CN109504911A - A kind of cupric vanadium high intensity high corrosion resistance austenitic stainless steel and preparation method thereof - Google Patents
A kind of cupric vanadium high intensity high corrosion resistance austenitic stainless steel and preparation method thereof Download PDFInfo
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Abstract
A kind of cupric vanadium high intensity high corrosion resistance austenitic stainless steel and preparation method thereof, alloying element content are as follows: C≤0.08, Ni=10.0~14.0, Cr=16.0~18.5, Mo=2.0~3.0, V≤0.34, Cu=0.2~0.8, Mn≤2.0, Si≤1.0, P≤0.035, S≤0.030, wherein 4.24 × (C-0.01)≤V≤4.24 × C, surplus Fe.After alloy smelting, coarse austenite grain is obtained by higher temperature solid solution so that VC is able to sufficiently broken, Dispersed precipitate through thermal deformation cogging and cold deformation.Lower 80 DEG C of logical hydrogen condition contains 5 × 10‑6F‑0.5mol/L H2SO4Alloy corrosion electric current is 6.4~9.7 μ A/cm in electrolyte2, 316 stainless steels are compared, corrosion rate is greatly lowered, and mechanical property is slightly better than 316 stainless steels.
Description
Technical field
The invention belongs to field of Austenitic stainless steel, be related to high corrosion-resistant austenitic stainless steel ingredient design and processing,
Heat-treating methods can be widely used for the energy, electric power, chemical field and daily life.
Technical background
Stainless steel is widely used in the fields such as the energy, electric power, chemical industry because having excellent mechanics and corrosion resistance.It is difficult to understand
Family name's body stainless steel is because it has good mechanical property, processability, corrosion resisting property and resistance to neutron irradiation performance, in nuclear power
It is widely used in industry.The key equipments such as presurized water reactor primary Ioops main pipeline, in-pile component, driving mechanism, main pump and pump shaft
Main material all use 304L, 316LN type austenitic stainless steel as structural material.These materials in high temperature and pressure and
It is on active service in the harsh chemical environment of water such as irradiation, not only to guarantee the integrality of structure, rushing for all kinds of special working medium must also be resisted
Brush and corrosion, to reduce abrasion and corrosion product in the activation of reactor core and reactor core external radiation field.
Pressurized-water reactor nuclear power plant primary Ioops main pipeline is to prevent core anti-under normal nuclear power station, improper, accident and operating condition of test
Fission product is answered to leak to the important barrier of containment.Therefore, being capable of high temperature resistant, high pressure resistant and corrosion resistant for main nuclear power pipeline
Erosion.The part main pipeline of early stage nuclear power station has selected low alloy steel, and the built-up welding stainless steel in pipe；Later main nuclear power pipeline
18-8 type austenitic stainless steel is generallyd use, ingredient and production technology are continuouslyd optimize, forms following several situations: (1) being stablized
The austenitic stainless steel of change: being added titanium (Ti) in 18-8 type stainless steel or niobium (Nb) improves intergranular corrosion resistance performance, but it is welded
It is bad and cause field trash excessively and influence the processing of bend pipe to connect performance；(2) austenitic stainless steel of standard 304 and 316: 304 is stainless
Steel reduces carbon content on the basis of 18-8 type austenitic stainless steel, and 316 steel joined 2% molybdenum (Mo) again, but they 480~
Extended stationary periods still have the tendency that " being sensitized " between 820 DEG C；(3) low-carbon 304L and 316L austenitic stainless steel: in original steel grade
On continue to reduce carbon content, obtain excellent intergranular corrosion resistance, welding performance and processing performance, but maximum problem is intensity
It is insufficient.The primary Ioops main pipeline of 2nd generation pressurized-water reactor nuclear power plant increases in austenitic matrix using Cast Duplex Stainless Steel
A small amount of ferrite (12%~20%), not only increases the intensity and hot-cracking resistance of material, additionally it is possible to inhibit stress corrosion
Occur.But no more than 20% otherwise more serious heat ageing phenomenon can occur for ferrite content.3rd generation presurized water reactor A P1000
The primary Ioops main pipeline of nuclear power station uses the 316LN austenitic stainless steel of solid forging, and it is stainless to belong to Ultra-low carbon control nitrogen austenitic
Steel is that nitrogen is added on the basis of 316L, can either improve the intensity of material, while still keeping higher plasticity and toughness water
It is flat.
In-pile component refers to that the entire infrastructure component in pressure vessel in addition to fuel assembly and associated components, component are numerous
It is more, structure is complicated, required precision is high, and need to bear the tests such as high temperature and pressure, neutron irradiation, coolant corrosion.Therefore, it reacts
The selection principle of in-pile component material is general are as follows: intensity is appropriate high, plasticity and toughness are good, can shock resistance and antifatigue；Neutron-absorbing circle
Face and neutron-capture cross section and artificial radioactivity are small；It is Flouride-resistani acid phesphatase, corrosion-resistant and good with coolant compatibility；Thermal expansion coefficient
It is small；Good welding and process for machining performance.The heap interior main body structural material of 2nd generation pressurized-water reactor nuclear power plant is usually austenite
Stainless steel, such as 304L, 304LN, 321,347,310, bolt class material is 316L N, 321H stainless steel, and certain special parts use
Martensitic stain less steel, such as the 1Cr13 of holddown spring.3rd generation presurized water reactor AP1000 nuclear power station, more powerful, longer life expectancy,
It is tighter to the ingredient and performance requirement of in-pile component.F304 the and F304H austenite stainless of its main structure material selection forging
Steel, holddown spring use follow-on 403 martensitic stain less steel.
The ventilation cleaning equipment of nuclear power station is mainly used for sending, in exhaust system, can be installed according to different applying working conditions different
The air filter unit of type.For realizing air cleaning, especially suitable for it is contaminated or pernicious gas give, exhaust system,
The health of system worker safety and ambient enviroment can be effectively protected.The ventilated purification apparatus majority of nuclear power plant is to use Ovshinsky
The stainless steel making of body.Austenitic stainless steel has excellent corrosion resistance, preferable anti-radiation performance.But nuclear power station is most
It build coastal area in, sea-air humidity is big, and salt content is high, and chloride ion is one of main inducing of Corrosion of Stainless Steel.For
Guarantee that the safety of nuclear power plant's air ventilation and purification system, the corrosion resistance that improves austenitic stainless steel are particularly important.
Sodium-cooled fast reactor is one of six kinds of alternative heap-type of forth generation nuclear power, is the second step of three step development plan of China's nuclear energy,
It is also an important ring for China's nuclear energy closed cycle.Sodium-cooled fast reactor compared with presurized water reactor, have temperature higher (500 DEG C or more),
The features such as irradiation dose is higher.To reactor core assembly structural material, such as Stainless Steel Cladding, more stringent requirements are proposed.Sodium-cooled fast reactor
The pipelines such as steam generator, heat exchanger are also required to a large amount of high performance Austenitic stainless steel pipe, such as 316Ti, 316H.
As it can be seen that the common austenitic stainless steel of nuclear power station has 304 (0Cr18Ni9), 304L (00Cr19Ni10) and 316L
(00Cr17Ni14Mo2).304 stainless steels are a kind of stainless steels of versatility, it is widely used in production and requires good comprehensive performance
The equipment and parts of (corrosion-resistant and mouldability).304 stainless steels have excellent corrosion resistance and preferable anti intercrystalline corrosion
Performance.304L stainless steel is the mutation of 304 relatively low stainless steels of phosphorus content, the occasion for needing to weld.It is lower carbon containing
Amount so that the carbide that is precipitated minimize in the heat affected area close to weld seam, and the precipitation of carbide may cause it is stainless
Steel generates intercrystalline corrosion in certain environment.Therefore the ability of the anti intercrystalline corrosion of 304L stainless steel is better than 304 stainless steels.316L is not
Rust steel is also known as titanium steel, adds Mo (2~3%), the stability of passivating film can be improved.316L stainless steel has outstanding resistance to spot corrosion
Property and resistance to intergranular corrosion, also with good resistance to chloride attack performance, in marine environment or aggressivity industrial atmosphere
Resistance to corrosion be greatly better than 304 stainless steels and 304L stainless steel.316L stainless steel > 304L for from corrosion resistance
Stainless steel > 304 stainless steels, super-low carbon stainless steel are better than the common stainless steel of same grade of steel again.Add Ti, Mo or solution treatment is prevention
The main method of stainless steel spot corrosion.
Under normal circumstances, stainless steel material has good corrosion resistance, in Nuclear Power Station Factory Building structure, numerous is
In equipment of uniting, stainless steel has very extensive application, from the large container inside nuclear island, pipeline, arrives various valves, gauge pipe
Line and the component of various equipment etc., stainless steel have satisfactory corrosion resisting property.Stainless steel Corrosion Resistant Mechanism is in its table
Oxygen in the elements such as face Cr and air generates one layer of very thin, fine and close, adherence is good passivating film, as one of protection screen
Barrier, corrosive medium and matrix are kept apart；Although the metal in passivating film protection still has certain respond, passivating film
There is good self-regeneration function.However the stainless steel materials such as nuclear power station pipeline, equipment local environment is complicated, in some conditions
Under be difficult to ensure the intact of passivating film, such as corroded by high-concentration chlorine ion, then can cause corrosion.Nuclear power plant equipment fortune
Row operating condition, environment are complicated, and in some special cases, stainless steel material not only cannot effectively resist corrosion, but also can go out
Now such as spot corrosion, intercrystalline corrosion, crevice corrosion, stress corrosion, phenomena such as, these local corrosions are not easy to realize, but with corrosion
Development, on equipment influence be fatal.External nuclear power station has more Corrosion of Stainless Steel cases and occurs, and suffers heavy losses.
The common Corrosion of Stainless Steel characteristic of nuclear power station is as follows:
(1) spot corrosion: being the local corrosion that metal surface is relatively concentrated in a very little position.Before real spot corrosion, no
Several microns of diameter of miniature recess is initially formed in the protective oxide layer for steel surface of becoming rusty, the swift and violent increase of this miniature recess is
The reason of causing stainless steel to corrode on a large scale.Stainless steel forms CrO after the acid wash passivation on surface3Or Cr2O3Oxidation film makes
It obtains stainless steel and plays maximum corrosion resistance, effectively block the erosion and destruction of corrosive media.Nuclear power plant's stainless steel equipment
There is a situation where corroding usually spot corrosion, the position that spot corrosion occurs is generally present in the passivating films such as gap, scratch surface and is destroyed
Surface.If stainless steel surface is moist and contains chloride ion, it can be partially formed strong acid dissolution passivating film, destroyed stable
Passive state leads to the corrosion of large area.Stainless steel corrodes in general air or fresh water environment, and surface will form one
The fine and close oxidation film of layer, is suppressed steel corrosion process.But under marine environment, air chloride ion content is higher, and chlorine
Ion is easy to the oxygen in substitutionary oxydation film and destroys oxidation film, this just makes to be difficult to establish under certain density chloride environment steady
Fixed passive state.With accumulation of the chloride ion in equipment, the concentration of chloride ion can be higher and higher, can get over to the corrosivity of stainless steel
Come bigger.
(2) intercrystalline corrosion: it is the common local corrosion of one kind of metal erosion, corrodes since metal surface, along gold
Belong to intercrystalline boundary to extend towards intra-die, weakens intercrystalline binding force significantly.It is a kind of selective corrosion, edge
Crystal boundary gos deep into metal inside can but be such that material loses in the case that this corrosion makes metal not see any sign on the outer surface
Its mechanical property is lost, or even material is made to lose intensity completely, it is one of highly harmful form of partial corrosion.Nuclear power station is logical
For wind cleaning equipment during long time running, the intergranular that chloride ions accumulated will lead to Stainless Steel Shell to a certain extent is rotten
Erosion.By the stainless steel of this corrosion, any corrosion or damage are not gone out on surface, but the crystal boundary area inside stainless steel suffers from
It destroys.Corrosion reaches a certain level the destruction that will result in component or equipment, will affect the safety fortune of entire nuclear power station when serious
Turn.There are excellent toughness, plasticity, weldability and corrosion resistance under austenitic stainless steel room temperature and low temperature, has and resist chemical attack
With electrochemical corrosion ability.
(3) corrosion fatigue: in nuclear power station operational process, coolant temperature, pressure change or start and stop reactor process are equal
Stress loading can be caused to act on primary Ioops main pipeline, while the high-temperature high pressure water in main pipeline can cause oxidation or rotten to inner wall
Erosion effect, therefore corrosion fatigue is also one of dominant failure mode of main pipeline material.
(4) stress corrosion: stress corrosion cracking (Stress corrosion cracking, SCC) is nuclear power primary Ioops peace
Full end different-metal material welding connector is in one of military service process important failure forms of aerial.During stress corrosion, nuclear power knot
Structure material works at high temperature under high pressure, simultaneously because the presence of the Crack-area region of high stress, so that splitting point can nearby generate
Creep.Since the water environment temperature of nuclear power primary Ioops is 288~340 DEG C, the creep of middle generation belongs under actual condition
" low temperature " (creep temperature is in 0.3TmHereinafter, TmFor the fusing point of material) creep, and split point there are the regions of high stress, it is easier to occur
Creep under " low temperature " high stress.Stainless steel material in high concentration basic solution or high temperature low concentration alkaline solution still
Can so it occur stress corrosion cracking (SCC), therefore its SCC behavior in high-temperature alkaline solution is always research emphasis.
Summary of the invention
The object of the present invention is to provide a kind of cupric vanadium high intensity high corrosion resistance austenitic stainless steels and preparation method thereof.This hair
Bright its technical problem of solution adds strong carbon the technical scheme adopted is that on the basis of 316 austenitic stainless steel alloy ingredient
Compound formation element vanadium (V) and austenite former copper (Cu), abbreviation 316-CV stainless steel.Its specific ingredient (quality percentage
Than) are as follows: C≤0.08, Ni=10.0~14.0, Cr=16.0~18.5, Mo=2.0~3.0, V≤0.34, Cu=0.2~
0.8, Mn≤2.0, Si≤1.0, P≤0.035, S≤0.030, wherein more than 4.24 × (C-0.01)≤V≤4.24 × C, Fe=
Amount.After alloy smelting, handled through overheating deforming cogging and cold deformation, so that the VC formed is able to sufficiently broken, Dispersed precipitate, then
By higher temperature solid solution, coarse grain austenite structure is obtained, higher-strength and corrosion resistance are made it have.
316 be U.S.'s trade mark, and corresponding China's stainless steel trade mark is 0Cr17Ni12Mo2；Corrosion resistance is stainless better than 304
Steel has good corrosion resistant performance in slurry and the production process of papermaking.And the 316 also resistance to ocean of stainless steel and aggressivity
The erosion of industrial atmosphere.The performance indicator of its plate are as follows: yield strength >=205MPa, tensile strength >=520MPa, elongation >=
40%, hardness≤HV200.
Contain the C not higher than 0.08% in 316 stainless steels.C in austenitic stainless steel is imitated with stronger solution strengthening
Fruit, but C is easy to form cementite Fe in conjunction with Fe3C is precipitated in lamella, the corrosion resistance of stainless steel is caused to be difficult to improve.Therefore,
Carbide V is added in the alloy, the spherical particle VC compound of high stability is formed, so that austenite crystal
The solid solution content of practical C is greatly lowered in grain, improves the corrosion resistance of stainless steel.Since the atomic weight of V is 50.94, and the original of C
Son amount is 12.01, and the atomic weight ratio of V, C are 4.24, as 4.24 × (C-0.01)≤V≤4.24 × C, as C content is
When 0.08%, the content of V is 0.30%~0.34%, and the solid solution content of practical C is not less than 0.01% in austenite grain, and not
Have the surplus of V element.
Cu is non-carbide forming element, is added in steel and will form substitution solid solution.The Cu of every addition 1.0% can in steel
The solution strengthening effect of 38~70MPa is generated, and copper adds the increment that caused yield strength increment is higher than tensile strength,
And then the yield tensile ratio of steel can be improved significantly.The Cu ion for not luring steel surface to dissolve out can destroy bacterium internal protein structure,
Inhibit the duplication and the synthesis of related protein/enzyme of DNA of bacteria, destroys the metabolic activity in bacterium, so that bacterium is lost activity, lead
Cause bacterial death.Therefore 1~3%Cu is often added in some weathering steel, improves the corrosiveness of the resistance to marine environment of alloy.
A small amount of Cu is added in the present invention, the deficiency of C element when being to make up high-temperature heat treatment there are one significance.
There are a large amount of Cr, Ni element in austenitic stainless steel, the segregation of Cr, Ni element be also cause the corrosion resistance of stainless steel be difficult into
The main reason for one step improves.Therefore it needs to promote Cr, Ni to spread and homogenize in soak, and the presence of C element, have
Conducive to the diffusivity for improving alloying element.Due to being added to carbide in the present invention, so that austenite grain
Middle C solid solution content is very low, is unfavorable for homogenizing, it is therefore desirable to supplement a small amount of Cu, improve diffusivity, overcome Cr, Ni element
Segregation further increases corrosion resistance.
The preparation method of the 316-CV stainless steel includes following key step:
(1) smelting and casting of 316-CV stainless steel
Selection electrical pure iron, crome metal piece, metal nickel plate, metal molybdenum, stainless steel waste material, fine copper plate, vanadium iron or vanadium metal,
Graphite block is raw material, after electric arc melting or induction melting, is cast into alloy cast ingot.
It, should not be using stainless steel industries producers such as Converter vacuum oxygen decarburization methods since alloy is added to the elements such as Cu, V
Method can only prepare alloy using electric arc melting or induction melting method.It takes vacuum or argon gas to protect when melting, avoids aoxidizing.
Stainless steel waste material is mainly the austenitic stainless steel waste material that 316,316L etc. has nickelic, Gao Ge, high molybdenum content, then
With the raw materials such as electrical pure iron, crome metal piece, metal nickel plate, metal molybdenum, fine copper plate, vanadium iron or vanadium metal, graphite block, described
Alloyage in the composition range of 316-CV stainless steel, controls the essential elements such as C, Cr, Ni, Cu, V in alloy, and Mn, Si,
P, the impurity elements such as S are guaranteed by the purity of raw material.
Bath temperature is kept for 1700 DEG C ± 20 DEG C when melting；Molten steel calmness 5~10 minutes before being poured, molten steel 1550 DEG C ±
50 DEG C, vacuum or argon for protecting pouring.According to subsequent product specification needs, the side's of being cast as ingot or billet.
(2) ingot casting thermal deformation cogging is processed
Hot forging, groove rolling or universal rolling cogging can be used in pipe, stick, line, profile and cold punching part, ingot casting；Plate can
Using flat roll mill hot rolling cogging.
Forging scheme is that slab is heated to 1250 DEG C ± 10 DEG C, forging of coming out of the stove after keeping the temperature 3~5 hours, and initial forging temperature is
1150 DEG C ± 20 DEG C, final forging temperature >=1000 DEG C, forging ratio >=2.0, ratio of elongation >=2.0, always than >=4.0；
Blank after hot forging carries out roll piercing again, can get tube billet；
Hot rolling scheme is that slab is heated to 1280 DEG C ± 10 DEG C, rolling of coming out of the stove after keeping the temperature 3~5 hours, hot rolling initial forging temperature
It is 1180 DEG C ± 20 DEG C, finishing temperature >=950 DEG C.The contraction percentage of area of groove rolling or universal rolling cogging answers >=60%；Plate
Material hot rolling is always lower to measure >=60%.
(3) cold deformation
Pipe, stick, line, profile can be used reciprocating type tube rolling, groove rolling, universal rolling or the method dialled drawn to carry out cold change
Shape obtains size, the specification of product requirement, and the total deformation of cold deformation is calculated according to the contraction percentage of area, is not less than 80%；
The stainless steel parts that mechanical industry needs can also use thermal deformation cogging raw material, then be obtained by cold stamping, cold
Forging ratio >=5.0 of punching press.If forging ratio is insufficient, stamping blanks should be handled using cold forging in advance, guarantee total cold deformation.
Plate uses cold-rolling deformation, cold rolling overall reduction >=80%.
The main purpose of thermal deformation and cold deformation is that the carbide in alloy is sufficiently broken；Big cold deformation is conducive to
Guarantee to form coarse brilliant tissue when subsequent heat processing.
(4) high-temperature heat treatment
It after cold deformation, is made annealing treatment at 1085 DEG C ± 30 DEG C, soaking time is 30 minutes~120 minutes, when heating
Using the inert gas shieldings such as vacuum or argon gas, nitrogen, helium；After annealing, using the gases such as water, oil or argon gas, nitrogen helium
Medium is quickly cooled down.
The purpose of soak is to form coarse recrystal grain, so that breaked spherical particle carbide is from crystal boundary
It is transferred to inside coarse recrystal grain, to mitigate grain boundary corrosion tendency.It is quickly cooled down in addition to can be to avoid a small amount of remnants
Outside the crystal boundary of carbide is precipitated, most important purpose is to control the segregation of Cu element, improves the solid solubility of Cu element, obtains high
Intensity and hardness.
According to the requirement of the size of product and Surface Quality, cooling medium is selected, when product size is larger, can be adopted
The liquid mediums such as water intaking, oil, which are realized, to be quickly cooled down, and thin plate or small part can take the fast quickly cooling of the gas mediums such as argon gas, nitrogen helium
But.
The implementation of above-mentioned high-temperature heat treatment method can be used heating in vacuum-air quenching, laser heating-water hardening, continuously add
Heat-high pressure gas quenching, gas shield heating-water (oil) are quenched.Carried out after annealing aligning or setting treatment, aligning or sizing at
The deflection of reason should be less than 2%.
316-CV stainless steel by above-mentioned high-temperature heat treatment obtains corrosion electricity using Ta Feier (Tafel) line extrapolation
Stream, as the foundation of comparative alloy corrosion resistance, and measures the hardness and tensile mechanical properties of alloy.
Ta Feier (Tafel) line extrapolation is a kind of method for measuring corrosion rate.Way is that electricity is made in metal sample
Pole is immersed in corrosive medium, is measured volt-ampere (E~I) data of stable state, is made log | I |~E figure, and by the straight of negative anodic polarization curve
Line part extends.Corresponding gained intersection point is logIcor, by corrosion current IcorDivided by the sample area of prior precise measurement
S0To get corrosion rate.This method is quickly time saving, the measurement suitable for metal homogeneous corrosion.
The water environment temperature of nuclear power primary Ioops is 288~340 DEG C, obtains the water ring of high pressure due to being difficult in measurement
Border, therefore select 80 DEG C of comparisons that corrosive nature is carried out as test temperature.The specific determination condition of corrosion rate are as follows: with 1cm2
Stainless steel is working electrode, using saturated calomel electrode as reference electrode, using platinized platinum as auxiliary electrode；Containing 5 × 10-6F-'s
The H of 0.5mol/L2SO4Electrolyte is heated to 80 DEG C with water bath, and is passed through hydrogen into electrolyte with the flow velocity of 20ml/min；
Linear sweep voltametry, sweep speed 2mV/s are carried out to sample.With the perseverance of electrochemistry constant potential tester or electrochemical workstation
Potentiometer function completes measurement, carries out Ta Feier (Tafel) to the polarization curve measured using the test software of instrument and is fitted, obtains
Obtain corrosion current.316 stainless steels of above method measurement corrosion current in room temperature is 74 μ A/cm2, it is 355 μ A/ at 80 DEG C
cm2。
Of the invention is mainly characterized by the basis of 316 stainless steel alloy, adds carbide V, reduces
The solid solubility of practical C in austenite grain；It adds Cu element and improves High temperature diffusion ability, avoid Cr, Ni Element segregation, and it is arrived
Solution strengthening effect；Subsequently through thermal deformation, cold deformation, causes carbide broken, be quenched by high temperature, form coarse crystalline substance
The super saturated solid solution of grain and Cu element is strengthened, and while so that alloy has higher hardness and intensity, has superior anti-corrosion energy
Power.For the corrosion current of 316-CV alloy after high temperature quenching treatment under logical hydrogen condition, 80 DEG C contain 5 × 10-6F-0.5mol/L
H2SO4It is 6.4~9.7 μ A/cm in electrolyte2, compared to 316 alloys, corrosion rate is greatly lowered.Hardness be 186~
195HV1, yield strength are 277~294MPa, and tensile strength is 583~610MPa, and elongation percentage 41~47% is closed better than 316
Gold.
Detailed description of the invention
1 polarization curve of Fig. 1 present example；
2 tensile mechanical properties curve graph of Fig. 2 present example；
3 corrosion surface electron microscope scanning figure of Fig. 3 present example.
Specific embodiment
Various method of smelting of the invention, casting method are not limited by following examples, any to want in right of the invention
The improvements and changes in range for asking book claimed are all within protection scope of the present invention.
Selection electrical pure iron, crome metal piece, metal nickel plate, metal molybdenum, stainless steel waste material, fine copper plate, vanadium iron or vanadium metal,
Graphite block is raw material, is configured to alloy in the composition range that invention requires.
For the requirement of shape, dimensions and surface quality, prepared stainless steel and its part are subsequent that machine can be used
Tool processing, polishing and corresponding chemical cleaning and polishing treatment, the present invention is not specifically limited.
Embodiment 1
Choosing electrical pure iron, crome metal piece, metal nickel plate, metal molybdenum, 316 stainless steel waste materials, fine copper plate, vanadium metal is original
Material, the stainless composition of steel of configuration are as follows: C=0.03, Ni=13.0, Cr=18.0, Mo=2.2, V=0.12%, Cu=0.2,
Mn=1.2, Si=0.8, P≤0.035, S≤0.030, Fe=surplus.Good corresponding raw material are weighed according to component requirements proportion
Afterwards, argon arc melting, bath temperature is kept for 1720 DEG C when melting；Molten steel is 10 minutes calm before being poured, and molten steel is 1650
DEG C, argon for protecting pouring.It is cast as billet.
Hot forging can be used in ingot casting, and the blank after hot forging carries out roll piercing again, obtains tube billet；Hot forging and oblique milling
Perforation is heated to 1260 DEG C, and heat preservation is come out of the stove forging after 5 hours, and initial forging temperature is 1170 DEG C, and 1020 DEG C of final forging temperature, breaking elongation
It is 3.
Pipe uses reciprocating type tube rolling, subsequent using empty drawing and fixed short core bar drawing, the total deformation of cold deformation
80% is calculated as according to the contraction percentage of area.
Tubing is made annealing treatment at 1115 DEG C, and soaking time is 30 minutes, is protected when heating using argon gas；After annealing,
Using water quenching cooling.
For the corrosion current of 316-CV alloy after high temperature quenching treatment under logical hydrogen condition, 80 DEG C contain 5 × 10-6F-'s
The H of 0.5mol/L2SO4It is 7.6 μ A/cm in electrolyte2, polarization curve is shown in Fig. 1.Hardness is 192HV1, and yield strength is
294MPa, tensile strength 583MPa, elongation percentage 42%.
Embodiment 2
Choosing 316 stainless steel waste materials, fine copper plate, vanadium iron is raw material, and the stainless composition of steel of configuration is as follows: C=0.04, Ni=
12.0, Cr=16.8, Mo=2.7, V=0.15, Cu=0.3, Mn=1.2, Si=0.7, P≤0.035, S≤0.030, Fe=
Surplus.
After weighing good corresponding raw material according to component requirements proportion, through vacuum induction melting, bath temperature is kept when melting
1680℃；Calm 5 minutes of molten steel before being poured, molten steel is at 1550 DEG C, vacuum pouring.The side's of being cast as ingot.
Slab is heated to 1270 DEG C, and heat preservation uses groove rolling cogging after coming out of the stove after 3 hours, it is 1160 DEG C that the beginning, which rolls temperature,
Finishing temperature=980 DEG C, rolling total contraction percentage of area is 62%；Using groove rolling obtain bar, rolling total deformation according to
The contraction percentage of area is calculated as 82%.Bar keeps the temperature 120 minutes at 1055 DEG C, and helium air quenching is taken after vacuum annealing.
For the corrosion current of 316-CV alloy after high temperature quenching treatment under logical hydrogen condition, 80 DEG C contain 5 × 10-6F-'s
The H of 0.5mol/L2SO4It is 8.5 μ A/cm in electrolyte2.Hardness is 190HV1, yield strength 285MPa, and tensile strength is
594MPa, elongation percentage 45%, tensile property curve are shown in Fig. 2.
Embodiment 3
Choosing electrical pure iron, crome metal piece, metal nickel plate, metal molybdenum, fine copper plate, vanadium iron, graphite block is raw material, configuration
Stainless composition of steel is as follows: C=0.05, Ni=12.0, Cr=18.0, Mo=2.2, V=0.21, Cu=0.4, Mn=0.8, Si=
0.5, P≤0.035, S≤0.030, Fe=surplus.
After weighing good corresponding raw material according to component requirements proportion, induction melting is protected through argon gas, bath temperature when melting
Kept for 1700 DEG C；Calm 7 minutes of molten steel before being poured, molten steel is at 1600 DEG C, argon for protecting pouring.It is cast as billet.
The Rolling With Universal Mill cogging of two pairs of parallel rolls can be used in ingot casting, after slab is heated to 1280 DEG C, heat preservation 4 hours
It comes out of the stove rolling, it is 1180 DEG C that the beginning, which rolls temperature, and finishing temperature is 1020 DEG C, rolls total contraction percentage of area and is calculated as 65%；
T-type profile is prepared into using universal rolling, total deformation is rolled according to the contraction percentage of area and is calculated as 85%；
It is made annealing treatment after cold rolling at 1100 DEG C, soaking time is 60 minutes, using nitrogen protection；Take continuous annealing
Furnace annealing is quickly cooled down after annealing with high pressure nitrogen.
For the corrosion current of 316-CV alloy after high temperature quenching treatment under logical hydrogen condition, 80 DEG C contain 5 × 10-6F-'s
The H of 0.5mol/L2SO4It is 9.7 μ A/cm in electrolyte2.Hardness is 187HV1, yield strength 277MPa, and tensile strength is
595MPa, elongation percentage 44%.
The electron microscope scanning figure of Fig. 3 corrosion surface, as can be seen from Figure 3, corrosion surface is very smooth, does not corrode
Product, but have many smooth apertures, the tiny carbide in surface, which preferentially corrodes, to fall off, and remaining smooth surface is homogeneous,
With stronger resistance to corrosion.
Embodiment 4
Choosing 316L stainless steel waste material, metal molybdenum, fine copper plate, vanadium metal, graphite block is raw material, the stainless composition of steel of configuration
It is as follows: C=0.06, Ni=13.0, Cr=18.5, Mo=2.5, V=0.25, Cu=0.5, Mn=1.3, Si=0.3, P≤
0.035, S≤0.030, Fe=surplus.
After weighing good corresponding raw material according to component requirements proportion, through vacuum induction melting, bath temperature is kept when melting
1690℃；Calm 8 minutes of molten steel before being poured, molten steel is at 1620 DEG C, vacuum pouring.The side's of being cast as ingot.
Ingot casting uses hot rolling cogging, and hot rolling scheme is that slab is heated to 1290 DEG C, rolling of coming out of the stove after keeping the temperature 3 hours,
Hot rolling initial forging temperature is 1200 DEG C, finishing temperature=950 DEG C, and hot rolling is always lower to measure=60%.
Plate uses cold-rolling deformation, cold rolling overall reduction=80%.
It is made annealing treatment after cold rolling at 1105 DEG C, soaking time is 45 minutes, and vacuum annealing, oil quenching are used when heating.
For the corrosion current of 316-CV alloy after high temperature quenching treatment under logical hydrogen condition, 80 DEG C contain 5 × 10-6F-'s
The H of 0.5mol/L2SO4It is 6.4 μ A/cm in electrolyte2.Hardness is 195HV1, yield strength 279MPa, and tensile strength is
610MPa, elongation percentage 47%.
Embodiment 5
Choosing electrical pure iron, crome metal piece, metal nickel plate, metal molybdenum, fine copper plate, vanadium iron, graphite block is raw material, configuration
Stainless composition of steel is as follows: C=0.07, Ni=13.0, Cr=17.0, Mo=2.5, V=0.29, Cu=0.7, Mn=0.6, Si=
0.3, P≤0.035, S≤0.030, Fe=surplus.
After weighing good corresponding raw material according to component requirements proportion, through argon atmosphere electric arc melting, bath temperature when melting
Kept for 1700 DEG C；Calm 6 minutes of molten steel before being poured, molten steel is at 1620 DEG C, argon for protecting pouring.The side's of being cast as ingot.
Hot forging can be used in ingot casting, and ingot casting is heated to 1255 DEG C, forging of coming out of the stove after keeping the temperature 3 hours, and initial forging temperature is
1150 DEG C, final forging temperature is 1050 DEG C, is forged always than being 4.0；
Groove rolling is carried out after hot forging and obtains line bar, and line bar, which carries out drawing again, dials deformation, and total deformation is according to the contraction percentage of area
It is calculated as 86%；
Cold pull wire is made annealing treatment at 1100 DEG C, and soaking time is 90 minutes, and vacuum protection, heat preservation are used when heating
After use high pressure argon gas air quenching.
For the corrosion current of 316-CV alloy after high temperature quenching treatment under logical hydrogen condition, 80 DEG C contain 5 × 10-6F-'s
The H of 0.5mol/L2SO4It is 7.8 μ A/cm in electrolyte2.Hardness is 186HV1, yield strength 285MPa, and tensile strength is
605MPa, elongation percentage 46%.
Embodiment 6
Choosing 316 stainless steel waste materials, fine copper plate, vanadium iron, graphite block is raw material, and the stainless composition of steel of configuration is as follows: C=
0.08, Ni=12.2, Cr=17.5, Mo=2.6, V=0.34, Cu=0.8, Mn=1.2, Si=0.6, P≤0.035, S≤
0.030, Fe=surplus.
After weighing good corresponding raw material according to component requirements proportion, through vacuum induction melting, bath temperature is kept when melting
1710℃；Calm 8 minutes of molten steel before being poured, molten steel is at 1580 DEG C, vacuum pouring.The side's of being cast as ingot.
Hot forging can be used in ingot casting.Forging scheme is that slab is heated to 1250 DEG C, and forging of coming out of the stove after keeping the temperature 3 hours is begun
Forging temperature is 1150 DEG C, and final forging temperature=1000 DEG C are forged always than=4.0；
Blank first uses cold forging to handle, then carries out cold punching pressing formation and obtain stamping parts, total forging ratio=5.0 of cold deformation.
It after cold deformation, is made annealing treatment at 1065 DEG C, soaking time is 85 minutes, using nitrogen gas protection and oil
It is cold.
For the corrosion current of 316-CV alloy after high temperature quenching treatment under logical hydrogen condition, 80 DEG C contain 5 × 10-6F-'s
The H of 0.5mol/L2SO4It is 9.0 μ A/cm in electrolyte2.Hardness is 193HV1, yield strength 286MPa, and tensile strength is
590MPa, elongation percentage 41%.
The performance detection of the preparation process of above-described embodiment 316-CV alloy obtained is as described below:
1. pair example alloy material carries out hardness test, load 1Kg, after making a call to 5 points using HVS-50 Vickers
It is averaged, is listed in table 1.
2. pair example alloy material carries out stretching experiment using almighty test machine, the nominal section of sample having a size of 1~2 ×
The rectangular specimen of 5 × 30mm takes the average value of the tensile strength of 3 same treatment samples, yield strength and elongation percentage to be listed in table 1
3. pair example alloy carries out corrosion current measurement, the condition of test are as follows: with corruption using CHI660D electrochemical workstation
Erosion face area is 1cm2Example alloy is working electrode, using saturated calomel electrode as reference electrode, using platinized platinum as auxiliary electrode；Contain
5×10-6F-0.5mol/L H2SO4Electrolyte is heated to 80 DEG C with water bath, and into electrolyte with the flow velocity of 20ml/min
It is passed through hydrogen；Linear sweep voltametry, sweep speed 2mV/s are carried out to sample.It is averaged after measuring 3 samples, is listed in table 1.
The ingredient and corrosion current, hardness and tensile property of 1 embodiment of table
The ingredients such as Mn, Si, P, S of each embodiment meet alloy invention and require in table 1, and Fe is surplus, is not arranged in table 1
Out.
Claims (5)
1. a kind of cupric vanadium high intensity high corrosion resistance austenitic stainless steel, it is characterised in that: the mass percent of stainless steel each element
Are as follows: C≤0.08, Ni=10.0~14.0, Cr=16.0~18.5, Mo=2.0~3.0, V≤0.34, Cu=0.2~0.8, Mn
≤ 2.0, Si≤1.0, P≤0.035, S≤0.030, wherein 4.24 × (C-0.01)≤V≤4.24 × C, surplus Fe.
2. the preparation method of cupric vanadium high intensity high corrosion resistance austenitic stainless steel as described in claim 1, it is characterised in that packet
Include following steps:
(1) smelting and casting of stainless steel
According to the mass percent of stainless steel each element, electrical pure iron, crome metal piece, metal nickel plate, metal molybdenum, stainless steel are chosen
Waste material, fine copper plate, vanadium iron or vanadium metal, graphite block are raw material, after electric arc melting or induction melting, are cast into alloy casting
Ingot；
Bath temperature is kept for 1700 DEG C ± 20 DEG C when melting；Molten steel calmness 5~10 minutes before being poured, molten steel is at 1550 DEG C ± 50
DEG C, vacuum or argon gas protective casting, the side's of being cast as ingot or billet；
(2) ingot casting thermal deformation cogging is processed
Pipe, stick, line, profile and cold punching part, ingot casting is using hot forging, groove rolling or universal rolling cogging；Plate uses plain-barreled roll
Milling train hot rolling cogging；
Forging scheme is that slab is heated to 1250 DEG C ± 10 DEG C, and forging of coming out of the stove after keeping the temperature 3~5 hours, initial forging temperature is 1150 DEG C
± 20 DEG C, final forging temperature >=1000 DEG C, forging ratio >=2.0, ratio of elongation >=2.0, always than >=4.0；
Blank after hot forging carries out roll piercing again, obtains tube billet；
Hot rolling scheme is that slab is heated to 1280 DEG C ± 10 DEG C, rolling of coming out of the stove after keeping the temperature 3~5 hours, and hot rolling initial forging temperature is
1180 DEG C ± 20 DEG C, finishing temperature >=950 DEG C；The contraction percentage of area of groove rolling or universal rolling cogging answers >=60%；Plate
Hot rolling is always lower to measure >=60%；
(3) cold deformation
Pipe, stick, line, profile using reciprocating type tube rolling, groove rolling, universal rolling or draw the method dialled to carry out cold deformation, obtain
Size, the specification of product requirement, the total deformation of cold deformation are calculated according to the contraction percentage of area, are not less than 80%；
The stainless steel parts that mechanical industry needs are obtained, the forging of cold stamping using thermal deformation cogging raw material, then by cold stamping
Than >=5.0；If forging ratio is insufficient, stamping blanks should be handled using cold forging in advance, guarantee total cold deformation；
Plate uses cold-rolling deformation, cold rolling overall reduction >=80%；
(4) high-temperature heat treatment
It after cold deformation, is made annealing treatment at 1085 DEG C ± 30 DEG C, soaking time is 30 minutes~120 minutes, and when heating uses
Vacuum or gas shield；After annealing, it is quickly cooled down using water, oil or argon gas, nitrogen helium atmosphere medium；
For stainless steel under logical hydrogen condition, 80 DEG C contain 5 × 10 after high temperature quenching treatment-6F-0.5mol/L H2SO4In electrolyte
Corrosion current is 6.4~9.7 μ A/cm2, compared to 316 alloys, corrosion rate is greatly lowered.Hardness is 186~195HV1,
Yield strength is 277~294MPa, and tensile strength is 583~610MPa, and elongation percentage 41~47% is better than 316 alloys.
3. the preparation method of cupric vanadium high intensity high corrosion resistance austenitic stainless steel as claimed in claim 2, it is characterised in that: institute
State protective gas are as follows: argon gas, nitrogen or helium.
4. the preparation method of cupric vanadium high intensity high corrosion resistance austenitic stainless steel as claimed in claim 2, it is characterised in that: step
Suddenly high-temperature heat treatment method described in (4) is with heating in vacuum-air quenching, laser heating-water hardening, laser heating-high pressure gas
Body quenching, gas shield heating-water quenching or gas shield heating-oil quenching.
5. the preparation method of cupric vanadium high intensity high corrosion resistance austenitic stainless steel as claimed in claim 2, it is characterised in that: move back
Aligning or setting treatment are carried out after fire, align or the deflection of setting treatment is less than 2%.
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