CN109898030A - A kind of modified valve stainless steel and preparation method thereof - Google Patents
A kind of modified valve stainless steel and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of modified valve stainless steel and preparation method thereof, the modified valve stainless steel includes carbon, silicon, manganese, phosphorus, sulphur, chromium, nickel, molybdenum, aluminium, titanium, niobium, boron, nitrogen, the elements such as iron.The present invention provides a kind of with excellent high temperature fatigue strength, wearability, the valve stainless steel of corrosion resistance, and preparation method simple possible can produce a kind of alternative materials of nickel-base alloy.
Description
Technical field
The present invention relates to metal material field, a kind of valve stainless steel and preparation method thereof is related in particular to.
Background technique
Engine breathing door controls fuel chamber's air inlet and exhaust, works at very high temperatures, and fuel burning generates
Contain CO3 2-、SO4 2-And Cl-Etc. the stronger ion of corrosivity, to form a kind of very strong environment of corrosivity.Therefore, valve
Material must have very high elevated temperature strength and hardness to avoid the generation of creep, while must also anti-corruption with higher
Corrosion energy.In recent years, developed from engine to directions such as high revolving speed, high-power and low burn oil consumption, as automotive service life is wanted
Continuous improvement is asked, the continuous promotion of waste gas emission standard is higher and higher to valve material requirement, therefore the high temperature of engine valve
The requirements such as fatigue strength, wear-resistant and valve material microstructure tissue are all significantly increased.The iron-based Ovshinsky developed at present
The body stainless steel trade mark, such as GH1015, GH1016, GH1035, GH2132 can meet the performance requirement of 650 DEG C or less operating temperatures,
But the fatigue strength under more elevated operating temperature can not be provided, creep is easy to produce, cause to crack.The Ni-based austenite of exploitation
Stainless steel, such as GH4033, GH4037, Nomonic 80A, though more iron-based austenitic stainless steel has better fatigue at high temperature strong
Degree, but should not forge and be machined, and be restricted by nickel element price, do not have economic and environment-friendly advantage.
The present invention is exactly to design a austenite that can be used for more elevated operating temperature not to solve the disadvantage that above-mentioned material
Rust steel provides outstanding high temperature fatigue strength, wearability, corrosion resistance, while reducing the usage amount of nickel element, reaches considerable
Economic benefit.
Summary of the invention
Goal of the invention: having an excellent high temperature fatigue strength the object of the present invention is to provide a kind of, wearability, corrosion resistance
Valve stainless steel；Another purpose of the invention is to provide the preparation method of above-mentioned material.
Technical solution: in order to achieve the above-mentioned object of the invention, a modification of the present invention type valve stainless steel, by weight percentage
When include following component:
Carbon: 0~0.20%；
Silicon: 0~1.00%；
Manganese: 0~1.00%；
Phosphorus: 0~0.035%；
Sulphur: 0~0.035%；
Chromium: 12.5~16.5%；
Nickel: 28.0~35%；
The modified valve stainless steel also comprises the following components by weight percentage:
Molybdenum: 0.20~1.50%；
Aluminium: 1.40~2.40%；
Titanium: 2.0~3.50%；
Niobium: 0.20~0.15%；
Remaining is iron and inevitable impurity.
It is advanced optimized as of the invention, the valve stainless steel is by weight percentage and including following component:
Carbon: 0~0.08%；
Silicon: 0~0.50%；
Manganese: 0~0.50%；
Phosphorus: 0~0.015%；
Sulphur: 0~0.010%；
Chromium: 13.5~15.5%；
Nickel: 30.0~33.5%；
The modified valve stainless steel also comprises the following components by weight percentage:
Molybdenum: 0.40~1.00%；
Aluminium: 1.60~2.20%；
Titanium: 2.30~2.90%；
Niobium: 0.40~0.90%；
Remaining is iron and inevitable impurity.
Carbon: carbon is the strong element for forming and stablizing austenite and expanding austenitic area in austenitic stainless steel.Make
For a kind of interstitial element, it is remarkably improved the intensity of austenitic stainless steel by solution strengthening, but in antirust and corrosion resistant makes
With under demand, especially under 450 DEG C~850 DEG C of working temperature of valve, carbon can be with the Gao Ge's of the formation of the chromium in steel
Cr23C6 type carbide is remarkably decreased the intergranular corrosion resistance ability of Valve Steel so as to cause chromium depletedization of part, to guarantee gas
The corrosion resistance of door steel, therefore it is understood by the inventors that the content of carbon should control 0.20% hereinafter, should preferably control 0~
0.08%.
Silicon: silicon is strong ferrite former, and addition element silicon is more in stainless steel, δ-ferrite of formation, therefore
The addition of element silicon is not suitable for forming the austenite structure of single stable, and be bound to austenite former nickel element to be improved
Content, for the use for reducing nickel content, therefore the silicone content in the present invention is no more than 1.00%；Simultaneously because silicone content exists
When 0.8%~1.0%, silicon along a large amount of segregations of crystal boundary, can increase the intercrystalline corrosion tendency of Valve Steel.Simultaneously because silicon atom atom
Radius is larger, is not easy to form interstitial atom, provides the position of strengthening effect aluminium atom to occupy, and since electronegativity is larger,
Covalent bond is formed with neighbouring atom, metallic bond resultant force is weakened, reduces crystal boundary binding force, held so as to cause Valve Steel high temperature
Long intensity and croop property reduce.Therefore silicone content should control below 0.5% most preferably.
Manganese: manganese is added in chromium nickel stainless steel, and the intensity of stainless steel can be improved, and makees since there is manganese strong austenite to stablize
With frequently as the substitute element use of nickel element, and harmful element element sulphur has stronger affinity in manganese and steel, can reduce
Adverse effect of the element sulphur to Valve Steel.But consider 0.1% manganese of every raising, the pitting potential of austenitic stainless steel about reduces
3% or so, decline Valve Steel corrosion-resistant ability.Therefore inventor recommends to control manganese content 1.0% hereinafter, practical control exists
0.5% or less
P and s: sulphur is easy in crystal boundary segregation, with the increase of its content, can serious reduction crystal boundary energy, it is strong
Crystal boundary is weakened, crystal boundary is easy to slide, crack, and alloy strength is caused sharply to decline.Especially at high temperature, the heat of sulphur is promoted
Activation, so that the sulphur of a part, the especially sulphur of dendrite arm to grain boundary decision, start the crystal boundary not weakened at room temperature originally also
Reduction makes Valve Steel generate red brittleness, reduces the ductility and toughness of steel.Aforementioned manganese influence it has been already mentioned that manganese can be reduced
The presence of the pitting potential of austenitic stainless steel, element sulphur can make this reducing effect more significant.The adverse effect of phosphorus shows
In the alloy eutectic phase that phosphorus is easily segregated in final set area in solidification, and since phosphorus can reduce the final set temperature of Valve Steel, expanding
Big solidification temperature range, so that the segregation of niobium and molybdenum can be promoted, and niobium and molybdenum are that stainless steel of the present invention improves stainless steel
Elevated temperature strength, the important element of wearability.So p and s content should be controlled 0~0.035%, phosphorus is preferably controlled in
0.015% hereinafter, sulphur is preferably controlled in 0.010% or less.
Chromium: chromium is to form and stablize ferritic element strongly, can reduce austenitic area, and chromium can promote the passivation of steel
And steel is made to keep stable passivation effect, to improve the oxidative resistance medium of steel and acid chloride medium performance.It is main
It is dissolved in the base, most important effect is the anti-oxidant and corrosion resistance for increasing alloy.When Cr content reaches critical value
Afterwards, alloy surface will form one layer of continuous, fine and close and good Cr2O3 oxidation film of attachment, can protect metal surface not by O, S
Effect with salt etc. and generate high-temperature oxydation and heat erosion, play a protective role Cr mainly to be dissolved state to alloy oxidation corrosion
It is present in matrix, plays the role of solution strengthening γ matrix.But when chromium content is excessively high, especially when chromium content is more than
When 20%, α-Cr is precipitated tendency and can greatly increase in tissue, and the disperse educt of this α-Cr can reduce the intensity of steel, to make
Valve Steel embrittlement.Therefore chromium should be controlled 12.5~16.5%, be preferably controlled in 13.5~15.5%；
Nickel: nickel is the primary alloy constituent in austenitic stainless steel, and main function is to form and stablize austenite, makes steel
Complete austenitizing tissue is obtained, to make steel that there is good intensity and corrosion resistance, while improving the heat of stainless steel
Mechanical stability, nickel only generate p-type semiconductor NiO film when aoxidizing, and oxidizing reaction rate and oxidation film rate of rise are all significant
Lower than Fe and Co.Since the lattice constant of NiO is small low with crystal middle-jiao yang, function of the spleen and stomach ion cavities concentration, NiO scale has fine and close well
Property and low oxidation rate.Therefore the addition of nickel element, the corrosion resistance of Valve Steel can be greatly increased.Nickel is also hardening constituent simultaneously
The important composition element of Ni3 (Al, Ti), Ni3Nb.Therefore the addition of nickel element greatly improves the high-temperature behavior of Valve Steel, but limited
In the restraining factors of nickel price, in order to reach the usage amount for reducing element, make material more for economic benefit, therefore nickel content is because of control
System should preferably be controlled 30.0~33.5% between 28.0~35%；
Titanium and aluminium: the affinity of titanium and carbon is far longer than chromium, preferential and carbon be combined into TiC chemical combination pass away addition titanium in steel can
To stablize carbon, the generation of CR23C6 is prevented, to achieve the purpose that prevent Sensitized grain boundary corrosion.Titanium and aluminium are as valve
The important alloying element of steel, can with nickel, the stable intermetallic compound of the formation such as niobium, such as γ ' phase Ni3 (Al, Ti), this metal
Between compound mutually there is orderly face-centred cubic structure, and the matrix isomorphism, lattice constant also very close to, at high temperature can for a long time with
Matrix keeps symbiosis and epibiosis, with this with particularly good solid solution strengthening effect.It is hardening constituent important in the present invention, simultaneously
γ ' mutually also has the ability of solid solution other elements, and such as Ta, Nb can form Ni3 (Al, Ti, Nb), and the solid solution of other elements adds
Enter, increases the effect of solution strengthening.While formation is this to have excellent hardening constituent, in titanium and higher aluminium content, titanium
η phase Ni3Ti can be also formed with nickel, it is in needle in metallographic structure that this composition phase with hexagonal structure, which does not dissolve other elements,
Shape distribution, can make steel become fragile, be a kind of harmful phase.In order to make up the loss that the reduction of nickel element uses bring performance, therefore group
Metallographic in knitting should control γ ' Ni3 (Al, Ti) as far as possible, the precipitation of Ni3 (Al, Ti, Nb) and γ " phase Ni3Nb prevents η
The precipitation of phase Ni3Ti.The type and quantity of precipitated phase depend primarily on the total amount and Ti/Al ratio of Al and Ti.Increase Al's and Ti
Total amount can significantly improve γ ' phase solid solubility temperature and volume fraction.After identical heat treatment, as Al and Ti content increases,
The size of γ ' phase is gradually increased, and from spherical shape to cubic again, into irregular shape transformed steel, η phase starts largely γ ' phase morphology
Increase, while the rate of rise of η phase is significantly increased, and becomes in alloy and mainly generates phase.Low Ti/Al is more general than alloy higher
It is used when temperature, high Ti/Al is necessary good hot corrosion resistance than alloy, but excessively high Ti/Al ratio then holds
Easily there is the η-Ni3Ti phase of coarse sheet, make alloy embrittlement, reduces intensity and plasticity.For the performance being optimal, Valve Steel
Middle Ti content, aluminium content should meet 1.5 >=W of following equation (Ti)/W (Al) >=1.1,4.0% >=W (Ti)+W (Al) >=5.0%.
In order to meet above-mentioned formula, Ti content should be controlled 2.00~3.50%；It should preferably control 2.30~2.90%, aluminium content
Because controlling 1.40~2.40%, should preferably control 1.60~2.20%
Niobium: niobium and C have stronger affinity, can promote the precipitation of MC type carbide, form stable Nb C and Ta C
Carbide, in the Valve Steel for forming γ phase, these carbide are largely deposited in γ phase, have strong precipitation strength, carefully
Change the effect of crystal grain.In addition in conjunction with C, most Nb and Ta elements nearly all enter γ ' phase, promote the precipitation of γ ' phase, prolong
The agglomeration of slow γ ' phase, so that the elevated temperature strength for improving alloy can be such that stacking fault energy reduces, easily when metallic matrix is added in niobium
The binding force for generating extended dislocation and solute atoms and solvent atom is stronger, diffusion activation energy is increased, to improve compacted
Pole-changing limit.Niobium can form γ " phase Ni3Nb with nickel simultaneously, it has orderly body-centered structure of the quartet, the dot matrix mispairing with γ matrix
Spend larger, aging precipitation speed is relatively slow, has outstanding precipitation enhancement, and Valve Steel is made to have excellent fatigue at high temperature
Intensity and wearability.But niobium has very strong electronegativity, the serious antioxygenic property for damaging alloy.Therefore niobium element content should control
Between 0.40~0.90%.
Molybdenum: molybdenum is effective solution strengthening element, can reduce alloy stacking fault energy, to improve the high-temperature behavior of alloy.
Molybdenum can significantly improve adding for γ, γ ' lattice misfit rate in alloy, the foundation of promotion two-phase interface dislocation network, while molybdenum element
Stacking fault energy can also be reduced by entering, to improve the croop property of alloy.In addition, can promote with the addition of molybdenum element
The pattern of γ ' phase changes to cube, and this γ ' with cubic morphology mutually has better strengthening effect.But when molybdenum is added
When excessive, the degree of supersaturation of molybdenum in matrix can be made excessive, brittlement phase can be promoted to be precipitated, deteriorate alloy property.Therefore inventor suggests
The content of molybdenum should be controlled 0.40~1.00%.
The preparation method of modified valve stainless steel of the invention includes: to weigh raw material in vaccum sensitive stove by quality proportioning
Middle melting, solution pours into consutrode and ingot casting is made in remelting refining in electroslag furnace, and ingot casting is forged at high temperature and is obtained
Stainless steel forgings.
The utility model has the advantages that a modification of the present invention type valve stainless steel and preparation method thereof, which provides one kind, has outstanding height
Warm fatigue strength, wearability, the valve stainless steel of corrosion resistance, while guaranteeing good thermal processability, preparation method simply may be used
Row, and there is certain economic benefit.
Specific embodiment
Here following embodiment must be noted that unless otherwise instructed, percentage all indicates mass percent.
Embodiment 1
Raw material is weighed by the composition proportion of table 1, melting is prepared into consutrode block in vaccum sensitive stove, then in electroslag
Vacuum consumable smelting being carried out in furnace, ingot casting being made, electroslag matches CaF2:76%, Al2O3:9%, TiO2:5%, MgO:10%.Casting
Ingot is forged at 1150 DEG C or so, is finally rolled into the alloy bar material of Φ 9mm on milling train after intermediate forging.Bar warp
1050 DEG C of 0.5h, 750 DEG C of 4h solution treatment.
Table 1
Embodiment 2
Raw material is weighed by the composition proportion of table 2, melting is prepared into consutrode block in vaccum sensitive stove, then in electroslag
Vacuum consumable smelting being carried out in furnace, ingot casting being made, electroslag matches CaF2:76%, Al2O3:9%, TiO2:5%, MgO:10%.Casting
Ingot is forged at 1150 DEG C or so, is finally rolled into the alloy bar material of Φ 9mm on milling train after intermediate forging.Bar warp
1050 DEG C of 0.5h, 750 DEG C of 4h solution treatment.
Table 2
Embodiment 3
Raw material is weighed by the composition proportion of table 3, melting is prepared into consutrode block in vaccum sensitive stove, then in electroslag
Vacuum consumable smelting being carried out in furnace, ingot casting being made, electroslag matches CaF2:76%, Al2O3:9%, TiO2:5%, MgO:10%.Casting
Ingot is forged at 1150 DEG C or so, is finally rolled into the alloy bar material of Φ 9mm on milling train after intermediate forging.Bar warp
1050 DEG C of 0.5h, 750 DEG C of 4h solution treatment.
Table 3
Embodiment 4
Raw material is weighed by the composition proportion of table 4, melting is prepared into consutrode block in vaccum sensitive stove, then in electroslag
Vacuum consumable smelting being carried out in furnace, ingot casting being made, electroslag matches CaF2:76%, Al2O3:9%, TiO2:5%, MgO:10%.Casting
Ingot is forged at 1150 DEG C or so, is finally rolled into the alloy bar material of Φ 9mm on milling train after intermediate forging.Bar warp
1050 DEG C of 0.5h, 750 DEG C of 4h solution treatment.
Table 4
Comparative example 1
Alloy cast ingot, forged rolling alloy bar material will be prepared into using conventional method by the ingredient of table 5.
Table 5
Comparative example 2
Alloy cast ingot, forged rolling alloy bar material will be prepared into using conventional method by the ingredient of table 6.
Table 6
Test example
It chooses the alloy bar material that above-mentioned 4 embodiments and test example obtain and carries out assessment of performance, it is anti-including high temperature
Tensile strength, elongation percentage, hardness, corrosion resistance, wearability.Test result is as shown in table 7.The specific experiment condition of experiment is as follows:
High-temperature mechanics experiment carries out at 750 DEG C of experimental temperature, and corrosion resistance experiment carries out at normal temperature, and sample size is Φ 9*
20mm, 10% acetum of etchant solution, when experiment a length of 24H.Wearability experimental method sample size Φ 9*20mm, experiment rub
The drag ring of the Φ 16*40*50 of secondary GCR15 steel machine addition, hardness 63HRC, revolving speed 200r/min are wiped, experiment load is
100N, experiment condition are dry friction, and experimental period is 60min Φ
7 the performance test results of table
As can be seen from the above table, the more common iron-based austenitic stainless steel of modified Valve Steel provided by the present invention has
More outstanding elevated temperature strength, corrosion resistance, wearability can reach or even surmount the performance of the higher nickel-base alloy of nickel content
Level has considerable economic benefit.
The above is only a preferred embodiment of the present invention, it should be pointed out that: for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (7)
1. a kind of modified valve stainless steel, it is characterised in that by weight percentage and including following component:
Carbon: 0~0.20%；
Silicon: 0~1.00%；
Manganese: 0~1.00%；
Phosphorus: 0~0.035%；
Sulphur: 0~0.035%；
Chromium: 12.5~16.5%；
Nickel: 28.0~35%；
The modified valve stainless steel also comprises the following components by weight percentage:
Molybdenum: 0.20~1.50%；
Aluminium: 1.40~2.40%；
Titanium: 2.0~3.50%；
Niobium: 0.20~0.15%；
Remaining is iron and inevitable impurity.
2. a kind of modified valve stainless steel according to claim 1, it is characterised in that by weight percentage and including such as
Lower component:
Carbon: 0~0.08%；
Silicon: 0~0.50%；
Manganese: 0~0.50%；
Phosphorus: 0~0.015%；
Sulphur: 0~0.010%；
Chromium: 13.5~15.5%；
Nickel: 30.0~33.5%；
The modified valve stainless steel also comprises the following components by weight percentage:
Molybdenum: 0.40~1.00%；
Aluminium: 1.60~2.20%；
Titanium: 2.30~2.90%；
Niobium: 0.40~0.90%；
Remaining is iron and inevitable impurity.
3. aluminium and Ti content meet following formula in a kind of modified valve stainless steel according to claim 1 or 2:
1.5 >=W (Ti)/W (Al) >=1.1,4.0% >=W (Ti)+W (Al) >=5.0%.
4. a kind of preparation method of modified valve stainless steel as claimed in claim 1 or 2 weighs raw material by quality proportioning and melts
Refining, solution pours into consutrode and ingot casting is made in remelting refining, and ingot casting is forged at high temperature and obtains stainless steel forgings.
5. the melting as claimed in claim 4 carries out in vaccum sensitive stove, the remelting refining carries out in electroslag furnace.
6. the smelting temperature as claimed in claim 4 is 1460~1490 DEG C.Electroslag remelting refines slag charge used by following heavy
Amount percentage at being grouped as: CaF2:76%, Al2O3:9%, TiO2:5%, MgO:10%.
7. the temperature of heats forged is 1140~1160 DEG C as claimed in claim 4.
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| CN111004976A (en) * | 2019-12-30 | 2020-04-14 | 钢铁研究总院 | Nickel-saving type air valve alloy and preparation method thereof |
| CN114752845A (en) * | 2021-01-08 | 2022-07-15 | 宝武特种冶金有限公司 | Nickel-saving high-carbon iron-based high-temperature alloy and preparation method thereof |
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| CN114752845A (en) * | 2021-01-08 | 2022-07-15 | 宝武特种冶金有限公司 | Nickel-saving high-carbon iron-based high-temperature alloy and preparation method thereof |
| CN114752845B (en) * | 2021-01-08 | 2023-09-08 | 宝武特种冶金有限公司 | Nickel-saving type high-carbon iron-based superalloy and preparation method thereof |
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