CN109609847A - A kind of copper tungsten enhancing austenitic stainless steel against corrosion and preparation method thereof - Google Patents

A kind of copper tungsten enhancing austenitic stainless steel against corrosion and preparation method thereof Download PDF

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CN109609847A
CN109609847A CN201811576390.1A CN201811576390A CN109609847A CN 109609847 A CN109609847 A CN 109609847A CN 201811576390 A CN201811576390 A CN 201811576390A CN 109609847 A CN109609847 A CN 109609847A
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stainless steel
corrosion
rolling
forging
temperature
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罗丰华
黄明初
吴子恺
李波
刘珏
李东阳
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Central South University
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/44—Ferrous alloys, e.g. steel alloys containing chromium with nickel with molybdenum or tungsten
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21C—MANUFACTURE OF METAL SHEETS, WIRE, RODS, TUBES OR PROFILES, OTHERWISE THAN BY ROLLING; AUXILIARY OPERATIONS USED IN CONNECTION WITH METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL
    • B21C37/00—Manufacture of metal sheets, bars, wire, tubes or like semi-manufactured products, not otherwise provided for; Manufacture of tubes of special shape
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/005—Modifying the physical properties by deformation combined with, or followed by, heat treatment of ferrous alloys
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C33/00—Making ferrous alloys
    • C22C33/04—Making ferrous alloys by melting
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/42—Ferrous alloys, e.g. steel alloys containing chromium with nickel with copper
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/58—Ferrous alloys, e.g. steel alloys containing chromium with nickel with more than 1.5% by weight of manganese
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D2211/00—Microstructure comprising significant phases
    • C21D2211/001—Austenite
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

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  • Mechanical Engineering (AREA)
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  • Metallurgy (AREA)
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  • Crystallography & Structural Chemistry (AREA)
  • Heat Treatment Of Steel (AREA)

Abstract

A kind of copper tungsten enhancing austenitic stainless steel against corrosion and preparation method thereof, alloying element content are as follows: C≤0.07, Ni=8.0~10.0, Cr=17.0~19.0, W≤1.07, Cu=0.2~0.8, Mn≤2.0, Si≤1.0, P≤0.035, S≤0.030, wherein 15.3 × (C-0.01)≤W≤15.3 × C, surplus Fe.After alloy smelting, coarse austenite grain is obtained by higher temperature solid solution so that WC 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 7.6~14.2 μ A/cm in electrolyte2, 304 stainless steels are compared, corrosion rate is greatly lowered, and mechanical property is slightly better than 304 stainless steels.

Description

A kind of copper tungsten enhancing austenitic stainless steel against corrosion and preparation method thereof
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 copper tungsten enhancing austenitic stainless steels against corrosion and preparation method thereof.The present invention solves Its technical problem adds strong carbide shape the technical scheme adopted is that on the basis of 304 austenitic stainless steel alloy ingredient At elemental tungsten (W) and austenite former copper (Cu), abbreviation 304-CW stainless steel.Its specific ingredient (mass percent) are as follows: C ≤ 0.07, Ni=8.0~10.0, Cr=17.0~19.0, W≤1.07, Cu=0.2~0.8, Mn≤2.0, Si≤1.0, P≤ 0.035, S≤0.030, wherein 15.3 × (C-0.01)≤W≤15.3 × C, Fe=surplus.After alloy smelting, through overheating deforming Cogging and cold deformation processing so that the WC formed is able to sufficiently broken, Dispersed precipitate, then by higher temperature solid solution, obtain thick Big crystal grain austenite structure, makes it have higher-strength and corrosion resistance.
304 be U.S.'s trade mark, and corresponding China's stainless steel trade mark is 0Cr18Ni9；304 stainless steels are common in stainless steel A kind of material, in the industry also referred to as 18/8 stainless steel.800 DEG C of high temperature resistant, have processing performance good, the high feature of toughness makes extensively For industry and furniture decoration industry and food medical industry.The performance indicator of its plate are as follows: yield strength >=205MPa, tension Intensity >=515MPa, elongation >=40%, hardness≤HV210.
Contain the C not higher than 0.07% in 304 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 W is added in the alloy, the spherical particle WC 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 W is 183.85, and C Atomic weight is 12.01, and the atomic weight ratio of W, C are 15.3, as 15.3 × (C-0.01)≤W≤15.3 × C, as C content is When 0.07%, the content of W is 0.92%~1.07%, and the solid solution content of practical C is not less than 0.01% in austenite grain, and not Have the surplus of W 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 304-CW stainless steel includes following key step:
(1) smelting and casting of 304-CW stainless steel
Choose electrical pure iron, crome metal piece, metal nickel plate, stainless steel waste material, fine copper plate, ferrotungsten or tungsten, graphite block Alloy cast ingot is cast into after electric arc melting or induction melting for raw material.
It, should not be using stainless steel industries producers such as Converter vacuum oxygen decarburization methods since alloy is added to Cu, elements such as w 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 that 304,304L etc. has nickelic, Gao Ge austenitic stainless steel waste material, then pure with electrician The raw materials such as iron, crome metal piece, metal nickel plate, fine copper plate, ferrotungsten or tungsten, graphite block, the 304-CW stainless steel at Divide alloyage in range, controls the essential elements such as C, Cr, Ni, Cu, W in alloy, and the impurity elements such as Mn, Si, P, S pass through The purity of raw material is guaranteed.
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%.
304-CW 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.304 stainless steel steel of above method measurement corrosion current in room temperature is 27.8 μ A/cm2, it is 1800 at 80 DEG C μA/cm2。。
Of the invention is mainly characterized by the basis of 304 stainless steel alloy, adds carbide W, 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 304-CW alloy after high temperature quenching treatment under logical hydrogen condition, 80 DEG C contain 5 × 10-6F-0.5mol/L H2SO4It is 7.6~14.2 μ A/cm in electrolyte2, compared to 304 alloys, corrosion rate is greatly lowered.Hardness be 196~ 206HV1, yield strength are 301~332MPa, and tensile strength is 576~596MPa, and elongation percentage 40~45% is closed better than 304 Gold.
Detailed description of the invention
4 polarization curve of Fig. 1 present example；
5 tensile mechanical properties curve graph of Fig. 2 present example；
6 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.
Select electrical pure iron, crome metal piece, metal nickel plate, stainless steel waste material, fine copper plate, ferrotungsten or tungsten, graphite block For raw material, alloy is configured 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, 304 stainless steel waste materials, fine copper plate, tungsten is raw material, configuration Stainless composition of steel it is as follows: C=0.03, Ni=9.5, Cr=17.0, W=0.40, Cu=0.2, Mn=1.2, Si=0.8, P≤ 0.035, S≤0.030, Fe=surplus.After weighing good corresponding raw material according to component requirements proportion, argon arc melting, Bath temperature is kept for 1720 DEG C when melting；Calm 10 minutes of molten steel before being poured, molten steel is at 1650 DEG C, argon for protecting pouring.Casting At 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 304-CW 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 14.2 μ A/cm in electrolyte2.Hardness is 200HV1, yield strength 312MPa, and tensile strength is 576MPa, elongation percentage 42%.
Embodiment 2
Choosing 304 stainless steel waste materials, fine copper plate, ferrotungsten is raw material, and the stainless composition of steel of configuration is as follows: C=0.04, Ni= 9.0, Cr=18.8, W=0.56, 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 304-CW 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 12.4 μ A/cm in electrolyte2.Hardness is 204HV1, yield strength 301MPa, and tensile strength is 593MPa, elongation percentage 40%.
Embodiment 3
Choosing electrical pure iron, crome metal piece, metal nickel plate, fine copper plate, ferrotungsten, graphite block is raw material, the stainless steel of configuration Ingredient is as follows: C=0.05, Ni=9.2, Cr=18.6, W=0.65, 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 304-CW 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 10.3 μ A/cm in electrolyte2.Hardness is 314HV1, yield strength 312MPa, and tensile strength is 583MPa, elongation percentage 44%.
Embodiment 4
Choosing 304L stainless steel waste material, fine copper plate, tungsten, graphite block is raw material, and the stainless composition of steel of configuration is as follows: C =0.06, Ni=8.8, Cr=18.5, W=0.88, 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 304-CW 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 9.8 μ A/cm in electrolyte2, polarization curve is shown in Fig. 1.Hardness is 196HV1, and yield strength is 325MPa, tensile strength 576MPa, elongation percentage 45%.
Embodiment 5
Choosing electrical pure iron, crome metal piece, metal nickel plate, fine copper plate, ferrotungsten, graphite block is raw material, the stainless steel of configuration Ingredient is as follows: C=0.07, Ni=9.0, Cr=18.0, W=1.0, Cu=0.7, Mn=0.6, Si=0.3, P≤0.035, and 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 304-CW 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 8.7 μ A/cm in electrolyte2.Hardness is 198HV1, yield strength 332MPa, and tensile strength is 588MPa, elongation percentage 41%.
Embodiment 6
Choosing 304 stainless steel waste materials, fine copper plate, ferrotungsten, graphite block is raw material, and the stainless composition of steel of configuration is as follows: C= 0.07, Ni=9.2, Cr=18.5, W=1.07, 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 304-CW 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.Hardness is 206HV1, yield strength 327MPa, and tensile strength is 581MPa, elongation percentage 42%.
The electron microscope scanning figure of Fig. 3 corrosion surface, as can be seen from Figure 3, corrosion surface is very smooth, and crystal grain is very coarse, Corrosion product is not remained, but there are many smooth apertures, is mainly distributed on intra-die, crystal boundary is seldom.This is because surface Tiny carbide, which preferentially corrodes, to fall off, and remaining smooth surface is homogeneous, and crystal boundary is clear, has stronger anticorrosive energy Power.
The performance detection of the preparation process of above-described embodiment 304-CW 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 copper tungsten enhancing austenitic stainless steel against corrosion, it is characterised in that: the mass percent of stainless steel each element are as follows: C≤ 0.07, Ni=8.0~10.0, Cr=17.0~19.0, W≤1.07, Cu=0.2~0.8, Mn≤2.0, Si≤1.0, P≤ 0.035, S≤0.030, wherein 15.3 × (C-0.01)≤W≤15.3 × C, surplus Fe.
2. the preparation method of copper tungsten enhancing austenitic stainless steel against corrosion as described in claim 1, it is characterised in that including as follows Step:
(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, stainless steel waste material, pure is chosen Copper sheet, ferrotungsten or tungsten, graphite block are that raw material is cast into alloy cast ingot after electric arc melting or induction melting；
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 7.6~14.2 μ A/cm2, compared to 304 alloys, corrosion rate is greatly lowered；Hardness is 196~206HV1, Yield strength is 301~332MPa, and tensile strength is 576~596MPa, and elongation percentage 40~45% is better than 304 alloys.
3. the preparation method of tungsten enhancing austenitic stainless steel against corrosion as claimed in claim 2, it is characterised in that: the protection gas Body are as follows: argon gas, nitrogen or helium.
4. the preparation method of tungsten enhancing austenitic stainless steel against corrosion as claimed in claim 2, it is characterised in that: step (4) institute The high-temperature heat treatment method stated, be with heating in vacuum-air quenching, laser heating-water hardening, laser heating-high pressure gas quenching, Gas shield heating-water quenching or gas shield heating-oil quenching.
5. the preparation method of tungsten enhancing austenitic stainless steel against corrosion as claimed in claim 2, it is characterised in that: carried out after annealing The deflection of aligning or setting treatment, aligning or setting treatment is less than 2%.
CN201811576390.1A 2018-12-22 2018-12-22 A kind of copper tungsten enhancing austenitic stainless steel against corrosion and preparation method thereof Withdrawn CN109609847A (en)

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Application publication date: 20190412