingot casting, prepared electroslag remelting electrode bar.
B) electroslag remelting: electroslag remelting selection Φ 160mm crystallizer, slag charge counterweight 5kg, proportioning (kg) by weight:
CaF2: 70 parts, CaO:20 part, Al2O3: 10 parts.Slag charge is toasted at a temperature of 800 DEG C 4h, step a) the electrode obtained rod Surface Oxygen
Change skin remove and guarantee without silt, water mark.Use the carbon electrode starting the arc, slag charge is melted and to molten condition, electrode bar is slowly inserted
In slag bath, control voltage 40～48V, electric current 3000～4500A, electroslag remelting.Electroslag remelting should carry out vulcanizing contracting before terminating, and mends
Contracting employing power decay method, feeding electric current decrease speed 0.007kA/s, after electroslag, should be by ingot casting indwelling in crystallizer
Cooling >=30min can the demoulding, finally obtain the ESR ingot of Φ 160mm specification.
C) forging: step b) gained ESR ingot is incubated 90min, 120 DEG C/h of programming rate, finish-forging temperature at a temperature of 1080 DEG C
Spend 830 DEG C.
Under one ton of Single arm, cogging is to 80 × 80mm square billet, forges to Φ 45mm pole the most again.
D) heat treatment: step c) gained pole is warming up to 1050 DEG C by 150 DEG C/h of programming rate in a vacuum furnace, insulation
2h, is cooled to 600 DEG C by 150 DEG C/h, then according to 120 DEG C/h is cooled to 200 DEG C, and air cooling of coming out of the stove.
3) alloy through car light, sample, test after obtain qualified seawater corrosion resistance high-saturation-induction-density alloy for magnetic bar.
This bar electromagnetic valve be applicable to sewage treatment project.
Embodiment 2
1) design of alloy
Alloying ingredient weight in this example is 500kg, each element proportioning (percentage composition by weight) 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 remaining
Amount.
2) preparation of alloy
A) melting: carry out dispensing according to above-mentioned alloy design proportioning, carry out vacuum melting, use secondary refining process, will
Fe, Cr, Mo press bed material and load crucible, start for the first time refine after power transmission to fine melt state, for the first time refining temperature 1600～
1650 DEG C, control vacuum >=10Pa, refining time 60min；After refine completes for the first time, add micro alloying element C, Si,
Mn, Nb, Ni, Cu, Zr, B, micro alloying element is put into feed compartment by small powder, is started second time essence after the stirring of abundant mechanical electromagnetic
Refining, for the second time refining temperature 1550～1600 DEG C during refine, control vacuum >=5Pa, refining time 40min；Refine for the second time
After end, regulation molten steel temperature to after 1520～1560 DEG C under argon atmosphere ~ 16kg/min speed is cast into Φ 200mm
Ingot casting, prepared electroslag remelting electrode bar.
B) electroslag remelting: the electroslag remelting in this example selects Φ 320mm crystallizer, slag charge counterweight 35kg, and proportioning is by weight
Amount part (kg): CaF2: 70 parts, CaO:20 part, Al2O3: 10 parts.Slag charge is toasted at a temperature of 800 DEG C 8h, step a) gained electricity
Extremely rod surface scale is removed and guarantees without silt, water mark.Use the carbon electrode starting the arc, slag charge is melted electrode to molten condition
Rod slowly inserts in slag bath, controls voltage 50～56V, electric current 7000～8500A, electroslag remelting.Electroslag remelting is carried out before terminating
Vulcanizing contracting, feeding uses power decay method, feeding electric current decrease speed 0.007kA/s, after electroslag, should by ingot casting indwelling in
In crystallizer cooling >=30min can the demoulding, finally obtain the ESR ingot of Φ 320mm specification.
C) forging: step b) gained ESR ingot is incubated 120min, 120 DEG C/h of programming rate, finish-forging at a temperature of 1120 DEG C
Temperature 800 DEG C.
Cogging under 2500 tons of quick forging machines is used to 120 × 120mm square billet, then to use 1 ton of Single arm to forge to Φ 80mm again
Pole.
D) heat treatment: step c) gained pole is warming up to 1050 DEG C by 120 DEG C/h of programming rate in a vacuum furnace, insulation
2h, is cooled to 600 DEG C by 150 DEG C/h, then according to 100 DEG C/h is cooled to 200 DEG C, and air cooling of coming out of the stove.
3) alloy through car light, sample, test after obtain qualified seawater corrosion resistance high-saturation-induction-density alloy for magnetic bar,
It is applicable to marine ship commercial power magnet valve.
Two. performance test
The alloy of Example 1-2 gained, does tests below:
1. the mechanical property of alloy
The Alloy At Room Temperature mechanical property such as table 1 below of the present invention:
The room-temperature mechanical property of table 1 alloy
| Rm, MPa | RP0.2, 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 decay resistance 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, in saturation induction density phase
In the case of when, more preferable sea water corrosion resistant and preferable mechanical performance are the most also had concurrently.
Claims (3)
1. a seawater corrosion resistance high saturated magnetic induction magnetically soft alloy, it is characterised in that each composition weight hundred of this alloy
Point content is:
Cr 18.0~25.0%；
Mo 0.5~3.0%；
Micro alloying element 0.16 ~ 2.8；
Fe is surplus, and described micro alloying element is C, Si, Mn, Nb, Ni, Cu, Zr, B.
Alloy the most according to claim 1, it is characterised 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.
Alloy the most according to claim 1, it is characterised in that: described micro alloying element each composition weight percentage composition
For, 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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