CN107779762B - A kind of enamel steel plate and its manufacturing method with excellent high temperature deformation performance - Google Patents

A kind of enamel steel plate and its manufacturing method with excellent high temperature deformation performance Download PDF

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Publication number
CN107779762B
CN107779762B CN201610772364.0A CN201610772364A CN107779762B CN 107779762 B CN107779762 B CN 107779762B CN 201610772364 A CN201610772364 A CN 201610772364A CN 107779762 B CN107779762 B CN 107779762B
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steel plate
enamel
temperature
particle
steel
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CN107779762A (en
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孙全社
王双成
王俊凯
姚士杰
鲁岩
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Baoshan Iron and Steel Co Ltd
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Baoshan Iron and Steel Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/04Ferrous alloys, e.g. steel alloys containing manganese
    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21DMODIFYING 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
    • C21D8/00Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/02Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • C21D8/0221Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the working steps
    • C21D8/0226Hot rolling
    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21DMODIFYING 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
    • C21D8/00Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/02Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • C21D8/0247Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the heat treatment
    • C21D8/0263Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the heat treatment following hot rolling
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/001Ferrous alloys, e.g. steel alloys containing N
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/02Ferrous alloys, e.g. steel alloys containing silicon
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/06Ferrous alloys, e.g. steel alloys containing aluminium
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/08Ferrous alloys, e.g. steel alloys containing nickel
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/12Ferrous alloys, e.g. steel alloys containing tungsten, tantalum, molybdenum, vanadium, or niobium
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/14Ferrous alloys, e.g. steel alloys containing titanium or zirconium
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/16Ferrous alloys, e.g. steel alloys containing copper
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/18Ferrous alloys, e.g. steel alloys containing chromium
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/18Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/32Ferrous alloys, e.g. steel alloys containing chromium with boron
    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21DMODIFYING 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
    • C21D2211/00Microstructure comprising significant phases
    • C21D2211/003Cementite
    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21DMODIFYING 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
    • C21D2211/00Microstructure comprising significant phases
    • C21D2211/005Ferrite

Abstract

The invention discloses a kind of enamel steel plates with excellent high temperature deformation performance, its chemical element mass percent are as follows: C:0.03~0.06%, Si:0.01~0.50%, Mn:0.5~1.2%, 0 < S≤0.035%, Al:0.005~0.05%, N:0.0055~0.010%, Ti:0.19~0.25%, Mo:0.10~0.20%, Nb≤0.03%, surplus are Fe and other inevitable impurity;The enamel uses the microstructure of steel plate to have ferrite and a TiN particle as precipitated phase, and the surface of the TiN particle is in plane, is formed with irreversible small hole between the TiN particle and surface ferrite crystal grain in curved surface.Correspondingly, the invention also discloses the manufacturing methods of the enamel steel plate described in one kind.

Description

A kind of enamel steel plate and its manufacturing method with excellent high temperature deformation performance
Technical field
The present invention relates to a kind of steel plate and its manufacturing method more particularly to a kind of enamel steel plate and its manufacturing methods.
Background technique
Enamel technique is exactly that the nature of glass enamel containing high silicon dioxide component is coated in after machine-shaping Steel matrix surface, one kind that then enamel is firmly bonded to steel matrix surface formation composite material after high temperature sintering add Work process, this composite material have the Common advantages such as the stability of glass and the intensity of steel, have good wearability, to each Kind acid, alkali, organic solvent have preferable corrosion resistance.Enamel technique is mainly used for glass-lined equipment and enamel accessory Such as glassed steel reaction vessels, enamel storage tank, enamel glass stirrer are fabricated, petrochemical industry, system doctor's pharmacy etc. are widely used in Industry.Glass-lined equipment, first by steel plate machine-shaping, welding and surface treatment, is applied later during processing and manufacturing It wards off and is sintered.To pass through 7~9 application of slips repeatedly and high temperature firings when enamel firing, generally to reach enough enamel layer thickness, disappear Except enamel coating surface defect, guarantee that enamel quality, the temperature of firing are up to 870~930 DEG C.
Enamel is most still with the ordinary constructions such as Q235 and Q245R, Q345R steel plate and pressure vessel with steel at present Based on steel plate, the design and use target of these steel plates is not intended to the purposes such as glass-lined equipment, and the composition characteristic of steel is to contain Carbon amounts is higher (C > 0.12%), and alloying element content is very low, and microstructure is based on ferrite+pearlite.It is being used for In the manufacture of glass-lined equipment, on the one hand lacking storage hydrogen trap, to be easy to produce squama quick-fried, simultaneously because phosphorus content height is produced in enamel firing Raw bubble is excessive excessively to be easy to cause bubble structure bad, damages enamel coating quality;On the other hand, due to multiple high temp to be passed through Firing continually occurs the dissolution and transformation (phase transformation) of pearlite, easily generates after being subjected to heating repeatedly, cooling procedure The deformation of steel plate ontology, the quality for severely impacting product even result in scrap of the product.
The hot rolled steel plate of enamel steel is main big using addition in order to improve the fish scaling resistance of steel plate in the prior art The titanium of amount, and improve the ratio of Ti/C, for example, Ti mass percent be 0.09~0.20%, Ti/C ratio be 1.5~ 3.0 or even Ti/C ratio is up to 5~15 etc..Purpose using this kind of method is that a large amount of tiny TiC particles are formed in steel, Become storage hydrogen trap by TiC particle, to prevent the generation squama during application of slip quick-fried.However, since TiC particle is being heated to 800 DEG C or more and when long-time heat preservation, can largely dissolve, and be precipitated in subsequent slow cooling and agglomeration, thus to steel plate Hydrogen storage capacity brings uncertainty.In addition, since there are pearlitic structrures in steel, with the dissolution and transformation (phase transformation) of pearlite Frequent generation, steel plate is also easy to produce high temperature deformation.
Because of this it may be desirable to obtain a kind of enamel steel plate, with high temperature deformation resistance performance, can satisfy in high temperature shape Under state repeatedly enamel firing without generate deformation.
Summary of the invention
One of the objects of the present invention is to provide a kind of enamel steel plate with excellent high temperature deformation performance, tools There is excellent application of slip performance, while also there is excellent high temperature deformation resistance performance.
Based on foregoing invention purpose, the present invention provides a kind of enamel steel with excellent high temperature deformation performance Plate, chemical element mass percent are as follows:
C:0.03~0.06%, Si:0.01~0.50%, Mn:0.5~1.2%, 0 < S≤0.035%, Al:0.005~ 0.05%, N:0.0055~0.010%, Ti:0.19~0.25%, Mo:0.10~0.20%, Nb≤0.03%, surplus Fe With other inevitable impurity;
The enamel uses the microstructure of steel plate to have ferrite and the TiN particle as precipitated phase, the TiN particle Surface be in plane, be formed with irreversible small hole between the TiN particle and surface ferrite crystal grain in curved surface.
In the enamel steel plate of the present invention with excellent high temperature deformation performance, other are inevitably miscellaneous Matter is primarily referred to as phosphorus, thus, the mass percent of impurity element P is limited to≤0.035%.
Inventor through a large number of experiments and test, discovery thermal deformation processing in, during enamel firing High temperature repeatedly is fired, due to being influenced by factors such as phase transformation, recrystallizations, be hardly formed around tiny precipitated phase largely, Permanent storage hydrogen trap.In view of the raw largely irreversible storage hydrogen trap, therefore hot-working steel plate of thermal deformation process relatively difficult labour The quick-fried phenomenon of squama is more prone to produce in the application of slip.Come it should be pointed out that hot-working steel plate only relies on a large amount of alloying element of addition A large amount of second phase particles are precipitated also to be difficult fundamentally to improve its fish scaling resistance.
In consideration of it, inventor is had found based on this, while enamel steel is fully taken into account to scaling resistance, adherence Property, the comprehensive performances such as anti-needle pore defect and intensity, plasticity, toughness and weldability matching requirement, in alloying element and processing After having carried out a large amount of research and experimental contrast analysis in terms of the matching of technological parameter, closed by each chemical component to steel The synergistic effect of reason designed to utilize each chemical element, creativeness propose the mass percent for controlling each chemical element, especially It is the mass percent of Ti and N, to obtain the relatively fine TiN particle of precipitated phase, and is formed using the particle irreversible Store hydrogen trap.The surface of the TiN particle is in plane, is formed between the TiN particle and surface ferrite crystal grain in curved surface There is irreversible small hole.Since the TiN particle is all even to be precipitated in molten steel at high operating temperatures, and in heat It is substantially insoluble in process, and overwhelming majority TiN particle will not be dissolved in firing range, therefore, this Slightly small hole is beneficial irreversible storage hydrogen trap.
It should be noted that in the technical scheme, the precipitated phase for forming storage hydrogen trap is not limited in TiN, TiN is handled In addition, there are also other precipitated phases can also form storage hydrogen trap, such as complex chemical compound (Ti, Nb) (C, N).In another example being in ball The TiS and TiC of shape particle, however the storage hydrogen trap effect of these precipitates is good without TiN.Especially TiC, due to its precipitation It is lower with solution temperature, influenced by hot-working and high temperature enamel firing technique big, the storage hydrogen trap served is restricted.
And enamel in the prior art with steel by control Ti/C ratio (as control Ti/C in 1~4 range) from And TiC particle being precipitated, and form storage hydrogen trap around its particle, this makes the prior art have following defects that form storage hydrogen Trap is more difficult, and since TiC precipitation or solution temperature are lower, is easy so that it is formed by storage hydrogen trap by hot-working or height The influence of temperature firing is significant, causes the fluctuation and variation of hydrogen storage performance.And technical solutions according to the invention pass through TiN particle institute The small hole formed overcomes drawbacks described above as irreversible storage hydrogen trap, uses to improve enamel of the present invention The fish scaling resistance of steel plate, and then ensure that the application of slip performance of steel plate.
In the enamel steel plate of the present invention with excellent high temperature deformation performance, steel plate is by repeatedly in height The lower sintering of temperature, yield strength decline is less, reflects steel plate with preferable resistance capacity to deformation.
The design principle of each chemical element of enamel steel plate of the present invention are as follows:
Carbon: carbon is to ensure that the key element of armor plate strength, and the mass percent of carbon increases, and intensity rises, plasticity and toughness Decline.Carbon and titanium generate TiC particle, can not only strengthen matrix, reduce the pearlitic structrure in steel, and the storage to steel is improved Hydrogen Energy power is also helpful.The mass percent of carbon is lower than 0.03%, and the amount of precipitated phase is less, causes the intensity of steel too low, however When the mass percent of carbon is higher than 0.06%, it is unfavorable for improving the high temperature deformation of steel.Therefore, it is used in enamel of the present invention The mass percent of the carbon of steel plate is limited to 0.03~0.06%.But as described above, due to the enamel technique of steel Temperature is high in the process, the time is long, and will be by being repeatedly repeated, so that the phase transformation of steel and the weight of recrystallization and TiC particle Within the temperature range of being close, so that TiC particle is extremely unstable in steel, therefore the present invention also passes through it for molten and precipitation The ingredient design of his element obtains stable, effective small hole as storage hydrogen trap.
Silicon: silicon plays solution strengthening effect in steel, while silicon can also improve the high temperature deformation resistance ability of steel, for improving Heatproof shock property between steel and the enamel coating of the application of slip is also advantageous.In general, steel plate is passing through blasting treatment, is warding off the normal of ground coat enamel Under technique, it can guarantee excellent adhesion property completely.But the mass percent of silicon is higher than 0.50% can be to the plasticity of steel and tough The performances such as property are unfavorable, are also unfavorable for welding.For this purpose, the mass percent control of the silicon of enamel steel plate of the present invention exists 0.01~0.50%.
Manganese: manganese is to strengthen matrix element, therefore the purpose that manganese is added essentially consists in the intensity for improving steel, but the quality hundred of manganese When dividing than being higher than 1.2%, the plasticity of steel can be seriously reduced.In addition, manganese is in steel and reaction of Salmon-Saxl generates manganese sulfide, the sulphur of general steel Changing manganese is in hairline shape, extremely harmful to the horizontal plastic property and toughness of steel plate, however, in enamel steel plate of the present invention In, due to there is an addition of appropriate titanium, manganese is mainly precipitated with spherical (Mn, Ti) S, it is entirely avoided the precipitation of simple manganese sulfide and It is adversely affected.In consideration of it, the mass percent of the manganese of enamel of the present invention steel plate is limited to 0.5-1.2%.
Sulphur: sulphur is the element for damaging the plasticity and toughness of steel plate, however, in technical solutions according to the invention, alloy Element ti can form compound with C, S and N.The technical program is come by forming comparatively fine TiN particle and TiS particle Form irreversible storage hydrogen trap.Therefore, enamel of the present invention is limited to 0 < S with the mass percent of sulphur in steel plate ≤ 0.035%.
Aluminium: aluminium is strong deoxidant element, since oxygen and titanium react easily in molten steel and forms field trash, consumes effective titanium, Therefore, it is necessary to add aluminium, deoxidation is carried out, to reduce the oxygen content in steel.The aluminium of enamel steel plate of the present invention Mass percent control controls Als≤0.05% 0.005~0.05%.
Nitrogen: in technical solutions according to the invention, alloying element Ti can form compound with C, S and N.This technology side Case is by forming comparatively fine TiN particle and TiS particle, to form irreversible storage hydrogen trap.Therefore, of the present invention The mass percent of nitrogen limits in enamel steel plate are as follows: 0.0055~0.010%.
Titanium and niobium: titanium and niobium are all strong carbon, nitride forming element.It is compared with titanium, niobium and nitrogen are precipitated to be formed in high temperature NbN and more stable precipitated phase, but its particle size ratio TiN is thin, it can be to avoid the adverse effect of coarse TiN.With this Meanwhile niobium can also form tiny NbC particle with carbon, and the intensity of steel can be improved.Therefore, it adds titanium and on the one hand niobium guarantees There are enough second phase particles to be precipitated, on the other hand can also avoid the formation of more coarse TiN particle.In addition, extra titanium It can react with carbon, generate relatively fine TiC particle.In consideration of it, the matter of the Ti of enamel steel plate of the present invention The mass percent that percentage control is measured in 0.19~0.25%, Nb controls below 0.03%.
Molybdenum: molybdenum is conducive to improve the adherence between steel and glass enamel coating, can also improve the high temperature resistant deformability of steel. But mass percent is excessively high to will increase cost.Therefore, the mass percent of molybdenum limits in enamel steel plate of the present invention It is 0.10~0.20%.
Further, in enamel steel plate of the present invention, also contain B:0.0005~0.005%.
In enamel steel plate of the present invention, addition boron element can further improve the fish scaling resistance of steel, Further, it is also possible to improve the intensity of steel.However, addition boron element also improves the temperature of Ac3, it is therefore, of the present invention to ward off Glass is limited to 0.0005~0.005% with the mass percent of boron in steel plate.
Further, in enamel steel plate of the present invention, meet Ti+ (48/93) × Nb >=4 × C+3.43 × N+1.5 × S, wherein Ti, Nb, C, S and N respectively indicate the mass percent of corresponding element;The microstructure also has work For the TiS particle of precipitated phase, the TiS particle is spherical in shape, and the TiS particle is used to form irreversible small hole.
In order to further improve the comprehensive performance of steel, its fish scaling resistance, plasticity and toughness, this case invention are especially improved People has carried out further restriction to the synergistic effect chemical element each in this case technical solution, meet Ti+ (48/93) × Nb >=4 × C+3.43 × N+1.5 × S, wherein Ti, Nb, C, S and N respectively indicate the mass percent of corresponding element.It designs former Reason are as follows: alloying element Ti can form compound with C, S and N in steel.Typically, since the Precipitation Temperature of TiN particle is high, The coarse plasticity and toughness that can damage steel of grain.Thus, the precipitation of TiN particle is avoided or reduced by reducing the mass percent of nitrogen. However, in the inventive solutions, in order to improve the performance of steel, inventor further passes through the above-mentioned element collaboration of control and closes System allows to be precipitated comparatively fine TiN particle and TiS so that limitation forms the precipitation quantity and temperature of TiN and TiS Son (catercorner length or diameter are not more than 4 μm).The hard phase TiN that these high temperature can be made to be precipitated is brought using this kind of mode And TiS, TiS particle be mainly in it is spherical, there is also gaps between matrix, while as TiN, and TiS particle is in hot-working Substantially insoluble in the process, therefore it can also form small hole between the matrix of steel, that is, store hydrogen trap.Even if being burnt accordingly It will not be dissolved at the overwhelming majority TiN and TiS particle granules in temperature range.Meanwhile to slab before hot-working By improving heating temperature and extending soaking time when being heated, so that a part dissolution of TiN particle granules, especially TiN preferentially at its grain corner or peripheral portion dissolution, so that TiN particle granules is attenuated, to improve steel plasticity and toughness have Benefit, while more tiny particle can be precipitated in the part TiN particle granules dissolved, also extremely have to storage hydrogen trap is increased later Benefit, to improve the fish scaling resistance of steel.In addition, will form a large amount of field trash when the mass percent of N, S are excessively high.
In addition, the formula also helps so that the strong carbon, nitride forming element such as titanium and niobium of sufficient amount, almost solid The carbon and nitrogen in steel are determined, have not had more carbon especially and form pearlitic structrure, in this way by inhibiting pearlitic structrure It generates, avoids the high temperature for leading to steel plate due to pearlite Solid State Transformation repeatedly during hot procedure and high temperature enamel firing Deformation.
Further, in enamel steel plate of the present invention, meet 0.02%≤Cu+Cr+Ni≤0.20%.
In order to further improve enamel steel plate of the present invention, technical solution of the present invention further defines alloy The addition of element meets 0.02%≤Cu+Cr+Ni≤0.20%, this is because: copper, chromium, nickel: it is the residual elements in steel, It, can be by the influence to surface film oxide to influence the adherence of the enamel of steel since these elements are deposited in surface of steel plate. The residual quantity (bringing in the steel scrap used when such as smelting) of these elements fluctuates bigger, the wave generated to enamel with plate property It is dynamic also bigger, it is unfavorable to the stability for improving enamel performance.Therefore, enamel steel plate of the present invention by copper, chromium with And nickel limits are as follows: 0.02%≤Cu+Cr+Ni≤0.20%.
Further, in enamel steel plate of the present invention, the TiN particle is in square or cuboid.
Further, in enamel steel plate of the present invention, microstructure is ferrite or ferrite+carburizing Body.
Due to not containing pearlite in technical solutions according to the invention, thus avoids the dissolution due to pearlite and turn Become (phase transformation) and lead to the deformation for generating steel plate ontology, deforms enamel steel plate of the present invention with excellent high temperature Performance.
Further, in enamel steel plate of the present invention, yield strength >=295MPa, tensile strength >= 400MPa, elongation percentage >=26%.
Another object of the present invention is to provide a kind of manufacturing methods of above-mentioned enamel steel plate, successively include step It is rapid:
(1) it smelts and casts;
(2) hot rolling: the heating temperature before slab rolling is 1150~1250 DEG C, soaking time=t × (0.5~1.5), Middle t is slab thickness, and unit mm, the unit of soaking time is min;1100~1200 DEG C of roughing rolling temperature of control, deformation Amount >=50%;Water-spraying control after roughing, control finish rolling start rolling temperature are 920~1000 DEG C, and finishing temperature is 870~920 DEG C, Deflection >=60%;
(3) cooling.
In the manufacturing method of the enamel steel plate of the present invention with excellent high temperature deformation performance, in order to protect Card enamel is unlikely to deform in high temperature with steel plate, and therefore, manufacturing method control process flow of the present invention is especially hot Each technological parameter during rolling makes steel plate have ferrite and the TiN particle as precipitated phase, the surface of the TiN particle In plane, irreversible small hole is formed between the TiN particle and surface ferrite crystal grain in curved surface.
In step (2), slab rolling before heating temperature be 1150~1250 DEG C and soaking time=t × (0.5~ 1.5), wherein t is slab thickness, and unit mm, the unit of soaking time is min, be because are as follows: be on the one hand to obtain uniform The austenite structure of change is partly dissolved the compound of titanium.Wherein, the calculation of soaking time are as follows: for example, Slab thickness is 230mm, then soaking time is 115~345min.
In addition, 1100~1200 DEG C of roughing rolling temperature of the control in step (2), deflection >=50% is for hot rolling Process carries out in austenite recrystallization section, to pass through repeat-rolling fining austenite grains.
At the same time, in step (2), water-spraying control after roughing, control finish rolling start rolling temperature is 920~1000 DEG C, Finishing temperature is 870~920 DEG C, deflection >=60%, it is ensured that phase transformation can be sufficiently completed after rolling.Meanwhile it is logical It crosses using deflection >=60%, so that forming a large amount of small hole in TiN particle periphery.
In step (3), cooling can take water cooling or slow cooling.Further, in manufacturing method of the present invention, In the step (3), average cooling rate≤10 DEG C/s is controlled.
In manufacturing method of the present invention, control average cooling rate≤10 DEG C/s, be because are as follows: in cooling procedure In, the titanium and carbon of solid solution can be precipitated in the form of compound, be evenly distributed in matrix in small and dispersed state, to reduce In flakes, and by controlling cooling rate, the ferritic structure in steel is refined for the transformation and aggregation of pearlite.In addition, cold But rate is higher than 10 DEG C/s, and the compound for being unfavorable for titanium is sufficiently precipitated, and will form residual stress in steel, causes to cause group The problems such as knitting unevenness.Therefore, step (3) controls average cooling rate≤10 DEG C/s in manufacturing method of the present invention.
Further, further include step (4) normalizing in manufacturing method of the present invention: normalizing temperature be 930~ 980℃。
Due in finishing temperature, the ferritic structure in steel is difficult to ensure as uniform equiax crystal, in order to obtain more preferable property Can enamel steel plate, step (4) normalizing can be added, to keep the Carbide Precipitation in steel more abundant, and can be with Ferritic structure is homogenized, internal residual stress is completely eliminated.
Enamel of the present invention with excellent high temperature deformation performance has good fish scaling resistance with steel plate, It is unlikely to deform at high temperature.In addition, enamel steel plate intensity, good plasticity and welding with higher of the present invention Property, the glass-lined equipment and accessory high particularly suitable for the production confrontation quick-fried performance requirement of squama.
The manufacturing method of enamel steel plate of the present invention with excellent high temperature deformation performance equally has upper State advantages and beneficial effects.In addition to this, the manufacturing approach craft process is simple, and saves manufacturing cost.
Detailed description of the invention
Fig. 1 is the micro-organization chart of the enamel steel plate with excellent high temperature deformation performance of the embodiment of the present invention 1.
Fig. 2 show the enamel of the embodiment of the present invention 1 with steel plate by 900 DEG C × 10min+ it is air-cooled → 950 DEG C × 10min+ is air-cooled → 870 DEG C × 10min+ air-cooled (continuous 5 processing when 870 DEG C × 10min) coprocessing 7 times after metallographic structure Photo.
Specific embodiment
There is excellent high temperature deformation performance to of the present invention below in conjunction with Detailed description of the invention and specific embodiment Enamel made further explanation with steel plate and its manufacturing method, however the explanation and illustration is not to of the invention Technical solution constitutes improper restriction.
Embodiment 1-7
Steel plate in above-described embodiment and comparative example is made using following step:
(1) it smelts and casts;
(2) hot rolling: the heating temperature before slab rolling is 1150~1250 DEG C, soaking time=t × (0.5~1.5), Middle t is slab thickness, and unit mm, the unit of soaking time is min;1100~1200 DEG C of roughing rolling temperature of control, deformation Amount >=50%;Water-spraying control after roughing, control finish rolling start rolling temperature are 920~1000 DEG C, and finishing temperature is 870~920 DEG C, Deflection >=60%;
(3) cooling: to control average cooling rate≤10 DEG C/s.The type of cooling can use water-spraying control or slow cooling.
It should be noted that, in order to further increase the performance of steel, further including step (4) normalizing in embodiment 2 and 7: Normalizing temperature is 930~980 DEG C.
Table 1 lists the percent mass proportioning of each chemical element of the enamel steel plate of each embodiment.
Table 1. (wt%, surplus are Fe and the other impurities element other than impurity element P)
Table 2 lists the specific process parameter of the manufacturing method of each embodiment.
Table 2
Enamel obtained by the above method with excellent high temperature deformation performance is surveyed with every mechanical property is carried out Examination and Hot Deformation Performance test, the correlation performance parameters that test measures are listed in Table 3 below.The test method of use are as follows: The glaze of application of slip test, we selected typical carries out, two-sided full package wet-process enamelling, using a ground coat enamel and an overglaze, is burnt into work Skill is according to the regulation of glaze, and ground coat enamel firing temperature is at 930~950 DEG C, and overglaze firing temperature is at 870~900 DEG C.
The mechanical property and the yield strength after multiple enamel firing that table 3 lists each embodiment.
Table 3
*: to the simulation enamel firing technique of 16mm thick steel plate: 900 DEG C × 10min+ is air-cooled → and 950 DEG C × 10min+ is air-cooled → 870 DEG C × 10min+ air-cooled (continuous 5 processing when 870 DEG C × 10min);To 20~24mm thick steel plate, temperature-resistant, phase is kept The time inside furnace answered extends to 15min;To 30mm thick steel plate, corresponding time inside furnace extends to 20min.
From table 3 it can be seen that each embodiment steel plate of this case yield strength >=345MPa, tensile strength >= 449MPa, elongation >=30%, illustrate that each embodiment enamel steel plate of this case has higher intensity and good stretching Ductility.
In addition, as can also be seen from Table 3, adherence grade of the enamel steel plate described in this case without the quick-fried phenomenon of squama and ground coat enamel Do not reach I grades, thus there is good application of slip performance, furthermore it can also be seen that warding off glass described in the technical program from table 3 Glass steel plate repeatedly after the enamel firing under above-mentioned high temperature, the numerical value of yield strength compared with original steel plate yield strength simultaneously Do not occur substantially gliding, this illustrates that the enamel steel plate has excellent high temperature deformation resistance ability.
Fig. 1 is the micro-organization chart of the enamel steel plate with excellent high temperature deformation performance of the embodiment of the present invention 1.
From figure 1 it appears that the microstructure of the enamel of embodiment 1 steel plate is ferrite, and in ferrite base TiN particle is distributed on body.
Fig. 2 show the enamel of embodiment of this case 1 with steel plate by 900 DEG C × 10min+ it is air-cooled → 950 DEG C × 10min Metallographic structure photo after+air-cooled → 870 DEG C × 10min+ air-cooled (continuous 5 processing when 870 DEG C × 10min) coprocessing 7 times.
From figure 2 it can be seen that its microstructure is uniform, equiaxial ferritic structure, and ferrite crystal grain is big Variation before small and enamel firing is little, and this also illustrates steel plates after multiple high temp is burnt into there is crystal grain resistant to high temperatures to grow up Ability is advantageous to raising or improvement elevated temperature strength and deformability.
It should be noted that the above list is only specific embodiments of the present invention, it is clear that the present invention is not limited to above real Example is applied, there are many similar variations therewith.If those skilled in the art directly exported from present disclosure or All deformations associated, are within the scope of protection of the invention.

Claims (10)

1. a kind of enamel steel plate with excellent high temperature deformation performance, which is characterized in that its chemical element quality percentage Than are as follows:
C:0.03~0.06%, Si:0.01~0.50%, Mn:0.5~1.2%, 0 < S≤0.035%, Al:0.005~ 0.05%, N:0.0055~0.010%, Ti:0.19~0.25%, Mo:0.10~0.20%, Nb≤0.03%, surplus Fe With other inevitable impurity;
Above-mentioned each chemical element meets Ti+ (48/93) × Nb >=4 × C+3.43 × N+1.5 × S, and wherein Ti, Nb, C, S and N points Not Biao Shi corresponding element mass percent;
The enamel uses the microstructure of steel plate to have ferrite and the TiN particle as precipitated phase, the table of the TiN particle Face is in plane, is formed with irreversible small hole between the TiN particle and surface ferrite crystal grain in curved surface.
2. enamel steel plate as described in claim 1, which is characterized in that it also contains B:0.0005~0.005%.
3. enamel steel plate as claimed in claim 1 or 2, which is characterized in that the microstructure also has as precipitation The TiS particle of phase, the TiS particle is spherical in shape, and the TiS particle is used to form irreversible small hole.
4. enamel steel plate as described in claim 1, which is characterized in that 0.02%≤Cu+Cr+Ni of its satisfaction≤ 0.20%.
5. enamel steel plate as described in claim 1, which is characterized in that the TiN particle is in square or cuboid.
6. enamel steel plate as described in claim 1, which is characterized in that its microstructure is ferrite or ferrite+infiltration Carbon body.
7. enamel steel plate as described in claim 1, which is characterized in that its yield strength >=295MPa, tensile strength >= 400MPa, elongation percentage >=26%.
8. the manufacturing method of the enamel steel plate as described in any one of claim 1-7, successively comprising steps of
(1) it smelts and casts;
(2) hot rolling: the heating temperature before slab rolling is 1150~1250 DEG C, soaking time=t × (0.5~1.5), wherein t For slab thickness, unit mm, the unit of soaking time is min;1100~1200 DEG C of roughing rolling temperature of control, deflection >= 50%;Water-spraying control after roughing, control finish rolling start rolling temperature are 920~1000 DEG C, and finishing temperature is 870~920 DEG C, deformation Amount >=60%;
(3) cooling.
9. manufacturing method as claimed in claim 8, which is characterized in that in the step (3), the average cooling rate of control≤ 10℃/s。
10. manufacturing method as claimed in claim 8, which is characterized in that further include step (4) normalizing: normalizing temperature be 930~ 980℃。
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