WO2018214682A1 - 一种热浸镀中锰钢及其制造方法 - Google Patents

一种热浸镀中锰钢及其制造方法 Download PDF

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WO2018214682A1
WO2018214682A1 PCT/CN2018/083848 CN2018083848W WO2018214682A1 WO 2018214682 A1 WO2018214682 A1 WO 2018214682A1 CN 2018083848 W CN2018083848 W CN 2018083848W WO 2018214682 A1 WO2018214682 A1 WO 2018214682A1
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manganese steel
hot
annealing
content
steel
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English (en)
French (fr)
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金鑫焱
张玉龙
胡广魁
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Baoshan Iron and Steel Co Ltd
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Baoshan Iron and Steel Co Ltd
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Priority to EP18806516.3A priority Critical patent/EP3633061B1/en
Priority to KR1020197035799A priority patent/KR20200003174A/ko
Priority to CA3064643A priority patent/CA3064643C/en
Priority to US16/616,118 priority patent/US11313021B2/en
Priority to JP2019565343A priority patent/JP6874163B2/ja
Publication of WO2018214682A1 publication Critical patent/WO2018214682A1/zh
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    • 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
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/04—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the coating material
    • C23C2/06—Zinc or cadmium or alloys based thereon
    • 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
    • C22C38/001—Ferrous alloys, e.g. steel alloys containing N
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21C—MANUFACTURE OF METAL SHEETS, WIRE, RODS, TUBES, PROFILES OR LIKE SEMI-MANUFACTURED PRODUCTS OTHERWISE THAN BY ROLLING; AUXILIARY OPERATIONS USED IN CONNECTION WITH METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL
    • B21C37/00—Manufacture of metal sheets, rods, wire, tubes, profiles or like semi-manufactured products, not otherwise provided for; Manufacture of tubes of special shape
    • B21C37/04—Manufacture of metal sheets, rods, wire, tubes, profiles or like semi-manufactured products, not otherwise provided for; Manufacture of tubes of special shape of rods or wire
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
    • B32B15/013—Layered products comprising a layer of metal all layers being exclusively metallic one layer being formed of an iron alloy or steel, another layer being formed of a metal other than iron or aluminium
    • 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
    • C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
    • C21D1/74—Methods of treatment in inert gas, controlled atmosphere, vacuum or pulverulent material
    • 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
    • C21D6/00—Heat treatment of ferrous alloys
    • C21D6/005—Heat treatment of ferrous alloys containing Mn
    • 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
    • C21D6/00—Heat treatment of ferrous alloys
    • C21D6/008—Heat treatment of ferrous alloys containing Si
    • 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 of ferrous metals or ferrous alloys by deformation combined with, or followed by, heat treatment
    • C21D8/02—Modifying the physical properties of ferrous metals or ferrous alloys by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • 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 of ferrous metals or ferrous alloys by deformation combined with, or followed by, heat treatment
    • C21D8/02—Modifying the physical properties of ferrous metals or ferrous alloys by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • C21D8/0247—Modifying the physical properties of ferrous metals or ferrous alloys by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the heat treatment
    • C21D8/0273—Final recrystallisation annealing
    • 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
    • C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
    • C21D9/52—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for wires; for strips ; for rods of unlimited length
    • C21D9/54—Furnaces for treating strips or wire
    • C21D9/56—Continuous furnaces for strip or wire
    • 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
    • C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
    • 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
    • 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
    • C21D2211/005—Ferrite

Definitions

  • the invention relates to the field of high-strength steel, in particular to a hot-dip-plated medium-manganese steel and a manufacturing method thereof.
  • Advanced high-strength steel is the best material to meet the weight reduction of automobiles and improve the safety of collision. With the continuous deepening of the development of advanced high-strength steel in the world's steel companies, steel grades with higher strength and higher elongation have been developed.
  • the Mn content of medium-manganese steel is usually 4-12%, which is lower than the high Mn content design of TWIP steel (Mn ⁇ 15%), but higher than the conventional high-strength steel Mn content design (about 1-3%). ).
  • the austenite content of the medium manganese steel at room temperature is more than 30%, and even more than half of it becomes the steel substrate structure, so that a sustained and significant TRIP effect is obtained during the deformation process, and the performance of the strong plastic product is more than 30 GPa ⁇ %.
  • the current medium manganese steel includes a C-Si-Mn system, a C-Mn-Al system, and a V-alloyed C-Mn-Al-Si system.
  • the surface of the manganese steel in cold rolling is prone to rust. Therefore, it is desirable to plate the surface of the medium manganese steel to avoid corrosion of the steel.
  • the most typical coating is hot-dip galvanizing.
  • medium manganese steel has a higher Mn content than conventional advanced high strength steel, making its hot dip galvanizing a challenge. This is because when the strip is annealed in a reducing atmosphere, although the atmosphere is reductive to Fe, it is oxidizing to elements such as Mn, Si, and Al, so these alloying elements are enriched during annealing of the strip. An oxide film that affects the wettability of the zinc liquid is formed on the surface of the strip, resulting in poor plating or plating adhesion.
  • the currently disclosed solutions mainly include improved composition design, controlled annealing atmosphere, pre-plating of metal before annealing, and pickling before immersion in plating solution.
  • the additive elements in the prior art include Sb, Sn, and the like.
  • Controlling the annealing atmosphere is another method to improve the platability of advanced high-strength steel, mainly including controlling the dew point of the annealing atmosphere, adjusting the content of H2 and H2O in the annealing atmosphere, etc.
  • the above parameters can be adjusted.
  • the plating property has a certain improvement effect, but the effect on the medium and high manganese steel with high Mn content is not obvious.
  • Chinese Patent Publication No. CN101506403B discloses a method of "coating a metal protective layer for hot-rolled or cold-rolled steel strip containing 6 wt% to 30 wt% of Mn", one being hot rolled steel strip or cold rolled steel.
  • a method of plating a metal protective layer is characterized in that, in order to produce a metal protective layer substantially free of an oxidation sublayer on the steel strip, the water content %H2O and hydrogen in the annealing atmosphere are adjusted according to the respective annealing temperatures T G in the following relationship:
  • the ratio %H2O/%H2 of the content %H2 is: %H2O/%H2 ⁇ 8 ⁇ 10 -15 ⁇ T G 3.529 .
  • the H2 content must be very high (such as 50% or even 100%), while the H2 content in the conventional hot-dip galvanizing line heating furnace is usually only 1-10%.
  • Chinese Patent Publication No. CN102421928B discloses a method of "hot-dip coating a flat steel product containing 2-35 wt% Mn and a flat steel product", and a zinc or zinc alloy pair containing 2-35 wt%.
  • a method of hot dip coating of a flat steel product of Mn is disclosed.
  • the annealing atmosphere of the method contains 0.01-85% by volume of H2, H2O and the remaining N2, and unavoidable impurities determined by technical conditions, the dew point of the annealing atmosphere is between -70 ° C and +60 ° C, wherein H 2 O the ratio / H2 conforms: 8 ⁇ 10 -15 ⁇ T G 3.529 ⁇ H2O / H2 ⁇ 0.957, thereby generating a thickness on the flat steel product is 20-400nm, at least Mn mixed oxide layer of the flat steel product is segmented cover .
  • the atmosphere in the conventional hot-dip galvanizing line heating furnace easily satisfies the above relationship, when the surface of the strip steel has a Mn mixed oxide of 20-400 nm, the galvanizing improvement effect is very limited.
  • Pre-plating is another method to improve the platability of high-strength steel.
  • the surface of the steel sheet before annealing such as Fe, Cu, Ni, Al and other metals
  • the oxides such as Si and Mn are formed on the steel substrate and controlled during the annealing process. The interface of the coating is thus avoided to enrich the surface.
  • Chinese Patent Publication No. CN100577843C discloses the name "steel strip plating method and steel strip provided with the coating layer", the steel strip comprising Mn: 6-30% by weight, the method is characterized in that An aluminum layer is applied to the steel strip prior to final annealing, and after final annealing, the coating is applied to the aluminum layer.
  • the key of this method is to first coat a surface of the medium manganese steel before annealing with a layer of aluminum (optional PVD method, the thickness of the aluminum layer is 50-1000 nm), which can inhibit the external oxidation of Mn.
  • the shortcoming of this pre-plating method is that the efficiency is very low, and it is difficult to meet the requirements of industrial continuous production. Moreover, the hardware investment of the pre-plating equipment will be very high.
  • the pickling method mainly relies on the acid washing to wash away the surface element enrichment formed during the annealing process, thereby eliminating the adverse effect of the surface oxide on the galvanizing.
  • Cispheral Patent Publication No. CN101730752B discloses the name "Method for hot dip galvanizing of AHSS or UHSS strip and obtained strip", a pair of dual phase steel, phase change induced plastic steel, phase transformation induced plastic assisted duplex
  • a method for hot dip galvanizing of steel or twin induced plastic steel strips characterized in that the strip is pickled and subsequently heated to a temperature below the continuous annealing temperature prior to hot dip galvanizing of the strip
  • the temperature below the continuous annealing temperature is between 400 ° C and 600 ° C, wherein Fe is reduced in the strip during or after heating to a temperature below the continuous annealing temperature and prior to hot dip galvanizing, and wherein Excess O2 is provided in the atmosphere during or after heating the strip and before the strip is reduced.
  • Chinese Patent Publication No. CN101952474B discloses a method for "metallizing a protective layer for hot rolled or cold rolled flat steel products containing 6-30% by weight of manganese", a pair containing 6-30% by weight of manganese.
  • the acid-washed flat steel product needs to be dried before being immersed in the molten pool to prevent the acid from entering the molten-dip processing equipment, and the flat steel product needs to be reheated to the bath temperature, and in order to avoid The flat steel product re-forms the oxide formation which impairs the plating result before it is immersed in the molten pool, and it is necessary to control the surface temperature not to exceed 700 ° C during the heating process.
  • the conventional hot-dip galvanizing unit is usually arranged by heating, soaking, cooling, hot dip plating, and re-cooling.
  • the method of the above two patents is to first cool the strip after soaking to the pickling temperature (usually at least below 100 ° C), then pickling, and then heating to the temperature of the immersion bath for hot dip coating.
  • the pickling section, the reheating section and the necessary temperature equalization section the industrial production line will be very long and the cost of the equipment will be very high.
  • Medium manganese steel has gained great attention in the steel industry and the automotive industry due to its high strength and high elongation.
  • the future application of manganese steel in hot dip coating is promising. Therefore, if an economical hot dip-plating medium-manganese steel and a method for producing the same are provided, the problem of platability of the medium-manganese steel can be solved, and the hot-dip-plated medium-manganese steel having excellent surface quality of the plating layer and excellent adhesion of the plating layer is obtained. It is of great significance to promote the industrial application of medium manganese steel and the weight reduction of automobiles.
  • An object of the present invention is to provide a hot-dip-plated medium-manganese steel which has the advantages of excellent surface quality of a plating layer, good plating adhesion, and excellent corrosion resistance.
  • a hot-dip-plated medium-manganese steel comprising a steel substrate and a plating layer on a surface of the steel substrate; wherein the mass percentage of the manganese steel in the hot dip plating is C: 0.1 to 0.3%, Si: 0.1 to 2.0%, Mn: 5 to 12%, Al: 1-2%, P ⁇ 0.02%, S ⁇ 0.02%, N ⁇ 0.005%, the balance being Fe and other unavoidable impurities; and the core structure of the steel substrate is Ferritic and austenitic, the surface layer of the steel substrate is a ferrite layer.
  • C It is a typical solid solution strengthening element in steel, and it can also improve the stability of austenite, and it is beneficial to retain a certain volume fraction of retained austenite at room temperature, thereby producing a phase change induced plasticity (TRIP) effect.
  • TRIP phase change induced plasticity
  • Si It is an essential element for deoxidation of steelmaking. Si not only has a certain solid solution strengthening effect, but also has the effect of inhibiting the precipitation of carbides. Once the Si content is less than 0.1%, it is difficult to obtain a sufficient deoxidation effect in the steel. However, too high a Si content will also affect the overall properties of the steel. In addition, an appropriate amount of Si can also act to prevent the precipitation of cementite, thereby improving the stability of austenite during cooling. In view of this, it is necessary to control the Si content in the steel sheet to be 0.1% to 2%, and preferably 0.3% to 1.5%.
  • Mn is an effective austenite stabilizing element.
  • the effect of Mn is similar to that of C, which can effectively improve the material stacking fault energy, lower the martensite transformation temperature Ms, and improve the austenite stability.
  • the increase in the Mn content leads to a decrease in the strength of the material. Therefore, under the premise of ensuring the stability of the austenite of the material, it is necessary to reduce the Mn content as much as possible. Therefore, the present invention limits the mass percentage of the Mn element to 5-12%.
  • Al It can effectively improve the resistance to delayed cracking of materials, but the addition of Al can significantly deteriorate the smelting and continuous casting properties of steel, which can easily lead to water blocking at continuous casting. Moreover, in the smelting and continuous casting process, the formation of a large amount of Al 2 O 3 reduces the fluidity of the molten steel to cause problems such as slag rolling, slab cracking, etc., and therefore the present invention limits the mass percentage of the Al element to 1-2%.
  • the main impurity elements in the steel sheet according to the present invention are P, S and N, and the less the impurity elements should be controlled, the finer the steel sheet thus obtained.
  • the impurity elements P, S and N are respectively set to be P ⁇ 0.02%, S ⁇ 0.02%, and N ⁇ 0.005%.
  • the surface layer of the steel substrate according to the present invention is a ferrite layer, and the ferrite layer can make the hot-dip-plated manganese steel according to the present invention have excellent platability and coating adhesion.
  • the MnO enrichment layer affects the platability of the steel sheet (ie, the surface quality of the plating layer) and the adhesion of the plating layer. Sex (ie, the plating layer and the steel substrate have poor bonding force and are easy to fall off).
  • the surface layer of the steel substrate with higher Mn content is a ferrite layer, because the Mn in the ferrite layer is much lower than the Mn content of the steel substrate, thereby The formation of a MnO-rich layer on the surface of the ferrite layer during the annealing process before hot dip plating is avoided, which is equivalent to hot dip plating on the surface of ordinary ferritic steel, so the platability (surface quality) and adhesion of the steel sheet are adhered. Sex (binding) will be greatly improved.
  • the ferrite layer has a thickness of 0.2 to 5 ⁇ m.
  • the present invention controls the thickness of the ferrite layer on the surface of the steel substrate to be 0.2 to 5 ⁇ m.
  • the grain size of the ferrite layer is >5 ⁇ m, the ferrite layer is excessively thick, and thus the grain size of the ferrite layer of the present invention is controlled to be ⁇ 5 ⁇ m.
  • the Mn content of the ferrite layer is lower than the Mn content of the steel substrate. This is because under the conditions of one annealing process, the Mn of the surface layer of the steel substrate diffuses to the surface of the steel substrate, thereby forming a lean layer of manganese on the surface of the steel substrate.
  • the Mn content of the ferrite layer is ⁇ 5%.
  • the Mn content of the ferrite layer is controlled to be ⁇ 2%.
  • the Al content of the ferrite layer is higher than the Al content of the steel substrate because a part of Al in the steel substrate diffuses to the surface layer of the steel substrate under the conditions of the primary annealing, resulting in an increase in the Al content of the surface layer of the steel substrate.
  • the Al content of the steel substrate is 1-2%, preferably, the Al content of the ferrite layer is > 1%, and the Al content is ⁇ 5%.
  • the ferrite layer has a C content lower than that of the steel substrate C. This is because a decarburization reaction occurs in the surface layer of the steel substrate under an annealing process condition, thereby forming a surface decarburization layer.
  • the C content of the ferrite layer is ⁇ 0.1%.
  • the microstructure of the core of the steel substrate is ferrite and austenite.
  • the hot-dip galvannealing manganese steel according to the present invention has a yield strength of 700-1000 MPa, a tensile strength of 950-1350 MPa, and an elongation at break of >25%.
  • the method for manufacturing manganese steel in hot dip plating according to the present invention comprises the following steps:
  • step (2) one annealing and pickling are performed on the continuous annealing line; the strip is heated on the continuous annealing line to a soaking temperature of 600 to 750 ° C, and the soaking time is 30 to 600 s, wherein the annealing atmosphere is N 2 , H 2 mixed gas, H 2 volume content of 0.5 to 10%, dew point of -20 ⁇ +20 ° C;; after annealing the strip steel cooled to below 100 ° C, and passed the H ion concentration of 0.1 ⁇ 5% acid The liquid is pickled, the temperature of the acid solution is 50-70 ° C, the pickling time is 1 to 10 s, and the mixture is taken up after rinsing and drying.
  • the annealing atmosphere is N 2 , H 2 mixed gas, H 2 volume content of 0.5 to 10%, dew point of -20 ⁇ +20 ° C
  • H ion concentration 0.1 ⁇ 5% acid
  • Step (3) secondary annealing and hot dip plating are performed on the continuous hot-dip galvanizing production line; the strip obtained in the step (2) is subjected to secondary annealing on the hot dip plating production line to complete hot dip plating, and the second annealing is performed.
  • the hot temperature is 600-850 ° C
  • the soaking time is 60-360 s
  • the annealing atmosphere is N2, H2 mixed gas, the H2 volume content is 2-10%, the dew point is -60 ⁇ +10 °C; the strip is cooled to 380 ⁇ After 500 ° C, the bath was immersed in hot dip plating.
  • the invention controls the soaking temperature of the primary annealing, the time, and the dew point of the annealing atmosphere, so that the Mn element forms a manganese oxide layer on the surface, and forms a lean manganese and a decarburized ferrite layer on the surface layer of the steel substrate, and then uses a pickling method. After one annealing, the manganese oxide layer on the surface of the steel sheet is washed away, and the ferrite layer on the surface of the steel substrate is retained. At the time of secondary annealing, good ferdibility is obtained by using the ferrite layer of the surface layer of the steel substrate.
  • the soaking temperature is defined in the step (2) to be 600-750 ° C because when the soaking temperature is lower than 600 ° C, the surface enrichment amount of the Mn element on the surface of the steel substrate is limited, so that the surface of the steel substrate cannot be formed. In the manganese-depleted layer, the ferrite layer cannot be obtained; when the soaking temperature is higher than 750 ° C, the Mn element forms a large amount of oxides in the ferrite layer, thereby deteriorating the formability of the surface ferrite layer. Further preferably, the soaking temperature in the step (2) is 650 to 700 °C.
  • the annealing atmosphere dew point is limited to -20 ° C to + 20 ° C. This is because the annealing atmosphere is reduced to Fe in the range of the above-mentioned annealing atmosphere dew point, but is oxidized to Mn.
  • the dew point is lower than -20 °C, the thickness of the ferrite layer on the surface of the steel substrate is ⁇ 0.2 ⁇ m.
  • the dew point is higher than +20 °C, the ferrite of the surface layer of the steel substrate will form a large amount of oxidized particles of Mn, which will affect Surface performance.
  • the annealing atmosphere has a dew point of -10 ° C to + 10 ° C.
  • the soaking time in step (2) is limited to 30-600 s. Further preferably, the soaking time in the step (2) is from 30 to 180 s.
  • the annealing atmosphere in the step (2) is a mixed gas of N 2 and H 2 , and the volume of H 2 is 0.5-10% by volume.
  • the principle of controlling the pickling concentration, temperature and time in the step (2) is to wash away the surface manganese oxide layer and retain the surface ferrite layer, so the acid concentration is too high, and the acid temperature is too high. If the high and pickling stays for too long, the ferrite layer on the surface will be washed away. If the manganese oxide formed during the annealing process is too thick and the pickling is insufficient, the residual oxide layer is also disadvantageous for the hot dip plating of the step (3). Therefore, the acid concentration ranges from 0.1 to 5%, the pickling temperature is from 50 to 70 ° C, and the pickling time is from 1 to 10 s.
  • Step (3) secondary annealing and hot dip plating are performed on the continuous hot-dip galvanizing production line; the strip obtained in the step (2) is subjected to secondary annealing on the hot dip plating production line to complete hot dip plating, and the second annealing is performed.
  • the hot temperature is 600-850 ° C
  • the soaking time is 60-360 s
  • the annealing atmosphere is N2, H2 mixed gas, the H2 volume content is 2-10%, the dew point is -60 ⁇ +10 °C; the strip is cooled to 380 ⁇ After 500 ° C, the bath was immersed in hot dip plating.
  • the annealing process parameters in the step (3) can be selected within a wide range, and the annealing atmosphere is not particularly controlled, and the same annealing atmosphere can be used to obtain the same as the ordinary ferrite material. Plating.
  • the ferrite layer of 0.2-5 ⁇ m already exists in the surface layer of the steel sheet obtained in the step (2), and the usual annealing temperature, holding time and dew point of the annealing atmosphere are used in the secondary annealing process, and Mn in the ferrite layer
  • the element content is low, and the Mn element in the steel substrate cannot form a manganese oxide layer on the surface over the ferrite layer, and the manganese element in the steel substrate forms only a small amount of internal oxidation in the ferrite layer.
  • the surface state is equivalent to the surface state of the ordinary mild steel, so that the plating property is not deteriorated in a wide range of process parameters.
  • the annealing temperature in the step (3) can be selected from 600 to 850 ° C, the holding time is 60 to 360 s, the annealing atmosphere H 2 content is 2 to 10%, and the annealing atmosphere dew point is -60 to +10 ° C.
  • the mass percentage of the plating liquid component is 0.1 ⁇ Al ⁇ 6%, 0 ⁇ Mg ⁇ 5%, and the balance is Zn and other unavoidable impurities.
  • the purpose of adding 0.1-6% of Al in the plating solution is that when the steel strip is immersed in the zinc pot, the Al in the plating solution first reacts with the steel strip to form a barrier layer, thereby suppressing Zn and Fe.
  • the diffusion between the layers avoids the formation of a zinc-iron alloy phase which adversely affects the forming properties of the coating.
  • the addition of Mg to the plating solution is advantageous for further improving the corrosion resistance of the plating layer.
  • the present invention limits Mg to 0 to 5%.
  • the content of Al and Mg is too high, the hardness of the plating layer is increased, which deteriorates the forming property of the plating layer.
  • the temperature of the strip into the zinc pot is 0-10 ° C higher than the bath temperature.
  • the bath temperature is 420-480 °C.
  • the method for manufacturing the manganese steel in the hot dip coating according to the present invention can be realized on the existing continuous annealing and continuous hot dip plating production lines without major adjustment, and has a good application prospect.
  • FIG. 1 is a schematic view showing the structure of a manganese steel in hot dip plating according to the present invention.
  • FIG. 2 is a view of the structure before hot dip coating of manganese steel in hot dip coating according to the present invention.
  • Figure 3 is a cross-sectional metallographic photograph of Example 1 of the present invention.
  • Example 4 is a surface Mn element depth distribution curve of Example 1 after one annealing and pickling, after secondary annealing, Example 2 after secondary annealing, and Comparative Example 1 after one annealing.
  • Fig. 1 shows the structure of a manganese steel in hot dip plating according to the present invention.
  • the hot-dip-plated medium-manganese steel according to the present invention comprises a steel substrate 1 and a plating layer 2 on the surface of the steel substrate 1, wherein 11 is a core structure of the steel substrate, and 12 is a surface layer of the steel substrate- Ferritic layer.
  • Figure 2 shows the microstructure of the hot dip plated manganese steel prior to hot dip coating according to the present invention.
  • the core structure 11 of the steel substrate is austenite + ferrite
  • the surface layer 12 of the steel substrate is a ferrite layer.
  • Fig. 3 shows a section metallographic phase of Embodiment 1 of the present invention. As shown in Fig. 3, 11 is a core portion of the steel substrate 1, 12 is a ferrite layer, and 2 is a plating layer.
  • the present inventors conducted detailed studies on the process parameters in the steps (2) and (3) in the method for producing manganese steel in hot dip plating according to the present invention.
  • Table 1 lists the chemical composition mass percentages of the hot-dip-plated manganese steels of Examples 1 to 20 and the conventional steel sheets of Comparative Examples 1-12. The balance is Fe and inevitable impurities
  • the content of the chemical components in the components I, II and III is controlled in the range of C: 0.1 to 0.3%, Si: 0.1 to 2.0%, Mn: 5 to 12%, and Al: 1-2. %, P ⁇ 0.02%, S ⁇ 0.02%, N ⁇ 0.005%.
  • the Mn content of the component IV is outside the range of the above components.
  • the strip is heated in a continuous annealing line to a soaking temperature of 600-750 ° C, and the soaking time is 30-600 s, wherein the annealing atmosphere is a mixture of N2 and H2, and the volume of H2 is 0.5. ⁇ 10%, dew point is -20 ⁇ +20°C; the strip after annealing is cooled to below 100°C, and acid washed with acid solution with H ion concentration of 0.1-5%, the acid temperature is 50-70 °C, pickling time 1 ⁇ 10s; after rinsing and drying, coiling;
  • the strip obtained in the step (2) is subjected to secondary annealing on the hot dip plating line to complete hot dip plating, and the soaking temperature of the second annealing is 600 to 850 ° C, both of which are
  • the hot time is 60-360s
  • the annealing atmosphere is N2, H2 mixed gas, the volume content of H2 is 2-10%, the dew point is -60 ⁇ +10 °C; the strip is cooled to 380-500 °C and then immersed in the bath for hot dip plating.
  • Table 2 lists the specific process parameters of the hot-dip-plated medium-manganese steel in Examples 1-20 and the conventional steel sheets of Comparative Examples 1-12.
  • Figure 4 shows the surface of Example 1 after one annealing and pickling (B1), after secondary annealing (B2), after Example 2 after secondary annealing (C) and Comparative Example 1 after one annealing (A) Mn element depth distribution curve.
  • A is an annealed steel sheet with an annealing temperature of 700 ° C, a soaking time of 120 s, and an annealing atmosphere dew point of -40 ° C.
  • the surface has a relatively obvious Mn enrichment, and the sub-surface lean manganese layer is not obvious. When the surface state is subjected to hot dip plating, the platability is poor.
  • B1 is the steel sheet of Example 1 which has been subjected to an annealing temperature of 650 ° C, a holding time of 100 s, an annealing atmosphere dew point of 0 ° C and acid pickling, and the surface manganese oxide has been acid washed off, and the subsurface has a thickness of about 1 ⁇ m. Manganese layer.
  • B2 is the surface Mn element depth distribution of the strip after the second annealing of the stripped steel of the first embodiment after the second annealing of the annealing temperature of 650 ° C, the holding time of 120 s, and the dew point of the annealing atmosphere of -10 ° C.
  • the surface of the B2 strip has a small amount of Mn enrichment, but is much lower than that of Comparative Example A. When the surface state is hot dip plated, it has good platability.
  • Example C is the depth distribution of the Mn element on the surface of the strip after the second annealing of the step 2 (2) and the step (3), wherein the annealing temperature in the step (2) is 650 ° C, the holding time is 120 s, and the dew point of the annealing atmosphere is 0. °C, the second annealing temperature in step (3) is 800 ° C, the holding time is 90 s, and the dew point of the annealing atmosphere is -50 ° C. Since the secondary annealing temperature of Example 2 is higher than the secondary annealing temperature of Example 1, and the secondary annealing atmosphere dew point is lower than the secondary annealing atmosphere dew point of Example 1, the surface Mn element enrichment ratio of Example 2 is implemented. Example 1 is obvious, but still lower than Comparative Example 1, and the plateability of the strip in this surface state is still good when hot dip plating.
  • Table 3 lists the respective performance parameters and microstructure characteristics of the hot dip plated manganese steel sheets of Examples 1-20 and the conventional steel sheets of Comparative Examples 1-12.
  • the platability can be judged by directly observing the appearance of the strip after plating with the naked eye. If the surface has no obvious iron, the plating property is good (indicated by ⁇ ), and if the surface has obvious iron, the plating property is poor (indicated by ⁇ ).
  • the method for detecting the adhesion of the plating layer is to take a sample having a length of 200 mm and a width of 100 mm on the strip, and to perform a 180-degree bending and flattening, and to use a tape to bend the bent position. If the zinc-free layer is not adhered by the tape or the surface of the plated surface of the bent surface which is adhered by the tape is not embossed, it means that the adhesion of the plating layer is good (indicated by ⁇ ); if the plating layer is stuck by the tape or the bent surface is adhered by the tape If the coating is raised, it means that the coating has poor adhesion (indicated by ⁇ )
  • the yield strength of Examples 1-20 is 700-1000 MPa, the tensile strength is 950-1350 MPa, and the elongation at break is >25%; the thickness of the surface ferrite layer of Example 1-20 steel substrate is 0.2-5 ⁇ m, the grain size of the surface ferrite layer is ⁇ 5 ⁇ m; and the platability and the adhesion of the plating layer are superior to those of Comparative Examples 1-10.
  • the embodiment forms a ferrite layer on the surface of the steel substrate in the step (2), the diffusion of Mn in the steel substrate to the surface of the steel sheet is suppressed in the step (3), which is advantageous for Al in the plating solution.
  • the ferrite layer forms an effective Fe-Al barrier layer, so that good platability and coating adhesion can be obtained.
  • Comparative Example 11-12 since the steel substrate component and the production method which are not limited by the present invention are not used, the plating property and the plating adhesion are good, but the steel substrate core is not made of ferrite + austenite, and the steel substrate is not provided.
  • the surface layer is the structural feature of the ferrite layer, and the elongation at break is low.

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Abstract

一种热浸镀中锰钢及其制造方法，该中锰钢包括钢基板和位于钢基板表面的镀层；该热浸镀中锰钢的成分质量百分比为C：0.1～0.3％，Si：0.1-2.0％、Mn：5～12％，Al：1-2％，P≤0.02％，S≤0.02％，N≤0.005％，余量为Fe和不可避免杂质；并且芯部组织为铁素体和奥氏体，钢基板表层为铁素体层。

Description

一种热浸镀中锰钢及其制造方法 技术领域
本发明涉及高强钢领域，尤其涉及一种热浸镀中锰钢及其制造方法。
背景技术
先进高强钢是满足汽车轻量化、提高碰撞安全性的最佳材料。随着世界各钢铁公司在先进高强钢开发方面的不断深入，具有更高强度、同时具有更高延伸率的钢种已陆续被开发出来。
在先进高强钢家族中，中锰钢的Mn含量通常为4-12％，低于TWIP钢高Mn含量设计(Mn≥15％)，但高于常规高强钢Mn含量设计(约1-3％)。中锰钢室温下的奥氏体含量大于30％，甚至超过半数成为钢基板组织，从而在变形过程中获得持续显著的TRIP效应，达到强塑积大于30GPa·％的性能。目前的中锰钢有C-Si-Mn系、C-Mn-Al系以及V微合金化的C-Mn-Al-Si系等。
但是冷轧中锰钢表面容易发生锈蚀，因此希望在中锰钢表面镀覆上金属镀层避免钢材受到腐蚀，其中最典型的镀层为热镀锌。然而，中锰钢相比于常规先进高强钢，其Mn含量较高，使其热镀锌成为一种挑战。这是因为当带钢在还原气氛中退火时，虽然气氛对Fe是还原性的，但是对Mn、Si、Al等元素是氧化性的，因此在带钢退火过程中，这些合金元素会富集到带钢表面形成影响锌液润湿性的氧化膜，从而导致漏镀或者镀层结合力较差。
为了消除合金元素表面富集对先进高强钢锌液润湿性的不利影响，目前公开的解决方法主要有改善成分设计、控制退火气氛、在退火前预镀金属、浸入镀液前酸洗等。
改善成分设计除了尽量降低有害元素的含量外，还可以通过添加其它元素改变Mn元素的表面富集状态，现有技术中的添加元素有Sb、Sn等。
控制退火气氛是另外一种改善先进高强钢可镀性的方法，主要包括控 制退火气氛露点，调节退火气氛中H2、H2O的含量等，当Mn、Si元素含量较低时，调节上述参数对可镀性有一定的改善作用，但对于Mn含量较高的中、高锰钢的效果不明显。
例如，中国专利公开号CN101506403B公开名称为“为含有6重量％至30重量％的Mn的热轧或冷轧钢带镀覆金属保护层的方法”，一种为热轧钢带或冷轧钢带镀覆金属保护层的方法。该方法的特征在于：为了在所述钢带上产生基本不存在氧化次层的金属保护层，按照各退火温度T G，以如下关系式来调节所述退火气氛中的水含量％H2O与氢气含量％H2的比值％H2O/％H2，所述关系式为：％H2O/％H2≤8·10 -15·T G 3.529。事实上，为了满足上述关系式，H2含量必须非常高(如50％，甚至100％)，而传统的热镀锌生产线加热炉内的H2含量通常只有1-10％。
又例如，中国专利公开号CN102421928B公开名称为“对含2-35重量％Mn的扁钢制品进行热浸镀层的方法和扁钢制品”，一种采用锌或锌合金对含2-35重量％Mn的扁钢制品进行热浸镀层的方法。该方法的退火气氛含有0.01-85体积％的H2、H2O和其余的N2、以及由技术条件决定的不可避免的杂质，该退火气氛的露点在-70℃和+60℃之间，其中，H2O/H2的比值符合：8·10 -15·T G 3.529≤H2O/H2≤0.957，从而在扁钢制品上生成厚度为20-400nm，至少分段式覆盖该扁钢制品的Mn混合氧化物层。虽然常规热镀锌线加热炉内气氛容易满足以上关系式，但当带钢表面存在20-400nm的Mn混合氧化物时，可镀锌改善效果十分有限。
预镀是另外一种改善高强钢可镀性的方法，通过在退火前的钢板表面预镀Fe、Cu、Ni、Al等金属，控制退火过程中Si、Mn等氧化物形成在钢基板与预镀层的界面上，从而避免在表面的富集。
例如，中国专利公开号CN100577843C公开名称为“钢带镀层方法以及设有所述镀层的钢带”，所述钢带以重量％计包含Mn：6-30％、所述方法的特征在于，在最终退火之前将铝层施加于所述钢带上，在最终退火之后，将所述镀层施加于所述铝层上。该方法的关键是需要在退火前的中锰钢表面先镀上一层铝(可选PVD的方法，铝层厚度50-1000nm)，起到抑制Mn元素的外氧化的作用。该预镀方法的不足之处在于效率非常低，很难满足工业化连续生产的要求，不仅如此，预镀设备的硬件投资也会非 常高。
酸洗方法主要是使带钢通过酸洗洗掉退火过程中形成的表面元素富集，从而消除表面氧化物对镀锌的不利影响。
例如，中国专利公开号CN101730752B公开名称为“对AHSS或者UHSS带材进行热浸镀锌的方法以及所得带材”，一种对双相钢、相变诱发塑性钢、相变诱发塑性辅助双相钢或者孪生诱发塑性钢带材进行热浸镀锌的方法，其特征在于，在对该带材进行热浸镀锌之前，对该带材进行酸洗并随后加热到低于连续退火温度的温度，该低于连续退火温度的温度在400℃到600℃之间，其中在加热到低于连续退火温度的温度期间或之后并且在热浸镀锌之前将带材中的Fe还原，并且其中在加热带材期间或之后并且在带材还原之前，在气氛中提供过量的O2。
又例如，中国专利公开号CN101952474B公开名称为“对含6-30重量％的锰的热轧或冷轧扁钢制品镀金属保护层的方法”，一种对含6-30重量％的锰的热轧或冷轧扁钢制品镀金属保护层的方法。该方法的主要特征在于，使扁钢制品在进入到热浸镀熔池之前先进行酸洗处理，在酸洗处理中，使扁钢制品经过至少两个酸洗池，从而使粘附在扁钢制品上的氧化锰清除。经过酸洗后的扁钢制品在浸入到熔池之前需先进行干燥处理以避免酸液进入到熔浸镀层处理设备中，同时还需要将扁钢制品重新加热到入池温度，且为了避免在扁钢制品浸入到熔池之前重新产生损害镀层结果的氧化物形成，需要控制表面温度在加热过程中不超过700℃。
然而，常规的热镀锌机组的布置通常是加热、均热、冷却、热浸镀、再冷却。以上两个专利的方法都是将均热后的带钢先冷却到酸洗温度(通常应至少低于100℃)，再进行酸洗，随后再加热到浸入熔池的温度进行热浸镀，加上酸洗段、再加热段及必要的温度均衡段，工业生产线会很长，装备的成本将非常高。
中锰钢以其高强度的同时具有高延伸率的优异性能已经获得了钢铁行业和汽车行业的高度关注，未来热浸镀中锰钢应用前景广阔。因此若能提供一种经济的热浸镀中锰钢及其制造方法，解决中锰钢可镀性的问题，获得镀层表面质量优异、镀层粘附性优良的热浸镀中锰钢，则对促进中锰钢的产业化应用及汽车轻量化有重要的意义。
发明内容
本发明的目的在于提供一种热浸镀中锰钢及其制造方法，该热浸镀中锰钢具有镀层表面质量优异、镀层附着性良好、耐蚀性优异的优点。
为实现上述目的，本发明的技术方案是：
一种热浸镀中锰钢，其包括钢基板和位于钢基板表面的镀层；其中，所述热浸镀中锰钢的成分质量百分比为C：0.1～0.3％，Si：0.1-2.0％、Mn：5～12％，Al：1-2％，P≤0.02％，S≤0.02％，N≤0.005％，余量为Fe和其它不可避免的杂质；并且所述钢基板的芯部组织为铁素体和奥氏体，钢基板的表层为铁素体层。
上述热浸镀中锰钢的各化学元素的设计原理为：
C：是钢中典型的固溶强化元素，同时其还可以提高奥氏体的稳定性，有利于在室温下保留一定体积分数的残余奥氏体，从而产生相变诱导塑性(TRIP)效应。当C元素含量低于0.1％时，钢的强度较低，而当C元素含量高于0.3％时，钢的性能则会恶化，尤其不利于钢材料的焊接性能。为此，在本发明所述的钢板中的C含量需要限定为0.1％～0.3％。
Si：是炼钢脱氧的必要元素。Si不仅有一定的固溶强化作用，还具有抑制碳化物析出的作用。一旦Si含量不到0.1％，难以在钢中获得充分的脱氧效果。然而，Si含量太高也会影响钢的综合性能。此外适量的Si元素还可以起到阻止渗碳体析出的作用，从而提高冷却过程中奥氏体的稳定性。鉴于此，需要将钢板中的Si含量控制为0.1％～2％，并优选为0.3％～1.5％。
Mn：是有效的奥氏体稳定化元素。在中锰钢中，Mn的作用与C类似，可有效提高材料层错能，降低马氏体转变温度Ms，提高奥氏体稳定性。另外，与普通碳钢中Mn的作用不同，在中锰钢中，Mn含量的提高会导致材料强度的降低，因此，在确保材料奥氏体稳定性的前提下，需要尽量降低Mn含量。因此本发明限定Mn元素的质量百分比含量为5-12％。
Al：可有效改善材料的抗延迟开裂性能，但是Al的加入会显著恶化钢材的冶炼和连铸性能，极易导致连铸时堵水口。而且在冶炼和连铸过程中，大量Al 2O 3的形成会降低钢液流动性，以导致卷渣、板坯开裂等问题， 因此本发明限定Al元素的质量百分比含量为1-2％。
在本发明所述的钢板中的主要杂质元素为P、S和N，这些杂质元素应当被控制得越少越好，由此所获得的钢板就越纯净。然而，根据生产过程的实际冶炼水平，将杂质元素控制得越低所产生的制造成本也就越高。综合钢材的纯净度指标和制造成本的控制，将杂质元素P，S和N分别设定为：P≤0.02％，S≤0.02％，N≤0.005％。
本发明所述的钢基板表层为铁素体层，该铁素体层可以使得本发明所述的热浸镀中锰钢具有优异的可镀性及镀层附着性。
由于中锰钢中的Mn元素在热浸镀前的退火过程中会形成严重的表面MnO富集层，该MnO富集层会影响钢板的可镀性(即镀层表面质量差)和镀层的附着性(即镀层与钢基板结合力较差，易脱落)。
为解决上述热浸镀中猛钢的两个问题，本发明在较高Mn含量的钢基板的表层为铁素体层，由于铁素体层中的Mn远低于钢基板的Mn含量，从而避免了热浸镀之前的退火过程中在铁素体层表面形成MnO富集层，相当于在普通的铁素体钢表面进行热浸镀，因此钢板的可镀性(表面质量)和镀层附着性(结合力)都会得到大大改善。
进一步，在本发明所述的热浸镀中锰钢中，所述的铁素体层的厚度为0.2-5μm。
在本发明所述的热浸镀中锰钢中，当铁素体层厚度<0.2μm时，无法有效抑制Mn和Al元素的外氧化，当其厚度>5μm时，需要更长的退火保温时间，因此本发明控制钢基板表面的铁素体层的厚度为0.2-5μm。
进一步，当铁素体层的晶粒尺寸>5μm时，会导致铁素体层过厚，因此本发明控制铁素体层的晶粒尺寸≤5μm。
进一步，铁素体层的Mn含量低于钢基板的Mn含量。这是因为在一次退火的工艺条件下，钢基板表层的Mn扩散至钢基板表面，从而在钢基板表层形成了贫锰层。通常铁素体层的Mn含量≤5％，优选的，铁素体层的Mn含量控制为≤2％。
进一步，铁素体层的Al含量高于钢基板的Al含量，这是因为在一次退火的工艺条件下，钢基板中一部分的Al扩散至钢基板表层，导致钢基板表层的Al含量升高。当钢基板Al含量为1-2％时，优选的，铁素体层 的Al含量＞1％，且Al含量＜5％。
在本发明所述的热浸镀中锰钢中，所述的铁素体层的C含量低于钢基板C含量。这是因为在一次退火工艺条件下，钢基板表层会发生脱碳反应，从而形成表层脱碳层。优选的，铁素体层的C含量≤0.1％。
所述钢基板芯部的微观组织为铁素体和奥氏体。
本发明所述的热浸镀中锰钢的屈服强度为700-1000MPa，抗拉强度为950-1350MPa，断裂延伸率＞25％。
本发明所述的热浸镀中锰钢的制造方法，包括如下步骤：
(1)制造带钢
(2)一次退火和酸洗
(3)二次退火和热浸镀。
其中，步骤(2)一次退火和酸洗在连续退火生产线上进行；将带钢在连续退火生产线上加热至均热温度600～750℃，均热时间为30～600s，其中退火气氛为N 2、H 2混合气体，H 2体积含量为0.5～10％，露点为-20～+20℃，；将退火后的带钢冷却至100℃以下，并经过H离子浓度为0.1～5％的酸液进行酸洗，酸液温度为50～70℃，酸洗时间1～10s；再经过漂洗烘干后卷取。
步骤(3)二次退火和热浸镀在连续热镀锌生产线上进行；将步骤(2)所获得的带钢在热浸镀生产线上进行二次退火并完成热浸镀，二次退火均热温度为600～850℃，均热时间为60～360s，退火气氛为N2、H2混合气体，H2体积含量为2～10％，露点为-60～+10℃；将带钢冷却至380～500℃后浸入镀液进行热浸镀。
本发明通过控制一次退火的均热温度、时间、退火气氛露点使得Mn元素在表面形成氧化锰层，在钢基板的表层形成贫锰和脱碳的铁素体层，之后用酸洗的方法将一次退退火后钢板表面的氧化锰层洗掉，保留钢基板表层的铁素体层。在二次退火时，利用钢基板表层的铁素体层获得良好的可镀性。
在所述步骤(2)中限定均热温度为600-750℃，是因为：当均热温度低于600℃时，钢基板表面Mn元素形成表面富集的量有限，从而无法形成钢基板表层贫锰层，无法获得铁素体层；当均热温度高于750℃时，Mn 元素会在铁素体层中形成大量的氧化物，从而恶化表层铁素体层的成形性。进一步优选的，步骤(2)中的均热温度为650-700℃。
进一步，在所述步骤(2)中，退火气氛露点限定为-20℃～+20℃。这是因为，在上述退火气氛露点范围内，退火气氛对Fe是还原的，但是对Mn是氧化的。当露点低于-20℃时，钢基板表层的铁素体层厚度<0.2μm，当露点高于+20℃时，钢基板表层的铁素体会形成大量的Mn的内氧化颗粒，从而会影响表层的性能。优选的，退火气氛露点为-10℃～+10℃。
优选的，为了实现更好的实施效果，步骤(2)中的均热保温时间限定为30-600s。进一步优选，步骤(2)中的均热保温时间为30-180s。
为了实现更好的实施效果，步骤(2)中的退火气氛为N 2、H 2混合气体，H 2体积含量为0.5-10％。
在本技术方案中，步骤(2)中的酸洗浓度、温度、时间的控制原则是将表面的氧化锰层洗掉而保留表层铁素体层，因此酸液浓度过高，酸液温度过高以及酸洗停留的时间过长，都会将表层的铁素体层洗掉。若退火过程中形成的氧化锰过厚，而酸洗不够，则残留的氧化物层也不利于步骤(3)的热浸镀。因此酸液浓度范围为0.1-5％，酸洗温度为50-70℃，酸洗时间为1-10s。
步骤(3)二次退火和热浸镀在连续热镀锌生产线上进行；将步骤(2)所获得的带钢在热浸镀生产线上进行二次退火并完成热浸镀，二次退火均热温度为600～850℃，均热时间为60～360s，退火气氛为N2、H2混合气体，H2体积含量为2～10％，露点为-60～+10℃；将带钢冷却至380～500℃后浸入镀液进行热浸镀。
在本发明技术方案中，步骤(3)中的退火工艺参数可以在很宽的范围内进行选择，不需要特别控制退火气氛，采用常规的退火气氛均可获得与普通铁素体材料相同的可镀性。这是因为在步骤(2)中获得的钢板表层已经存在0.2-5μm的铁素体层，在二次退火过程中使用常用的退火温度、保温时间和退火气氛露点，铁素体层中的Mn元素含量较低，且钢基板中的Mn元素并不能越过铁素体层在表面形成氧化锰层，钢基板中的锰元素仅在铁素体层中形成少量内氧化。换句话说，对于经过步骤(2)处理的钢板，表面状态相当于普通的软钢的表面状态，从而在较宽的工艺参数范 围内都不会出现可镀性差的情况。
优选的，步骤(3)中的退火温度可选择600～850℃，保温时间60～360s，退火气氛H 2含量为2～10％，退火气氛露点为-60～+10℃。
进一步，在所述步骤(3)中，镀液成分的质量百分含量为0.1≤Al≤6％，0＜Mg≤5％，余量为Zn及其它不可避免的杂质。
在所述步骤(3)中，镀液中添加0.1-6％的Al的目的是当带钢浸入锌锅时，镀液中的Al首先和带钢反应形成阻挡层，从而抑制Zn和Fe之间的扩散，避免形成对镀层成形性能有不利影响的锌铁合金相。镀液中添加Mg有利于进一步提高镀层的耐蚀性，然而Mg含量超过5％，则表面氧化增加，不利于生产，因此，本发明限定Mg在0-5％。并且Al、Mg含量过高镀层硬度增加，会恶化镀层的成形性能。
优选的，为了实现更好的实施效果，带钢入锌锅温度比镀液温度高0-10℃。
优选的，镀液温度为420-480℃。
本发明的有益效果在于：
(1)通过在带钢表层形成铁素体层，解决了中锰钢可镀性差的问题，实现了中锰钢良好的可镀性及镀层附着性，从而提高了中锰钢的耐蚀性。
(2)本发明所述的热浸镀中锰钢的制造方法可以在现有的连续退火和连续热浸镀生产线上实现，而无需做较大调整，具有很好的推广应用前景。
附图说明
图1为本发明所述的热浸镀中锰钢的结构示意图。
图2为本发明所述的热浸镀中锰钢热浸镀之前的组织。
图3为本发明实施例1的截面金相照片。
图4为实施例1在一次退火并酸洗后、二次退火后，实施例2在二次退火后以及对比例1在一次退火后的表面Mn元素深度分布曲线。
具体实施方式
下面结合附图和实施例对本发明所述的热浸镀中锰钢及其制造方法 做进一步的解释和说明，然而该解释和说明并不对本发明的技术方案构成不当限定。
图1显示了本发明所述的热浸镀中锰钢的结构。如图1所示，本发明所述的热浸镀中锰钢包括钢基板1和位于钢基板1表面的镀层2，其中，11为钢基板的芯部组织，12为钢基板的表层--铁素体层。
图2显示了本发明所述的热浸镀中锰钢在热浸镀之前的组织。如图2所示，钢基板的芯部组织11为奥氏体+铁素体，钢基板的表层12为铁素体层。
图3显示了本发明实施例1的截面金相。如图3所示，11为钢基板1的芯部，12为铁素体层，2为镀层。
针对本发明所述的热浸镀中锰钢的制造方法中步骤(2)和步骤(3)中的工艺参数，本发明人进行了详细的研究。
表1列出了实施例1-20的热浸镀中锰钢以及对比例1-12的常规钢板的化学成分质量百分比。其中余量为Fe及不可避免的杂质
从表1可以看出，成分I、II、III中化学成分质量百分含量范围控制在：C：0.1～0.3％，Si：0.1-2.0％、Mn：5～12％，Al：1-2％，P≤0.02％，S≤0.02％，N≤0.005％。成分IV的Mn含量在上述成分范围之外。
表1            单位wt％
  C Mn Al Si N P S
I 0.2 7.2 1.5 0.19 0.02 0.008 0.007
II 0.2 10.1 1.6 0.54 0.03 0.017 0.005
III 0.2 12.0 1.2 0.13 0.018 0.015 0.01
IV 0.18 2.0 1.0 0.2 0.011 0.008 0.01
实施例1-20中的热浸镀中锰钢钢采用以下步骤：
(1)制造带钢；
(2)一次退火和酸洗：将带钢在连续退火生产线上加热至均热温度600～750℃，均热时间为30～600s，其中退火气氛为N2、H2混合气体， H2体积含量为0.5～10％，露点为-20～+20℃，；将退火后的带钢冷却至100℃以下，并经过H离子浓度为0.1～5％的酸液进行酸洗，酸液温度为50～70℃，酸洗时间1～10s；再经过漂洗烘干后卷取；
(3)二次退火和热浸镀：将步骤(2)所获得的带钢在热浸镀生产线上进行二次退火并完成热浸镀，二次退火均热温度为600～850℃，均热时间为60～360s，退火气氛为N2、H2混合气体，H2体积含量为2～10％，露点为-60～+10℃；将带钢冷却至380～500℃后浸入镀液进行热浸镀。
表2列出了实施例1-20中的热浸镀中锰钢以及对比例1-12的常规钢板的具体工艺参数。
图4显示了实施例1在一次退火并酸洗后(B1)、二次退火后(B2)，实施例2在二次退火后(C)以及对比例1在一次退火后(A)的表面Mn元素深度分布曲线。
其中，A是对比例1是一次退火温度为700℃、均热时间为120s、退火气氛露点为-40℃时的退火钢板，表面存在较明显的Mn富集，次表面贫锰层并不明显，该表面状态进行热浸镀时，可镀性较差。
B1为实施例1经过一次退火温度为650℃、保温时间为100s、退火气氛露点为0℃并且经过酸洗后的钢板，表面的氧化锰已被酸洗掉，次表面存在约1μm厚的贫锰层。
B2为实施例1经过酸洗后的B1带钢又经过步骤(3)二次退火温度650℃、保温时间120s、退火气氛露点为-10℃的二次退火后带钢的表面Mn元素深度分布，B2带钢表面有少量的Mn富集，但远低于对比例A，该表面状态进行热浸镀时，具有良好的可镀性。
C为实施例2经过步骤(2)和步骤(3)二次退火后带钢表面Mn元素深度分布，其中步骤(2)中一次退火温度为650℃、保温时间为120s、退火气氛露点为0℃，步骤(3)中二次退火温度为800℃，保温时间为90s，退火气氛露点为-50℃。由于实施例2的二次退火温度高于实施例1的二次退火温度，且二次退火气氛露点低于实施例1的二次退火气氛露点，因此实施例2的表面Mn元素富集比实施例1明显，但依然低于对比例1，该表面状态的带钢进行热浸镀时，可镀性依然良好。
表3列出了实施例1-20中的热浸镀中锰钢板以及对比例1-12的常规 钢板的各性能参数及组织特征。
其中，可镀性的判断方法是：使用肉眼直接观察镀后带钢外观。若表面无明显露铁则可镀性良好(用○表示)，若表面有明显露铁则可镀性较差(用×表示)。
镀层附着性的检测方法是：在带钢上取长200mm、宽100mm的试样，进行180度折弯后压平，使用胶带粘折弯位置。若无锌层被胶带粘下或者被胶带粘过的折弯面镀层表面不起毛，则表示镀层附着性良好(用○表示)；如有镀层被胶带粘下或者被胶带粘过后的折弯面镀层起毛，则表示镀层附着性较差(用×表示)
由表3可以看出，实施例1-20的屈服强度为700-1000MPa，抗拉强度为950-1350MPa，断裂延伸率>25％；实施例1-20钢基板表层铁素体层的厚度为0.2-5μm，表层铁素体层的晶粒尺寸≤5μm；并且可镀性以及镀层附着性均优于对比例1-10。
这是因为：当实施例在步骤(2)中在钢基板表层形成了铁素体层，从而在步骤(3)中抑制了钢基板中的Mn扩散至钢板表面，有利于镀液中Al和铁素体层形成有效的Fe-Al阻挡层，从而可获得良好的可镀性和镀层附着性。
另外，对比例11-12因未采用本发明所限定的钢基板成分和制造方法，虽然可镀性和镀层附着性良好，但不具备钢基板芯部为铁素体+奥氏体，钢基板表层为铁素体层的组织特征，同时断裂延伸率较低。
需要注意的是，以上列举的仅为本发明的具体实施例，显然本发明不限于以上实施例，随之有着许多的类似变化。本领域的技术人员如果从本发明公开的内容直接导出或联想到的所有变形，均应属于本发明的保护范围
表2
Figure PCTCN2018083848-appb-000001
Figure PCTCN2018083848-appb-000002
表3
Figure PCTCN2018083848-appb-000003
Figure PCTCN2018083848-appb-000004

Claims (21)

  1. 一种热浸镀中锰钢，包括钢基板和位于钢基板表面的镀层；其特征在于：所述热浸镀中锰钢的钢基板成分质量百分比为：C：0.1～0.3％，Si：0.1-2.0％、Mn：5～12％，Al：1-2％，P≤0.02％，S≤0.02％，N≤0.005％，余量为Fe和不可避免杂质；且所述钢基板的芯部组织为铁素体和奥氏体，钢基板的表层为铁素体层。
  2. 如权利要求1所述的热浸镀中锰钢，其特征在于，所述铁素体层的厚度为0.2-5μm。
  3. 如权利要求1或2所述的热浸镀中锰钢，其特征在于，所述铁素体层的晶粒尺寸≤5μm。
  4. 如权利要求1或2或3所述的热浸镀中锰钢，其特征在于，所述铁素体层中Mn含量低于钢基板Mn含量。
  5. 如权利要求1或2或3或4所述的热浸镀中锰钢，其特征在于，所述铁素体层中Mn含量≤5％。
  6. 如权利要求1或2或3或4或5所述的热浸镀中锰钢，其特征在于，所述铁素体层中Mn含量≤2％。
  7. 如权利要求1～6任何一项所述的热浸镀中锰钢，其特征在于，所述铁素体层中Al含量高于钢基板Al含量。
  8. 如权利要求1～7任何一项所述的热浸镀中锰钢，其特征在于，所述铁素体层中Al含量＞1％。
  9. 如权利要求1～8任何一项所述的热浸镀中锰钢，其特征在于，所述铁素体层中Al含量＜5％。
  10. 如权利要求1～9任何一项所述的热浸镀中锰钢，其特征在于，所述铁素体层中含有Al的氧化物。
  11. 如权利要求1～10任何一项所述的热浸镀中锰钢，其特征在于，所述铁素体层中C含量低于钢基板C含量。
  12. 如权利要求1～11任何一项所述的热浸镀中锰钢，其特征在于，所述铁素体层中C含量≤0.1％。
  13. 如权利要求1所述的热浸镀中锰钢，其特征在于，所述镀层的厚度为5-200μm。
  14. 如权利要求1至13任一项所述的热浸镀中锰钢，其特征在于，所述热浸镀中锰钢的屈服强度在700-1000MPa，抗拉强度在950-1350MPa，断裂延伸率在25％以上。
  15. 如权利要求1-14任一项所述的热浸镀中锰钢的制造方法，其特征是，包括如下步骤：
    1)带钢制造；
    2)一次退火和酸洗
    将带钢在连续退火生产线上加热至均热温度600～750℃，均热时间30～600s，其中退火气氛为N 2、H 2混合气体，H 2体积含量为0.5～10％，露点为-20～+20℃；将退火后的带钢冷却至100℃以下，并经过H离子浓度为0.1～5％的酸液进行酸洗，酸液温度为50～70℃，酸洗时间1～10s；再经过漂洗烘干后卷取；
    3)二次退火和热浸镀
    将步骤2)所获得的带钢在热浸镀生产线上进行二次退火并完成热浸镀，二次退火均热温度为600～850℃，均热时间60～360s，退火气氛为N 2、H 2混合气体，H 2体积含量为2～10％，露点为-60～+10℃；将带钢冷却至380～500℃后浸入镀液进行热浸镀。
  16. 如权利要求15所述的热浸镀中锰钢的制造方法，其特征在于，步骤(2)中所述的均热温度为600～700℃。
  17. 如权利要求15所述的热浸镀中锰钢的制造方法，其特征在于，步骤(2)中所述的均热时间为30～180s。
  18. 如权利要求15所述的热浸镀中锰钢的制造方法，其特征在于，步骤(2)中所述的退火气氛露点为-10～+10℃。
  19. 如权利要求15所述的热浸镀中锰钢的制造方法，其特征在于，步骤(3)中所述的镀液成分的质量百分含量为：0.1≤Al≤6％，0＜Mg≤5％，余量为Zn及其它不可避免的杂质。
  20. 如权利要求15所述的热浸镀中锰钢的制造方法，其特征在于，步骤(3)中所述的退火气氛露点为-60～-20℃。
  21. 如权利要求15所述的热浸镀中锰钢的制造方法，其特征在于，步骤(3)中所述镀液温度为420-480℃。
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