CN115449712B - High-strength pickled plate and preparation method thereof - Google Patents

High-strength pickled plate and preparation method thereof Download PDF

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Publication number
CN115449712B
CN115449712B CN202211116737.0A CN202211116737A CN115449712B CN 115449712 B CN115449712 B CN 115449712B CN 202211116737 A CN202211116737 A CN 202211116737A CN 115449712 B CN115449712 B CN 115449712B
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pickling
plate
cooling
strength
pickled
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CN115449712A (en
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郑秀敏
王飞洋
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Zhejiang Southeastern New Wood Technology Co ltd
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Zhejiang Southeastern New Wood Technology Co ltd
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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
    • C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21B—ROLLING OF METAL
    • B21B1/00—Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations
    • B21B1/22—Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations for rolling plates, strips, bands or sheets of indefinite length
    • B21B1/24—Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations for rolling plates, strips, bands or sheets of indefinite length in a continuous or semi-continuous process
    • B21B1/26—Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations for rolling plates, strips, bands or sheets of indefinite length in a continuous or semi-continuous process by hot-rolling, e.g. Steckel hot mill
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21B—ROLLING OF METAL
    • B21B15/00—Arrangements for performing additional metal-working operations specially combined with or arranged in, or specially adapted for use in connection with, metal-rolling mills
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21B—ROLLING OF METAL
    • B21B45/00—Devices for surface or other treatment of work, specially combined with or arranged in, or specially adapted for use in connection with, metal-rolling mills
    • B21B45/02—Devices for surface or other treatment of work, specially combined with or arranged in, or specially adapted for use in connection with, metal-rolling mills for lubricating, cooling, or cleaning
    • B21B45/0203—Cooling
    • B21B45/0209—Cooling devices, e.g. using gaseous coolants
    • B21B45/0215—Cooling devices, e.g. using gaseous coolants using liquid coolants, e.g. for sections, for tubes
    • B21B45/0218—Cooling devices, e.g. using gaseous coolants using liquid coolants, e.g. for sections, for tubes for strips, sheets, or plates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21B—ROLLING OF METAL
    • B21B45/00—Devices for surface or other treatment of work, specially combined with or arranged in, or specially adapted for use in connection with, metal-rolling mills
    • B21B45/04—Devices for surface or other treatment of work, specially combined with or arranged in, or specially adapted for use in connection with, metal-rolling mills for de-scaling, e.g. by brushing
    • B21B45/06—Devices for surface or other treatment of work, specially combined with or arranged in, or specially adapted for use in connection with, metal-rolling mills for de-scaling, e.g. by brushing of strip material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21B—ROLLING OF METAL
    • B21B45/00—Devices for surface or other treatment of work, specially combined with or arranged in, or specially adapted for use in connection with, metal-rolling mills
    • B21B45/04—Devices for surface or other treatment of work, specially combined with or arranged in, or specially adapted for use in connection with, metal-rolling mills for de-scaling, e.g. by brushing
    • B21B45/08—Devices for surface or other treatment of work, specially combined with or arranged in, or specially adapted for use in connection with, metal-rolling mills for de-scaling, e.g. by brushing hydraulically
    • 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
    • C21D11/00—Process control or regulation for heat treatments
    • C21D11/005—Process control or regulation for heat treatments for cooling
    • 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
    • C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • C21D8/0205—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips of ferrous alloys
    • 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
    • C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • C21D8/0221—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the working steps
    • C21D8/0226—Hot rolling
    • 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
    • C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • C21D8/0278—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips involving a particular surface treatment
    • 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
    • C22C38/002—Ferrous alloys, e.g. steel alloys containing In, Mg, or other elements not provided for in one single group C22C38/001 - C22C38/60
    • 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
    • C22C38/005—Ferrous alloys, e.g. steel alloys containing rare earths, i.e. Sc, Y, Lanthanides
    • 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
    • C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
    • C23G1/04—Cleaning or pickling metallic material with solutions or molten salts with acid solutions using inhibitors
    • C23G1/06—Cleaning or pickling metallic material with solutions or molten salts with acid solutions using inhibitors organic inhibitors
    • C23G1/061—Cleaning or pickling metallic material with solutions or molten salts with acid solutions using inhibitors organic inhibitors nitrogen-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
    • C23G1/04—Cleaning or pickling metallic material with solutions or molten salts with acid solutions using inhibitors
    • C23G1/06—Cleaning or pickling metallic material with solutions or molten salts with acid solutions using inhibitors organic inhibitors
    • C23G1/063—Cleaning or pickling metallic material with solutions or molten salts with acid solutions using inhibitors organic inhibitors heterocyclic compounds
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
    • C23G1/04—Cleaning or pickling metallic material with solutions or molten salts with acid solutions using inhibitors
    • C23G1/06—Cleaning or pickling metallic material with solutions or molten salts with acid solutions using inhibitors organic inhibitors
    • C23G1/065—Cleaning or pickling metallic material with solutions or molten salts with acid solutions using inhibitors organic inhibitors sulfur-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
    • C23G1/08—Iron or steel
    • C23G1/088—Iron or steel solutions containing organic acids
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21B—ROLLING OF METAL
    • B21B15/00—Arrangements for performing additional metal-working operations specially combined with or arranged in, or specially adapted for use in connection with, metal-rolling mills
    • B21B2015/0057—Coiling the rolled product

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  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)

Abstract

The application relates to a high-strength pickled plate and a preparation method thereof, wherein the pickled plate comprises the following raw materials in percentage by mass: c:0.49 to 0.54 percent of Si:0.25 to 0.45 percent of Mn:0.60 to 0.75 percent, B: 0.02-0.04%, al: 0.015-0.04%, ce: 0.2-0.4%, and the balance of Fe and unavoidable impurities, wherein the total amount of each component is 100%. According to the pickling plate, B and Ce elements are introduced into the pickling plate, so that the adhesion force of iron scales can be reduced, and the problem that pits appear in pickling can not be caused while the strength of the pickling plate is improved. In the preparation method, sodium silicate, fatty alcohol polyoxyethylene ether sodium sulfate and vitamin C are added into cooling water cooled by laminar flow; the cooling speed can be increased, and the content of ferroferric oxide in the ferric oxide skin layer can be reduced, so that the pickling is easier and the pickling is easier. In the pickling process, the corrosion inhibitor is added into the pickling solution, so that the steel surface layer can be protected from multiple aspects, the surface defects are reduced, and the comprehensive performance of the pickling plate is improved.

Description

High-strength pickled plate and preparation method thereof
Technical Field
The application relates to the technical field of steel rolling, in particular to a high-strength pickled plate and a preparation method thereof.
Background
The pickling plate mainly produces carbon-containing steel, and the pickling is mainly used for removing iron scales on the surface of the hot rolled coiled plate, wherein the iron scales are divided into three layers from outside to inside: fe (Fe) 2 O 3 、Fe 3 O 4 And FeO, wherein the FeO is loose in texture and directly attached to the steel plate substrate, when acid liquor flows in along gaps of the iron scale and contacts the steel plate substrate, chemical reaction can occur to generate hydrogen, and the hydrogen acts on the loose FeO to form a mechanical stripping effect, so that the iron scale on the surface of the acid-washed plate can be well removed through acid washing.
In order to increase the strength of the pickled plate, in general, silicon element is introduced into the composition of the pickled plate, and the silicon can promote M in the pickled plate 2 The decomposition of C carbide plays a role in refining the particles of carbide in the steel; silicon can be dissolved in the matrix of steel to play a role in solid solution strengthening; more importantly, silicon can improve the austenite hardenability and improve the purity of ferrite; therefore, the strength of the pickled plate can be improved to a great extent by introducing the silicon element. However, too high a silicon content results in the formation of a fayalite phase at the interface between the iron oxide and the steel matrix, which increases the adhesion of the iron oxide scale to the steel matrix, making it more difficult for the iron oxide scale to elute during pickling, resulting in the iron oxide scale remaining and pressing in, and manifesting as pitting after pickling.
In order to reduce the silicon content, the current common method is to add P or V element to replace part of Si in the formula, but the addition of the P or V element can reduce the generation of pit to a certain extent, but the effect is not good, and the strength of the pickled plate can be reduced to a certain extent. It is therefore necessary to develop a method that can better remove the pits of high strength pickled plates.
Disclosure of Invention
In order to further improve the comprehensive performance of the pickled plate, the application aims to provide a high-strength pickled plate and a preparation method thereof.
In a first aspect, the present application provides a high-strength pickled plate, which adopts the following technical scheme:
the high-strength pickled plate comprises the following raw materials in percentage by mass: c:0.49 to 0.54 percent of Si:0.25 to 0.45 percent of Mn:0.60 to 0.75 percent, B: 0.02-0.04%, al: 0.015-0.04%, ce: 0.2-0.4%, and the balance of Fe and unavoidable impurities, wherein the total amount of each component is 100%.
Through adopting above-mentioned technical scheme, in this application on original pickling board raw materials's composition, introduced B element and Ce element. The element B reacts with silicon oxide in the matrix at the interface to form composite oxide with low melting point, so that the adhesion of the iron scale is reduced, and the iron oxide skin layer can be removed better. The Ce element can improve the compatibility of Si and Fe and reduce FeSiO at the interface 4 The phase is separated out, so that the adhesion of the oxide scale at the interface is reduced; and Ce can form oxide with O, can reduce the oxidation of Fe matrix, thus reduce the thickness of ferric oxide cortex; more importantly, ce can generate CeO with O 2 Which releases Ce during the pickling process 4+ It can complex silicate ion, thus can soften SiO 2 The effect of the layer reduces the adhesion of the oxide scale.
In a second aspect, the present application provides a method for preparing a high strength pickled plate, comprising the steps of:
batching according to the raw materials of the pickling plate, and casting into a plate blank; heating the slab, and then performing high-pressure water descaling; rough rolling and finish rolling are carried out on the plate blank after descaling, air cooling is carried out after finish rolling is finished, laminar flow inter-cooling is carried out after cooling is carried out at a set temperature, and coiling is carried out after cooling to the set temperature; then uncoiling, pickling, flushing, drying and coiling to obtain a pickled plate;
wherein, the cooling water adopted for cooling between laminar flows contains sodium silicate, fatty alcohol polyoxyethylene ether sodium sulfate and vitamin C.
By adopting the technical scheme, the iron scale on the surface of the pickling hot rolled steel plate is divided into three layers from outside to inside: fe (Fe) 2 O 3 、Fe 3 O 4 And FeO, wherein the loose FeO texture is the easiest to remove, the greater the specific gravity of FeO in the iron scale is, the more obvious the stripping effect is, and the more thoroughly the iron scale is removed; in order to make the scale on the surface of the steel sheet easier to clean by pickling, the proportion of FeO layer on the surface of the steel sheet must be increased.
In the present applicationAdding sodium silicate, fatty alcohol polyoxyethylene ether sodium sulfate and vitamin C into cooling water cooled between laminar flows; compared with pure water, the viscosity of water (similar to gel with low viscosity) can be increased after the sodium silicate and the fatty alcohol-polyoxyethylene ether sodium sulfate are added, and cations and anions (similar to salt water) can be ionized in the water, so that the cooling capacity is high, the cooling speed can be increased to 80-90 ℃/min. FeO will be eutectoid at about 450 ℃ to produce a reaction of 4 feo=fe 3 O 4 +Fe, reaction product Fe 3 O 4 Easy to attach on the steel plate substrate, difficult to clean by pickling, and in the method, the interlayer cooling process is further adjusted, so that the steel plate is rapidly cooled to 350 ℃, eutectoid reaction is effectively avoided, the proportion of FeO layers on the surface of the steel plate can be increased, and Fe difficult to clean can be reduced 3 O 4 Is generated; in order to further slow down the alkalinity of the eutectoid reaction, ferrous ions are added, the ferrous ions have certain reducibility, and can slow down the speed of the eutectoid reaction, thereby further reducing Fe 3 O 4 Is generated. The fatty alcohol polyoxyethylene ether sodium sulfate added in the method has strong foaming capacity, and generated bubbles can soften iron oxide scale, so that the iron oxide scale can be better removed in the subsequent pickling process.
Preferably, the heating temperature is 1150-1250 ℃, and the heat preservation time is 40-80 min.
By adopting the technical scheme, the heating temperature can be used for fully dissolving the components, so that the strength of the pickling plate is ensured.
Preferably, the total reduction of rough rolling is 50-60%, and the outlet temperature of the rough rolling mill is 1020-1080 ℃; the total reduction of rough rolling is 40-50%, and the outlet temperature of the finishing mill is 830-860 ℃.
By adopting the technical scheme, the rolling process can meet the requirement of the thickness of a finished product, is beneficial to obtaining ferrite grains with consistent shape, small distortion and few internal dislocation, and achieves the aim of low yield ratio.
Preferably, in the air cooling, the air cooling is performed until the temperature of the slab is 730-760 ℃.
By adopting the technical scheme, the dislocation movement in ferrite grains is facilitated in the temperature range of finish rolling and air cooling, and the dislocation density in the grains can be effectively reduced; the residence time in the temperature section is prolonged, which is favorable for mass dispersion and precipitation of carbonitride in steel; the dislocation inside ferrite grains may interact with the precipitated carbonitride, enhancing the dislocation density in the steel sheet, thereby increasing the deformation resistance of the steel sheet.
Preferably, the mass concentration of the sodium silicate, the fatty alcohol polyoxyethylene ether sodium sulfate and the vitamin C in the cooling water is 0.2-0.5wt%, 0.6-0.9wt% and 0.05-0.07 wt% respectively.
By adopting the technical scheme, the cooling speed can be controlled to be 80-90 ℃/min by controlling the concentration of sodium silicate, fatty alcohol polyoxyethylene ether sodium sulfate and vitamin C; the temperature difference between water and the slab is not changed by adding the substances, but the heat transfer speed and the heat release speed can be increased, so that the temperature can be reduced more quickly without affecting the performance of the slab.
The pickling and flushing process specifically comprises the following steps:
washing the plate blank by adopting a pretreatment solution, carrying out acid washing on the plate blank for 2-3 times by using an acid washing liquid after washing, and carrying out washing by adopting an aqueous solution for 4-5 times after the acid washing is finished;
the pickling solution comprises the following components in percentage by mass: 30-45% of 40wt% of hydrochloric acid, 1-5% of sulfuric acid of 75wt%, 0.2-0.5% of ethylenediamine tetraacetic acid, 1-3% of propylsulfide, 0.5-0.8% of zinc oxide, 0.5-1.5% of dicycloalkylamine nitrite, 3-4% of ethanol and the balance of water, wherein the sum of the components is 100%.
Through adopting above-mentioned technical scheme, at first adopt pretreatment solution to wash the processing in this application, can be that the iron oxide scale layer takes place swelling and not hard up to can be better carry out the pickling. In the pickling solution, propyl sulfide, zinc oxide and dicycloalkyl amine nitrite are added as corrosion inhibitors, and after the oxide layer is removed, the three can protect the Fe layer from being corroded in multiple aspects; wherein, the propyl sulfide can be adsorbed on the surface of steel, so that the electrode reaction which causes corrosion when the steel is pickled is blocked; zinc epoxy acid is a grease type substance, has stronger adsorption capacity to the surface layer of Fe metal and poorer adsorption capacity to iron oxide, so that the zinc epoxy acid can be efficiently adsorbed on the surface of iron to play a role in isolating acidic medium; dicycloalkylamine nitrite is a vapor phase corrosion inhibitor that inhibits further oxidation of ferrous metal. The occurrence of pit in the pickling process can be better avoided through the mutual cooperation of the three corrosion inhibitors.
Preferably, the pretreatment solution comprises the following components in percentage by mass: 2-3% of nano titanium dioxide, 4-5% of sodium dodecyl sulfonate, 10-15% of ethanol and the balance of water, wherein the sum of the components is 100%.
By adopting the technical scheme, the pretreatment liquid contains nano titanium dioxide, has smaller particle size and a large number of polar groups on the surface, so that the nano titanium dioxide can be attached to micro pits and cracks of the ferrite cortex, the ferrite cortex can be uniformly dissolved in the subsequent pickling process, the pickling quality is improved, and the occurrence of pits is reduced; the sodium dodecyl sulfonate has better foamability and surface activity, can swell and loosen an oxidation skin layer, so that the acid washing is better, and the ethanol is added to improve the dispersibility of the nano titanium dioxide, so that the treatment liquid is more uniformly dispersed.
In summary, the present application includes at least one of the following beneficial technical effects:
1. according to the pickling plate, B and Ce elements are introduced into the pickling plate, so that the adhesion force of iron scales can be reduced, and the problem that pits appear in pickling can not be caused while the strength of the pickling plate is improved.
2. In the preparation method, sodium silicate, fatty alcohol polyoxyethylene ether sodium sulfate and vitamin C are added into cooling water cooled by laminar flow; the cooling speed can be increased, and the content of ferroferric oxide in the ferric oxide skin layer can be reduced, so that the pickling is easier and the pickling is easier.
3. In the pickling process, the corrosion inhibitor is added into the pickling solution, so that the steel surface layer can be protected from multiple aspects, the surface defects are reduced, and the comprehensive performance of the pickling plate is improved.
Detailed Description
Example 1
The raw material composition of the pickled plate in this example can be seen in table 1, and the specific preparation method is as follows:
s1, preparing materials according to raw materials of the pickling plate, and casting into a plate blank;
s2, heating the plate blank to 1200 ℃, preserving heat for 1h, and then performing high-pressure water descaling; rough rolling is carried out on the plate blank after descaling according to the total rolling reduction of 60%, and the outlet temperature of the rough rolling mill is controlled to be 1050 ℃; after finishing rough rolling, performing finish rolling according to the total rolling reduction of 40%, and controlling the outlet temperature of a finishing mill to be 850 ℃; air-cooling to 750 ℃ of the steel plate, and performing inter-laminar cooling to 350 ℃ of the air-cooled steel plate for about 5 minutes, wherein the mass concentration of sodium silicate, fatty alcohol polyoxyethylene ether sodium sulfate and vitamin C in cooling water used in the inter-laminar cooling is respectively 0.4wt%, 0.7wt% and 0.06wt%; and coiling the cooled steel plate.
S3: uncoiling the coiled steel plate, flushing the steel plate by adopting a pretreatment solution (the pretreatment solution comprises, by mass, 3% of nano titanium dioxide, 4% of sodium dodecyl sulfate, 12% of ethanol and 81% of water), pickling the treated steel plate by adopting a pickling solution for 2 times (the pickling solution comprises, by mass, 40% of hydrochloric acid, 40% of sulfuric acid, 4% of ethylene diamine tetraacetic acid, 0.3% of propylsulfide, 0.7% of zinc oxide, 1.0% of dicycloylamine nitrite, 4% of ethanol and 48% of water), flushing the steel plate by adopting water for 5 times after pickling, drying, and coiling to obtain the pickled plate.
Examples 2 to 4
The raw material compositions of the pickled plates in examples 2 to 4 are shown in Table 1, and the preparation method is the same as that in example 1.
Comparative example 1
The composition of comparative example 1 can be seen in Table 1, and is substantially the same as example 3 except that element B was not added.
Comparative example 2
The composition of comparative example 1 can be seen in Table 1, and is substantially identical to example 3, except that Ce element is not added.
Example 5
The raw material composition of the pickled plate in this example can be seen in table 1, and the specific preparation method is as follows:
s1, preparing materials according to raw materials of the pickling plate, and casting into a plate blank;
s2, heating the plate blank to 1150 ℃, preserving heat for 80min, and then performing high-pressure water descaling; rough rolling is carried out on the plate blank after descaling according to the total reduction of 50%, and the outlet temperature of the rough rolling mill is controlled to be 1080 ℃; after finishing rough rolling, performing finish rolling according to the total rolling reduction of 50%, and controlling the outlet temperature of a finishing mill to be 830 ℃; air-cooling to 730 ℃ of the steel plate, and performing laminar flow inter-cooling to 350 ℃ for about 4min, wherein the mass concentration of sodium silicate, fatty alcohol polyoxyethylene ether sodium sulfate and vitamin C in cooling water used in the laminar flow inter-cooling is respectively 0.2wt%, 0.9wt% and 0.05wt%; and coiling the cooled steel plate.
S3: uncoiling the coiled steel plate, flushing the steel plate by adopting a pretreatment solution (the pretreatment solution comprises 2% of nano titanium dioxide, 5% of sodium dodecyl sulfate, 10% of ethanol and 83% of water by mass), pickling the treated steel plate for 3 times by adopting a pickling solution (the pickling solution comprises 30% of hydrochloric acid by weight, 5% of sulfuric acid by weight, 0.2% of ethylenediamine tetraacetic acid by weight, 3% of propylsulfide, 0.5% of zinc oxide, 0.5% of dicycloylamine nitrite, 4% of ethanol and 56.8% of water by mass), flushing the steel plate by adopting water for 5 times after pickling, drying and coiling to obtain the pickled plate.
Example 6
The raw material composition of the pickled plate in this example can be seen in table 1, and the specific preparation method is as follows:
s1, preparing materials according to raw materials of the pickling plate, and casting into a plate blank;
s2, heating the plate blank to 1250 ℃, preserving heat for 40min, and then performing high-pressure water descaling; rough rolling is carried out on the plate blank after descaling according to the total reduction of 55%, and the outlet temperature of the rough rolling mill is controlled to be 1020 ℃; after finishing rough rolling, performing finish rolling according to the total rolling reduction of 45%, and controlling the outlet temperature of a finishing mill to be 860 ℃; air-cooling to 760 ℃ of the steel plate, and performing inter-laminar cooling to 350 ℃ for about 4.5min, wherein the mass concentration of sodium silicate, fatty alcohol-polyoxyethylene ether sodium sulfate and vitamin C in cooling water used in the inter-laminar cooling is 0.5wt%, 0.6wt% and 0.07wt% respectively; and coiling the cooled steel plate.
S3: uncoiling the coiled steel plate, flushing the steel plate by adopting a pretreatment solution (the pretreatment solution comprises 2% of nano titanium dioxide, 5% of sodium dodecyl sulfate, 10% of ethanol and 83% of water by mass), pickling the treated steel plate by adopting a pickling solution for 2 times (the pickling solution comprises 45% of hydrochloric acid by weight of 40% of sulfuric acid by weight of 75% of sulfuric acid by weight of 0.4% of ethylenediamine tetraacetic acid by weight of 1% of propylsulfide, 0.8% of zinc oxide, 1.5% of dicycloylamine nitrite, 4% of ethanol and 46.3% of water by weight of the steel plate by mass), flushing the steel plate by adopting water for 5 times after pickling, drying and coiling to obtain the pickled plate.
TABLE 1
Figure SMS_1
Example 7
Example 7 is substantially identical to example 3, except for the difference in step S2, which is as follows:
s2, heating the plate blank to 1200 ℃, preserving heat for 1h, and then performing high-pressure water descaling; rough rolling is carried out on the plate blank after descaling according to the total rolling reduction of 60%, and the outlet temperature of the rough rolling mill is controlled to be 1050 ℃; after finishing rough rolling, performing finish rolling according to the total rolling reduction of 40%, and controlling the outlet temperature of a finishing mill to be 850 ℃; and then air-cooling the steel plate to 750 ℃, carrying out laminar flow inter-cooling on the air-cooled steel plate to 350 ℃, wherein the cooling time is about 11min, and coiling the cooled steel plate by using common industrial water for the laminar flow inter-cooling.
Example 8
Example 8 is substantially identical to example 3, except for the difference in step S2, which is as follows:
s2, heating the plate blank to 1200 ℃, preserving heat for 1h, and then performing high-pressure water descaling; rough rolling is carried out on the plate blank after descaling according to the total rolling reduction of 60%, and the outlet temperature of the rough rolling mill is controlled to be 1050 ℃; after finishing rough rolling, performing finish rolling according to the total rolling reduction of 40%, and controlling the outlet temperature of a finishing mill to be 850 ℃; air-cooling to 750 ℃ of the steel plate, and performing inter-laminar cooling to 350 ℃ of the air-cooled steel plate for about 5min, wherein the mass concentration of sodium silicate and fatty alcohol polyoxyethylene ether sodium sulfate in cooling water used in the inter-laminar cooling is 0.4wt% and 0.7wt% respectively; and coiling the cooled steel plate.
Example 9
Example 9 is substantially identical to example 3, except for the difference in step S2, which is as follows:
s2, heating the plate blank to 1200 ℃, preserving heat for 1h, and then performing high-pressure water descaling; rough rolling is carried out on the plate blank after descaling according to the total rolling reduction of 60%, and the outlet temperature of the rough rolling mill is controlled to be 1050 ℃; after finishing rough rolling, performing finish rolling according to the total rolling reduction of 40%, and controlling the outlet temperature of a finishing mill to be 850 ℃; air-cooling to 750 ℃ of the steel plate, and performing inter-laminar cooling to 350 ℃ of the air-cooled steel plate for about 7min, wherein the mass concentration of the fatty alcohol polyoxyethylene ether sodium sulfate and the vitamin C in cooling water used in the inter-laminar cooling is 0.7wt% and 0.06wt% respectively; and coiling the cooled steel plate.
Example 10
Example 10 is substantially identical to example 3, except for the difference in step S2, which is as follows:
s2, heating the plate blank to 1200 ℃, preserving heat for 1h, and then performing high-pressure water descaling; rough rolling is carried out on the plate blank after descaling according to the total rolling reduction of 60%, and the outlet temperature of the rough rolling mill is controlled to be 1050 ℃; after finishing rough rolling, performing finish rolling according to the total rolling reduction of 40%, and controlling the outlet temperature of a finishing mill to be 850 ℃; air-cooling to 750 ℃ of the steel plate, and performing laminar flow inter-cooling to 350 ℃ of the air-cooled steel plate for about 5min, wherein the mass concentration of sodium silicate and vitamin C in cooling water used in the laminar flow inter-cooling is 0.4wt% and 0.06wt% respectively; and coiling the cooled steel plate.
Example 11
Example 11 is substantially identical to example 3, except that the pickling solution used in step S3 is different from the pickling solution in the following composition by mass: 40wt% of hydrochloric acid 40%,75wt% of sulfuric acid 4%, 0.3% of ethylenediamine tetraacetic acid, 7.7% of ethanol and 48% of water.
Example 12
Example 11 is substantially identical to example 3, except that the pickling solution used in step S3 is different,
the pickling solution comprises the following components in percentage by mass: 40% of 40% by weight of hydrochloric acid, 4% of 75% by weight of sulfuric acid, 0.3% of ethylenediamine tetraacetic acid, 0.7% of zinc oxide, 1.0% of dicycloalkylamine nitrite, 6% of ethanol and 48% of water
Example 13
Example 11 is substantially identical to example 3, except that the pickling solution used in step S3 is different,
the pickling solution comprises the following components in percentage by mass: the pickling solution comprises the following components in percentage by mass: 40% of hydrochloric acid, 4% of sulfuric acid of 75% of ethylene diamine tetraacetic acid of 0.3%, 2% of propylenesulfide, 1.0% of dicycloalkylamine nitrite, 4.7% of ethanol and 48% of water.
Example 14
Example 11 is substantially identical to example 3, except that the pickling solution used in step S3 is different,
the pickling solution comprises the following components in percentage by mass: the pickling solution comprises the following components in percentage by mass: 40wt% of hydrochloric acid, 40wt% of sulfuric acid, 4wt% of ethylene diamine tetraacetic acid, 0.3 wt% of propylsulfide, 0.7wt% of zinc oxide, 5wt% of ethanol and 48 wt% of water.
Example 15
Example 11 is substantially identical to example 3, except that step S3 is not treated with the pretreatment solution, as follows:
s3: uncoiling the coiled steel plate, pickling the steel plate for 2 times by using pickling solution (the mass percentage of the pickling solution is 40wt% of hydrochloric acid 45%,75wt% of sulfuric acid 1%, 0.4% of ethylenediamine tetraacetic acid, 1% of propylenesulfide, 0.8% of zinc oxide, 1.5% of dicycloalkyl amine nitrite, 4% of ethanol and 46.3% of water), washing the steel plate for 5 times by using water after the pickling is finished, drying, and coiling to obtain the pickled plate.
Performance tests were performed on the pickled plates prepared in examples 1 to 15 and comparative examples 1 to 2;
surface conditions: the basic condition of the surface was visually observed.
Performance test: 10 groups of examples 1-4 and comparative examples 1-2 were selected, and the acid-washed panels were tested for tensile strength and surface roughness according to GB/T228.1-2010 and GB/T2523-2008, respectively, and the corresponding tensile strength and roughness were recorded and averaged.
TABLE 2
Figure SMS_2
As can be seen from the data in table 2, in examples 1 to 4, the raw material ratio was mainly changed, and the surface roughness and tensile strength were changed to a certain extent with the change of the raw material ratio, but the surface was basically maintained in a relatively stable state as a whole, and the surface was basically free of pits and pits, and the overall performance was good.
Comparative examples 1 and 2 were each free of addition of B element and Ce element, and from the comparison of the properties of comparative example 1 and example 3, pitting occurred on the surface and the surface roughness was significantly improved, probably because the higher Si content resulted in a high degree of bonding of the oxide skin layer and the base steel sheet layer, uneven pickling was insufficient, and pitting occurred. The surface condition is worse in comparison of the performance of comparative example 2 and example 3, probably because Ce can reduce Si precipitation at the interface and has a softening effect on SiO 2 As it allows optimization of its performance.
Examples 5 and 6, in which the proportions of the raw materials and the process parameters were varied, were varied in their properties over a certain range, but were maintained substantially in a relatively stable state.
Examples 7 to 10 mainly change the composition of cooling water for intercooling, and from the viewpoint of performance data, example 7 showed a significant increase in surface roughness compared with example 3, probably because of the cooling using a combination of 3 componentsThe cooling speed of the water can be changed, so that Fe generated by FeO eutectoid reaction is better avoided 3 O 4 Thereby increasing the content of FeO in the ferric oxide skin layer and better realizing the removal. Examples 8 to 10 are mainly characterized in that one reagent is added to cooling water, and from the aspect of performance, the surface roughness of the pickling plate is increased to a certain extent compared with that of example 3, which indicates that the synergistic effect of 3 components can better improve the overall performance of the pickling plate.
Examples 11 to 14 mainly changed the composition of the pickling solution, and example 11 was completely free of the corrosion inhibitor component, and the surface roughness was significantly improved as compared with example 3, probably because the corrosion inhibitor could better protect the steel plate substrate, thereby making the pickling more uniform. Examples 12-14, which mainly reduce one of the pickling solutions, have different levels of surface roughness improvement compared with example 3, which means that the synergistic effect of the corrosion inhibitors in example 3 can better promote the pickling effect.
In example 15, the pretreatment solution was not used for the treatment, and the surface roughness in example 15 was significantly improved compared with that in example 3, which indicates that the pretreatment solution can better improve the pickling effect and make the pickling more uniform.
The foregoing are all preferred embodiments of the present application, and are not intended to limit the scope of the present application in any way, therefore: all equivalent changes in structure, shape and principle of this application should be covered in the protection scope of this application.

Claims (5)

1. The preparation method of the high-strength pickled plate is characterized by comprising the following steps of: batching according to the raw materials of the pickling plate, and casting into a plate blank; heating the slab, and then performing high-pressure water descaling; rough rolling and finish rolling are carried out on the plate blank after descaling, air cooling is carried out after finish rolling is finished, laminar flow inter-cooling is carried out after cooling is carried out at a set temperature, and coiling is carried out after cooling to the set temperature; then uncoiling, pickling, flushing, drying and coiling to obtain a pickled plate; wherein, the raw materials of the pickling plate consist of the following components in percentage by mass: c:0.49 to 0.54 percent of Si:0.25 to 0.45 percent of Mn:0.60 to 0.75 percent, B: 0.02-0.04%, al: 0.015-0.04%, ce: 0.2-0.4%, and the balance of Fe and unavoidable impurities, wherein the total amount of each component is 100%; the cooling water used for cooling between laminar flows contains sodium silicate, fatty alcohol polyoxyethylene ether sodium sulfate and vitamin C;
the pickling and flushing process specifically comprises the following steps: washing the plate blank by adopting a pretreatment solution, pickling the plate blank for 2-3 times by using pickling solution after the washing is finished, and washing the plate blank for 4-5 times by adopting an aqueous solution after the pickling is finished; the pickling solution comprises the following components in percentage by mass: 30-45% of 40wt% of hydrochloric acid, 1-5% of 75wt% of sulfuric acid, 0.2-0.5% of ethylenediamine tetraacetic acid, 1-3% of propylsulfide, 0.5-0.8% of zinc oxide, 0.5-1.5% of dicycloalkylamine nitrite, 3-4% of ethanol and the balance of water, wherein the sum of the components is 100%; the pretreatment solution consists of the following components in percentage by mass: 2-3% of nano titanium dioxide, 4-5% of sodium dodecyl sulfonate, 10-15% of ethanol and the balance of water, wherein the sum of the components is 100%.
2. The method for preparing the high-strength pickled plate according to claim 1, wherein the heating temperature is 1150-1250 ℃, and the heat preservation time is 40-80 min.
3. The method for preparing the high-strength pickled plate according to claim 1, wherein the total reduction of rough rolling is 50-60%, and the outlet temperature of the rough rolling mill is 1020-1080 ℃; the total reduction of rough rolling is 40-50%, and the outlet temperature of the finishing mill is 830-860 ℃.
4. The method for producing a high-strength pickled plate according to claim 1, wherein the air cooling is performed until the temperature of the plate blank is 730-760 ℃.
5. The method for preparing the high-strength pickled plate according to claim 1, wherein the mass concentrations of sodium silicate, fatty alcohol-polyoxyethylene ether sodium sulfate and vitamin C in cooling water are respectively 0.2-0.5wt%, 0.6-0.9wt% and 0.05-0.07 wt%.
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