CN115029632B - High-corrosion-resistance galvanized hot-formed hardened steel, parts and components thereof and preparation method - Google Patents
High-corrosion-resistance galvanized hot-formed hardened steel, parts and components thereof and preparation method Download PDFInfo
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Classifications
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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
-
- 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
- C22C38/04—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
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/22—Ferrous alloys, e.g. steel alloys containing chromium with molybdenum or tungsten
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/24—Ferrous alloys, e.g. steel alloys containing chromium with vanadium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/26—Ferrous alloys, e.g. steel alloys containing chromium with niobium or tantalum
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/28—Ferrous alloys, e.g. steel alloys containing chromium with titanium or zirconium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/32—Ferrous alloys, e.g. steel alloys containing chromium with boron
-
- 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
- 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
- C23C2/34—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the shape of the material to be treated
- C23C2/36—Elongated material
- C23C2/40—Plates; Strips
Abstract
The invention discloses a high corrosion-resistant galvanized hot-formed hardened steel, parts and a preparation method thereof, wherein the high corrosion-resistant galvanized hot-formed hardened steel comprises a substrate and a coating; the substrate comprises the following components in percentage by mass: 0.12 to 0.35 percent of C, 0.08 to 2.12 percent of Si, 0.42 to 10.00 percent of Mn, 0.03 to 0.12 percent of Al, 0.02 to 0.65 percent of Cr, less than or equal to 1.12 percent of Mo, 0.02 to 0.25 percent of Nb + V + Ti, 0.0003 to 0.005 percent of B, less than or equal to 0.012 percent of S, less than or equal to 0.08 percent of P, and the balance of Fe and inevitable impurities; the plating layer comprises the following components in percentage by mass: 0.15 to 0.45 percent of Al, 0.05 to 2.50 percent of Fe, 0.08 to 3.2 percent of La, 0.12 to 5.0 percent of Ce, less than or equal to 3.0 percent of Si and Mn, less than or equal to 3.5 percent of Mg and Cr, and the balance of Zn and inevitable impurities. The substrate and the zinc layer structure and component design meet the requirement of wide heating process window above complete austenitization (AC 3), the hot austenite of the substrate hot forming steel has higher stability, lower Ms, and right shift of Bs and Fs precipitation temperature, bainite, ferrite or martensite phases cannot be precipitated in the low-temperature hot forming process, and mixed crystals or multi-phase structures cannot occur to cause that Zn easily permeates into grain boundaries to cause brittleness.
Description
Technical Field
The invention relates to galvanized hot forming steel, in particular to high-corrosion-resistance galvanized hot forming hardened steel, parts and preparation methods thereof.
Background
The hot forming steel adopts the technical scheme of austenitizing heating and high-temperature zone deformation, not only realizes the strength of the steel up to 1500-2100 MPa, but also solves the quality problems of parts such as rebound, cracking, low dimensional precision and the like of the ultra-high strength steel, and is more and more widely applied to the manufacturing of automobile parts. Bare plate hot forming steel generally has the disadvantages of surface oxidation, decarburization, poor corrosion resistance, requirement of shot blasting treatment and the like, and is gradually replaced by plating hot forming steel. The current commercially used plated hot forming steel accounts for about 70% of the yield of hot forming steel, and is the mainstream product of hot forming steel.
The coating hot forming steel mainly comprises two series of Al-based coatings and Zn-based coatings; wherein the Al-based plating layer comprises Al-Si, al-Si-Cu, al-Si-Re, al-Si-Ni and the like, the Al-10 percent Si plating layer has higher commercialization degree and the widest application, is a patent product of AnSailomta, has 90 percent of market share, and almost monopolizes the domestic market. The Zn-based coating comprises GI hot-dip pure zinc and GA alloying hot dip galvanizing products, and the Otto Union is successfully researched and developed in 2006 and is put into the market; at present, only companies such as the Olympic Games, the Ansai Lemitota and the Xinri iron have mature product supply markets. The German theson Krupp successfully develops an electrogalvanized Zn-Ni product and is applied, but the cost is too high, the corrosion resistance is inferior to GI and GA, and the large-scale application stage is not reached. In addition, scholars at home and abroad develop Zn-Al, zn-Al-Mg and other coating layers in laboratories, and the Zn-Al coating layer is a composite coating layer.
The plated hot formed steel forming process includes direct hot forming and indirect hot forming processes. The direct hot forming process is to heat the steel plate to austenitizing temperature, keep the temperature for a certain time and then directly transfer the steel plate into a die with a cooling system for stamping and forming and pressure-maintaining quenching. The indirect hot forming process is to perform a certain amount of steel plates by cold stamping, then heat the steel plates to austenitizing temperature, preserve heat for a certain time, and transfer the steel plates to a die with a cooling system for final forming and quenching. The Al-based coating is produced by adopting a direct hot forming mode, and has short production flow, high yield and low production cost. The Al-Si coating is easy to generate microcracks in the heating and hot forming processes, the microcracks do not extend to the substrate, the brittleness of the substrate is not caused, and the corrosion resistance of the coating is reduced; when the cold forming amount exceeds 8%, the aluminum-silicon plating layer is easy to crack and reduce the corrosion resistance, so that the aluminum-silicon plating layer cannot adopt an indirect hot forming process and is only suitable for producing parts with simple section shapes. The Zn-based coating can be produced by adopting a direct hot forming process and an indirect hot forming process. The Zn-based coated hot formed steel is susceptible to liquid metal embrittlement (LMIE) and solid metal embrittlement (SMIE) using the direct hot forming process, and therefore the austenite heating and hot forming process window is narrow. The Zn-based coating can distribute most of deformation to the cold forming process by adopting an indirect hot forming process, and cracks are not easy to generate due to good cold forming performance, so that a wider process window is provided in the subsequent austenitizing process and the hot forming process, and a part product with a complicated section shape can be produced.
The hot-dip galvanized hot-formed steel has cathode protection capability for the aluminum-silicon coating, because the electrode potentials of Zn and Fe are-0.762V and-0.439V respectively, the electrode potential of the Zn coating is more negative, the cathode protection effect on the steel plate substrate at the damaged coating part is good, and the corrosion resistance is good even at the cut. After austenitizing heat treatment and hot forming are carried out on the hot-galvanized hot-formed steel, the Zn content in a coating is reduced, so that the electrode potential is increased, and the corrosion resistance is reduced; meanwhile, fe element in the substrate diffuses to the zinc layer in the austenitizing heating and hot forming processes, so that the content of Fe in the zinc layer is increased, the melting point of the zinc layer is increased, the permeation of Zn to the austenite grain boundary of the substrate is inhibited, the brittleness tendency of liquid metal is reduced, and the evaporation of the surface Zn element is reduced. Therefore, the diffusion of Fe and Zn elements in the hot working process cannot simultaneously improve the cathodic protection capability of the coating and reduce the brittleness tendency of liquid metal in the hot forming process.
EP2045360A1 provides a composite coating technique, the coating structure being an upper zinc layer containing > 99% Zn, < 1% Al and a lower alumino-silicon layer containing 90-10% Al-Si; the upper zinc layer after hot forming of the coating contains 80% Zn, 16% Al, 2% Si, the lower layer contains 40% Al, 30% Fe, 20% Zn, 5% Si. According to the technology, two different layer structures are arranged at the upper part and the lower part through two times of hot dipping, so that the production difficulty and the commercialization difficulty are high.
International patent application WO2008102012A1 provides a Zn + Mg + Al plating layer comprising 0.3 to 4.0wt% Mg, 0.05 to 6.0wt% Al, and further comprising up to 1 or more additional elements 0.2wt%, the remainder being Zn and unavoidable impurities. Wherein 0.2wt% of the additional elements comprise Sb, pb, ti, ca, mn, sn, la, ce, cr, ni, zr, bi, wherein Sb, pb, sn, bi are used for forming spangles on the surface of the plating layer, the additional elements can improve the generation of zinc dross, change the corrosion resistance of the plating layer less than Mg and Al elements, and make the plating layer more expensive.
Chinese patent application CN104302802A provides a steel sheet with a sacrificial cathodic protective coating comprising: between 5 and 50wt% Zn, between 0.1 and 15wt% Si, and optionally up to 10wt% Mg and up to 0.3wt% additional elements in terms of cumulative content; the coating further comprises: a protective element selected from the group consisting of between 0.1wt% and 5wt% tin, between 0.01wt% and 0.5wt% indium, and combinations thereof; wherein 0.3wt% of the additional element comprises Sb, pb, ti, ca, mn, la, ce, cr, ni, zr or Bi; these different elements may in particular improve the corrosion resistance of the coating or even its brittleness or adhesion.
Chinese patent application CN112011752A provides a solution for a thermosetting part of a GA coating, the coating structure before thermosetting is composed of a gamma-FeZn phase and an alpha-Fe (Zn) phase rich in Fe, wherein the volume of the gamma-FeZn phase accounts for 10-20%. The patent application does not describe the composition design of the hot dip coating bath and describes the alloying process in detail.
Chinese patent application CN110777319A provides an aluminum-based Si-Mg-Cu-REM plated steel sheet, the plating layer comprises the components of plating solution by mass%, including Si:2.0 to 7.5%, mg:0.08 to 2.5%, cu:0.1 to 2.0%, REM:0.08 to 1.0 percent, and the balance of Al and inevitable impurities, and is mainly characterized by corrosion resistance and formability.
The Chinese patent application CN 112139335A adds a procedure of removing oxidation layer by boiling water after the zinc layer is heated, the heated sheet material is transferred to a boiling water tank for removing oxidation layer by high-pressure boiling water, and the sheet material is blown by gas after being taken out of the boiling water tank. The process has the defect of difficult control of the cooling speed.
Disclosure of Invention
The technical problem to be solved by the invention is to provide the high corrosion resistant galvanized hot forming hardened steel; also provides a preparation method of the high corrosion resistant galvanized hot forming hardened steel without generating liquid metal brittleness or influencing the crack propagation of the coating; also provides a high corrosion-resistant galvanized hot-formed hardened steel part; also provides a preparation method of the high corrosion-resistant galvanized hot-formed hardened steel part.
In order to solve the technical problems, the technical scheme adopted by the galvanized hot-forming hardened steel is as follows: it comprises a substrate and a plating layer;
the substrate comprises the following components in percentage by mass: 0.12 to 0.35 percent of C, 0.08 to 2.12 percent of Si, 0.42 to 10.00 percent of Mn, 0.03 to 0.12 percent of Al, 0.02 to 0.65 percent of Cr, less than or equal to 1.12 percent of Mo, 0.02 to 0.25 percent of Nb + V + Ti, 0.0003 to 0.005 percent of B, less than or equal to 0.012 percent of S, less than or equal to 0.08 percent of P, and the balance of Fe and inevitable impurities;
the plating layer comprises the following components in percentage by mass: 0.15 to 0.45 percent of Al, 0.05 to 2.50 percent of Fe, 0.08 to 3.2 percent of La and/or 0.12 to 5.0 percent of Ce, less than or equal to 3.0 percent of Si and Mn, less than or equal to 3.5 percent of Mg and Cr, and the balance of Zn and inevitable impurities.
Further, the plating layer comprises a zinc plating layer and a diffusion layer, and the diffusion layer contains a suppression layer; the zinc coating layer mainly consists of eta phase, the diffusion layer mainly consists of alpha Fe and gamma phase, and the inhibition layer mainly consists of Fe 2 Al 5 。
Further, the zinc coating contains the following components: 0.08 to 2.20 percent of solid solution Fe, 0.08 to 0.45 percent of Al, 0.08 to 1.4 percent of La and/or 0.12 to 2.0 percent of Ce, less than or equal to 3.0 percent of Si and Mn and less than or equal to 3.5 percent of Mg and Cr. Preferably, in the components of the galvanized layer, si/Mn is more than or equal to 1.1, and Mg/Cr is more than or equal to 0.8.
Further, the alpha Fe in the diffusion layer is more than or equal to 80 percent, and the average content of main solid solution elements is as follows: 0.34 to 1.45 percent of Al, 0.1 to 2.5 percent of La, 0.2 to 3.1 percent of Ce, less than or equal to 15.0 percent of Si and Mn and less than or equal to 2.4 percent of Mg and Cr.
The preparation method of the galvanized hot-forming hardened steel comprises the following steps: hot dip coating the hardened steel sheet; the plating solution comprises the following components in percentage by mass: 0.12 to 0.35 percent of Al, 0.005 to 0.06 percent of Fe, 0.08 to 3.2 percent of La and/or 0.12 to 5.0 percent of Ce, less than or equal to 3.0 percent of Si and Mn, less than or equal to 3.5 percent of Mg and Cr, more than or equal to 1.1 percent of Si/Mn, more than or equal to 0.8 percent of Mg/Cr and the balance of Zn and inevitable impurities.
Further, the hot dip plating process comprises the following steps: the temperature Ts 410-475 ℃ of the hardened steel plate in a zinc pot, the temperature Tz 420-475 ℃ of the plating solution and the hot dipping time 3-10 s; the temperature of Ts and Tz meets the condition that Ts-Tz is less than or equal to 40 ℃.
The galvanized hot forming hardened steel part is prepared from the high-corrosion-resistance galvanized hot forming hardened steel, and comprises a substrate and a coating; the coating comprises a surface oxidation layer, a Zn-Fe alloy matrix layer and a diffusion layer from the outer surface to the substrate in sequence;
the surface oxide layer mainly comprises Al 2 O 3 、MgO、MnO、SiO 2 、ZnO、CeO、La 2 O 3 One or more of;
the Zn-Fe alloy matrix layer comprises alpha Fe, a gamma phase and an intermediate alloy phase, and the intermediate alloy phase comprises Zn x Si y Fe z 、Zn x Mn y Fe z And ZnMg 2 (ii) a The Zn-Fe alloy matrix layer comprises the following components: 40-70% of Fe and 20-50% of Zn;
the diffusion layer mainly comprises solid-solution Zn, si, mn, ce and/or Re alpha Fe, and the diffusion layer comprises the following components: fe is more than or equal to 80 percent, and Zn is less than or equal to 5 percent.
The preparation method of the galvanized hot-forming hardened steel part comprises the following steps: cold stamping, preforming, trimming and austenitizing heat treatment are carried out on the galvanized hot-formed hardened steel; transferring to a cooling device, cooling and removing an oxidation layer; and then transferring the blank to a mold for shaping or low-temperature thermoforming.
Further, the cooling and oxidation layer removing process comprises the following steps: and reducing the temperature of the blank to be 10-20 ℃ above the precipitation temperature of ferrite or bainite by adopting a water cooling or air cooling mode.
Further, the shaping or low-temperature hot forming process comprises the following steps: the pressure maintaining time is 4-8 s, and the quenching cooling speed is more than or equal to 27 ℃/s; when Mn in the substrate is less than or equal to 3.0wt%, the hot stamping temperature ranges from 450 ℃ to 760 ℃; when the Mn content in the substrate is more than 3.0wt% and less than or equal to 10.0wt%, the hot stamping temperature range is 350-660 ℃.
Adopt the produced beneficial effect of above-mentioned technical scheme to lie in: the substrate and the structure and the component design of the zinc layer coated on the substrate meet the requirement of a wide heating process window above complete austenitization (AC 3), the hot austenite of the substrate hot forming steel has higher stability, lower Ms, and right shift of the precipitation temperature of Bs and Fs, bainite, ferrite or martensite phases cannot be precipitated in the low-temperature hot forming process, and brittleness caused by easy penetration of Zn into a grain boundary due to mixed crystals or a multi-phase structure cannot be generated; when the parts are produced, a hot forming and cooling process window with low critical cooling speed and the temperature lower than the traditional hot forming by about 50-200 ℃ can be adopted, ferrite (Fs) and bainite (Bs) are avoided to be separated out, the brittleness of liquid metal or the crack propagation of a coating layer influencing the fatigue performance of a substrate cannot occur under the condition of the process window, and the manufactured parts have high cathodic protection anti-corrosion performance, welding performance, mechanical performance, bending performance, fatigue performance and the like.
The parts of the invention adopt a low-temperature hot forming process, the hot forming temperature range is obviously 50-200 ℃ lower than that of the traditional hot forming process, the deformation is limited to be less than or equal to 20 percent of the total deformation of the parts under the condition of lower temperature, and even under the condition of no deformation, the hot forming is not easy to cause the generation of zinc layer cracks.
Drawings
The invention is described in further detail below with reference to the drawings and the detailed description.
FIG. 1 is the morphology distribution of a coating inhibition layer after hot dip coating according to the invention;
FIG. 2 shows the coating texture of a hot-dip coated steel sheet according to example 4 of the present invention;
FIG. 3 is a heating process window with Mn content not more than 3.0wt% and thickness not less than 0.7mm and not more than 1.4mm in the present invention;
FIG. 4 shows a heating process window with Mn content less than or equal to 3.0wt%, thickness of 1.4mm less than or equal to 3.0mm in the present invention;
FIG. 5 shows a heating process window with Mn content less than or equal to 3.0wt%, thickness greater than 3.0mm and less than or equal to 4.0 mm;
FIG. 6 shows a heating process window with Mn content less than or equal to 10.0wt% and thickness less than or equal to 1.4mm and greater than or equal to 3.0 wt%;
FIG. 7 shows a heating process window with Mn content less than or equal to 10.0wt% and Mn thickness less than or equal to 3.0mm and 3.0wt% and more than or equal to 3.0wt% in the present invention;
FIG. 8 shows a heating process window with Mn content less than or equal to 10.0wt% and Mn thickness less than or equal to 4.0mm and 3.0wt% and 3.0 mm;
FIG. 9 is a schematic comparison of the low temperature hot truing/forming quench of the present invention with a conventional hot forming process.
Detailed Description
The limiting conditions influencing the austenitizing heating process window range of the zinc-based coating steel plate are 3, wherein liquid metal is brittle, namely zinc or zinc-iron liquid phase permeates into an austenite crystal boundary in the heating process to cause cracking of a zinc layer and a substrate; (2) melting, evaporating and oxidizing the zinc layer; (3) The Fe and Zn contents of the zinc layer are controlled to realize the matching of the cathodic protection corrosion resistance and the welding performance. If the coating components, the coating structure, the substrate, the coating thickness and the like of the hot-dip galvanized hot-forming steel are not properly designed, the austenitic heating and hot-forming process window for manufacturing the part is very narrow, namely the controllable ranges of parameters such as heating temperature, heating rate, heat preservation time and the like are very small, the fatigue performance, the cathodic protection corrosion resistance and the welding performance qualification rate of the produced part are low, and the evaporation/melting/oxidation of a zinc layer can also influence production equipment. Based on the above principle, the plating solution and the plating layer of the high corrosion-resistant galvanized hot-formed hardened steel are designed as follows.
(1) In order to enlarge a heating process window and a hot forming process window and improve the performance of parts, the galvanized hot forming hardened steel is designed with the following plating solution components and plating layer components.
Plating solution component (wt): 0.12 to 0.35 percent of Al, 0.005 to 0.06 percent of Fe, 0.08 to 3.2 percent of La and/or 0.12 to 5.0 percent of Ce, less than or equal to 3.0 percent of Si and Mn, less than or equal to 3.5 percent of Mg and Cr, more than or equal to 1.1 percent of Si/Mn, more than or equal to 0.8 percent of Mg/Cr and the balance of Zn and inevitable impurities;
plating layer composition (wt): 0.15 to 0.45 percent of Al, 0.05 to 2.50 percent of Fe, 0.08 to 3.2 percent of La and/or 0.12 to 5.0 percent of Ce, less than or equal to 3.0 percent of Si and Mn, less than or equal to 3.5 percent of Mg and Cr, and the balance of Zn and inevitable impurities. The action mechanism of each element in the coating is as follows:
al element is mainly used for controlling Fe in coating 2 Al 5 The formation of the inhibition layer controls the generation of the brittle phase of the Zn-Fe alloy and the thickness of the diffusion layer through the inhibition layer. When the Al content of the bath exceeds 0.15wt%, continuous Fe can be realized by the usual hot dip plating process 2 Al 5 Inhibiting the formation of layers, but inhibiting the composition, thickness, scale of layersThe size, distribution and the like are influenced by the annealing temperature, the atmosphere of annealing dew point/hydrogen and the like, the hot dip plating temperature/time and other processes. In order to increase the cold forming performance of the hot-dip galvanized layer and avoid generating micro cracks or defects in the cold forming process, the thickness of an alloy layer and the generation of a Zn-Fe brittle phase need to be controlled, so that the control of the generation of a continuous, compact and uniform (100-200 nm) inhibition layer in the hot-dip galvanizing process is critical. In addition, the more critical point is that the mutual diffusion process of Fe and Zn elements is controlled by a restraining layer in the range of 450-700 ℃ in the austenitizing heating process, the infiltration of Zn or Zn-Fe liquid phase to the crystal grain boundary of matrix grains is restrained, and the generation of liquid metal brittleness is reduced; in addition, al in the zinc layer can diffuse to the surface of the zinc layer to form compact Al through the austenitizing heating process 2 O 3 Film, reduced evaporation and oxidation of Zn, but too high content of Al 2 O 3 The film is unfavorable to coating and welding performance, and the preparation method removes the film through a pre-cooling process.
La and Ce elements can effectively purify plating solution components, realize the uniform distribution of Zn, al and other elements in the plating solution, and the uniformly distributed Al reacts with the substrate during hot dipping, thereby being beneficial to forming continuous and straight Fe 2 Al 5 An inhibiting layer that inhibits brittleness of the liquid metal; in addition, la and Ce can refine the grain size of a zinc layer in an original coating layer, and refine alloy phases of Zn, fe, si and Mn, zinc magnesium and a metallographic MgZn formed in an austenitizing heating process 2 The alloy phase is a high-melting-point phase, can obviously delay the formation of liquid zinc and zinc-iron phases and inhibit the liquid zinc and zinc-iron phases from permeating into a matrix and a matrix grain boundary; the refined coating structure and the intermediate phase obviously improve the density of the zinc layer, thereby improving the corrosion resistance of the coating. Ce, la and the like in patent applications WO2008102012A1 and CN104302802A are added as additional elements, the content is lower than 0.3wt%, and the aims of controlling the morphology of an inhibition layer and effectively refining the size of an alloy phase in a plating layer cannot be achieved in the composition range. The galvanized steel realizes the precise control of the continuity of the inhibition layer and the control of the surface state in the hot dip plating process by adding higher content.
The addition of Si and Mn elements in the plating solution improves the melting point of a Zn layer, reduces the evaporation of Zn in the austenitizing heating process, and in addition, the Si and Mn elements and Zn and Fe in the plating layer form a ternary or quaternary master alloy phase which greatly retards the liquid zinc from permeating to a matrix grain boundary. The Si and Mn are added in a composite way, so that the phase distribution of the master alloy is more uniform, and the Si/Mn ratio is more than or equal to 1.1, and the best uniform distribution state is obtained. In patent application CN104302802A, 0.1wt% to 15wt% of Si is added, preferably the Si content is in the range of 1wt% to 15wt%, and the additional element Mn content is less than 0.3wt%, preferably 0.01wt%, the technology mainly improves the high temperature oxidation resistance of the coating through Si, reduces the stripping of the coating at a temperature of above 650 ℃, and reduces the over-thick zinc-iron alloy layer in the hot dip plating process; according to the technology, the production cost is increased by adopting high-content Si, an excessively thick intermediate alloy phase is easily formed, the distribution uniformity control difficulty is high, and the corrosion resistance is not favorably improved. The galvanized steel designs that two elements of Si and Mn are matched for use to form an intermediate alloy phase, the total content of the two elements is lower than 3wt%, the production cost is reduced, the distribution uniformity of the intermediate alloy phase is improved by interaction, more importantly, the grain size of the intermediate alloy is refined by matching with the rare earth elements of Ce and La, and the corrosion resistance of a zinc layer is improved.
The Mg content in the plating solution improves the corrosion resistance of Zn layer cathode protection and cut protection, but when the content exceeds 3wt%, the corrosion resistance rate is reduced quickly; in addition, mgZn is separated out from Mg and Zn in the solidification process of the plating solution 2 The phase is uniformly distributed in the coating, so that the hardness and the surface friction state of the coating can be improved; the Cr element in the coating diffuses to the surface of the Zn layer in the austenitizing heating process to form Cr 2 O 3 Oxide film to prevent Zn from evaporating and to suppress Al 2 O 3 Forming; the compound action of Cr, mg and Al elements controls the surface friction state of the plating layer at high temperature, can effectively reduce the friction coefficient of a Zn layer at the high temperature, and reduces the generation of liquid metal brittleness (LIME) or solid metal brittleness (SIME) in the hot stamping process. The composite addition of Mg and Cr elements is that the Mg/Cr ratio is controlled to be more than or equal to 0.8, so that a good surface state effect can be obtained, the optimal high-temperature surface friction coefficient is obtained, and the high-temperature friction coefficient at 700 ℃ can be reduced to 0.2-0.3. In patent application CN104302802A, 10wt% Mg was added, and it is preferably used in the range of 3wt% to 6wt%, mainlyFor improving the cathodic protection performance of the zinc layer, and actually, when the Mg content in the zinc layer exceeds 3wt%, the corrosion resistance of the zinc layer tends to be reduced. Patent applications WO2008102012A1 and CN110777319A, which adopt a design of 0.3 to 4.0wt% mg and 0.08 to 2.5% mg, respectively, can improve the coating cathodic protection corrosion resistance, but are liable to form rough oxides MgO and ZnO on the coating surface during austenitizing heating, increase the coating surface friction coefficient, are disadvantageous to the hot stamping process, and may cause a problem of solid metal brittleness of the zinc layer. The galvanized steel designs the cooperation application of two elements of Mg and Cr, not only improves the problem of corrosion resistance protection of the cathode of the coating, but also removes rough ZnO and MgO layers through a pre-cooling process, reserves a fine Zn, mg, cr and Al mixed oxide layer, reduces the surface friction coefficient in a hot state, improves the stability of hot stamping forming, improves the crack expansion of the coating and improves the performance.
The Fe content in the plating solution is controlled to be 0.005-0.06 wt%, and the low-iron content in the plating solution is controlled to reduce the generation of zinc slag. The hot dip coating process promotes the Fe in the steel plate to diffuse to a zinc layer, the Fe content reaches 0.02-2.50 wt% after hot dip coating, the higher Fe content in the coating improves the melting point of the coating and reduces the generation trend of liquid metal brittleness. The galvanized hot forming steel continues to expand towards the zinc layer in the subsequent austenitizing heating or hot forming process, the higher the Fe content in the coating is, the better the welding performance of the coating is, the higher the hardness is, but the too high Fe content causes the Fe content in the zinc layer to be low, so that the cathode protection capability of the coating is reduced, and the Fe content in the zinc layer of the part is controlled to be 40-70 wt%.
(2) Factors influencing the austenitizing and hot forming process window of the zinc-based coating steel plate also comprise control of chemical elements of the substrate. The AC3 point temperature of the coated steel plate is properly reduced through the control of alloy elements, so that the substrate can realize austenitization under a lower temperature condition, and simultaneously, the condition that a zinc layer is subjected to heat treatment at a lower temperature to realize Fe diffusion is met, and the evaporation and oxidation of Zn are reduced. The design of the alloy elements can reduce the precipitation temperature of ferrite and bainite, so that hot forming can be carried out at a lower temperature, and the brittleness of liquid metal, particularly the brittleness of solid metal, is reduced. In addition, the addition of alloy elements in the substrate has important influence on the mechanical properties after hot dipping and hot forming, and the addition of the alloy elements can improve the cold forming property after hot dipping and the mechanical properties and fatigue property after hot forming.
Substrate alloy composition design (wt): 0.12 to 0.35 percent of C, 0.08 to 2.12 percent of Si, 0.42 to 10.00 percent of Mn, 0.03 to 0.12 percent of Al, 0.02 to 0.65 percent of Cr, less than or equal to 1.12 percent of Mo, 0.02 to 0.25 percent of Nb, V and Ti, 0.0003 to 0.005 percent of B, less than or equal to 0.012 percent of S, less than or equal to 0.08 percent of P, and the balance of Fe and inevitable impurities.
The mechanism of action of each element in the substrate is as follows:
the C element has great influence on Ac3, fs and Bs, the C content is increased by 0.1wt%, the complete austenitizing temperature AC3 temperature can be effectively reduced by 20 ℃, the bainite precipitation temperature BS point is reduced by 27 ℃ in the cooling process, and the precipitation of ferrite is delayed. The treatment range of an austenitizing heating process and a hot forming process window can be effectively expanded by increasing the content of C. Meanwhile, the content of C influences the mechanical properties of the galvanized hot forming steel, the strength of martensite after hot forming is greatly improved through solid solution strengthening, and in addition, C is a strong austenite stability element, so that certain residual austenite content after annealing is obtained, and the toughness, the fatigue property and the like of the steel plate are improved.
Mn can greatly reduce the AC3 and BS temperatures, 1wt% Mn can reduce the AC3 temperature by 20.7 ℃, reduce the Bs by 90 ℃ in the hot forming process, and delay ferrite transformation. Therefore, the window range of an austenitizing heating process and a hot forming process can be effectively enlarged by increasing the content of Mn. Meanwhile, the Mn element is beneficial to obtaining a certain amount of stable residual austenite on the steel plate substrate of the part, and the mechanical property of the galvanized steel plate part is improved. When the Mn content is increased to the range of 5wt% -10 wt%, a martensite + austenite Q & P structure is obtained, the tensile strength can reach more than 1500MPa, the elongation reaches more than 15%, the Ac3 temperature is as low as 740 ℃, complete austenitization can be realized at the temperature, and the evaporation and oxidation of Zn are greatly reduced by carrying out heat treatment at the temperature.
The effect of adjusting the AC3 temperature by the Si element is not obvious, but BS and FS points can be reduced, a heat treatment process is realized at a lower temperature, and the reduction of the brittleness of liquid metal and the brittleness of solid metal is facilitated; si has a strong solid solution strengthening effect, can inhibit the generation of pearlite, improves the carbon content of austenite and the volume content of residual austenite, and improves the toughness and the fatigue performance of hot forming steel parts.
The Al element has similar action with the Si element, can inhibit the generation of pearlite, improves the stability of austenite, and greatly improves the AC3 temperature due to overhigh Al content.
Cr and Mo are mainly used for improving the hardenability of the hot forming steel when the Mn content in the steel is relatively low, and the comprehensive martensite content can be obtained at the cooling speed of 25 ℃/s.
Nb, V and Ti are mainly used for improving the strength of a hot forming steel substrate through precipitation strengthening and fine grain strengthening, and the galvanized steel is realized by adding one, two or three elements, wherein the element control range is 0.10-0.25 wt%.
The B element greatly improves the hardenability of the hot forming steel within 50 ppm.
P and S belong to impurity elements, and are within the reasonable production range, so that the production is smooth, the production cost is reduced, and the fatigue property of the steel plate is improved.
The thickness of the substrate is 0.70-4.00 mm. The substrate hot dip as-plated mechanical properties: the yield strength is 350-500 MPa, the tensile strength is 500-780 MPa, the elongation is 10-25%, the n value is more than or equal to 0.12, and the r value is more than or equal to 0.70.
(3) The galvanized steel sheet is designed and controlled precisely for ensuring a wider austenitizing heating process window and a wider heat treatment process window.
The coating organizational structure is designed as follows: at least one surface of the substrate is provided with a plating layer; double-sided equal-thickness or different-thickness plating; the coating is 8.0-24 μm in thickness (single side) and 50-200 g/m in weight (single side) 2 ；
The coating structure comprises the following components from the surface to the substrate: a surface layer (oil film, passivation film, or the like); a zinc coating layer, and Al, fe, ce, la, si, mn, mg and/or Cr elements are dissolved in solid solution; a diffusion layer; the diffusion layer includes a suppression layer.
The surface layer is an oil film or a passive film plus the oil film. When an oil film is adopted, the thickness of the oil film is 500-800 mg/m 2 (ii) a When the passive film and the oil film are adopted for treatment, the thickness of the passive film is 20-50 mg/m 2 The thickness of the oil film is 500-800 mg/m 2 (ii) a The surface roughness Ra of the plating layer is 0.6-1.5 mu m. The surface layer ensures that better friction coefficient in a surface state and a high-temperature state can be obtained after cold stamping.
The thickness of the zinc coating is 6-20 μm, and the zinc coating mainly comprises eta phase, wherein the zinc coating comprises the following components in percentage by weight: 0.02 to 2.20 percent of solid solution FeO, 0.08 to 0.45 percent of Al, 0.08 to 1.4 percent of La and/or 0.12 to 2.0 percent of Ce, less than or equal to 3.0 percent of Si + Mn, less than or equal to 3.5 percent of Mg + Cr, more than or equal to 1.1 percent of Si/Mn and more than or equal to 0.8 percent of Mg/Cr. The zinc layer with the components and the thickness can ensure that the melting point and the high-temperature oxidation resistance are high enough in the subsequent austenite heating and heat treatment processes, and the zinc layer is beneficial to effectively controlling the evaporation and oxidation of surface Zn to obtain a good surface state and a good friction coefficient.
The thickness of the diffusion layer is 2-4 mu m, the diffusion layer accounts for less than or equal to 40 percent of the thickness of the galvanized layer and mainly consists of alpha Fe and gamma phase, wherein the content of alpha Fe is more than or equal to 80 percent; average content of solid solution elements (wt): 0.34 to 1.45 percent of Al, 0.1 to 2.5 percent of La and/or 0.2 to 3.1 percent of Ce, less than or equal to 15.0 percent of Si + Mn and less than or equal to 2.4 percent of Mg + Cr; wherein Si/Mn is more than or equal to 1.1, and Mg/Cr is more than or equal to 0.8.
The inhibition layer is positioned in the diffusion layer, the thickness of the inhibition layer is 100-200 nm, the thickness of the inhibition layer accounts for 5-10% of the thickness of the diffusion layer, and the inhibition layer is mainly Fe 2 Al 5 (ii) a As shown in figure 1, the inhibition layer is flat (parallel to the interface of the substrate and the coating), continuous and compact, so that Fe can be effectively diffused into the zinc coating in the subsequent heat treatment process, and Zn can be effectively inhibited from permeating into the austenite grain boundary of the substrate. The diffusion layer and the inhibition layer with the structure are beneficial to controlling the diffusion of Fe and Zn elements in the austenitizing heating and hot forming processes, thereby controlling the brittleness and the cathodic protection performance of the liquid metal.
(4) The coating design of the galvanized hot forming hot-hardening steel part sequentially comprises the following steps from the outer surface to the substrate: a surface oxidation layer, a Zn-Fe alloy matrix and a diffusion layer.
The surface oxide layer is mainly made of Al 2 O 3 、MgO、MnO、SiO 2 、ZnO、CeO、La 2 O 3 The thickness is 1.0-2.0 μm, the oxide is fine and uniform, and the particle size is less than 3 μm; the depth of the surface oxidation layer is less than 2 mu m, the roughness is lower, the normal coating performance is not influenced, and the oxidation layer can be removed by shot blasting to further improve the coating performance.
The Zn-Fe alloy matrix layer consists of alpha Fe, a gamma phase and a master alloy phase, and the master alloy phase comprises Zn x Si y Fe z 、Zn x Mn y Fe z 、ZnMg 2 (ii) a The Zn-Fe alloy matrix layer contains 40-70 wt% of Fe, 20-50 wt% of Zn and 10-35 mu m of thickness, and has good cathodic protection performance and welding performance.
The diffusion layer consists of alpha Fe with Zn, si, mn, ce and/or Re elements dissolved in solid solution, wherein the Fe content is more than or equal to 80wt%, the Zn content is less than or equal to 5%, and the thickness is 4-6 μm.
The mechanical properties of the galvanized hot-formed hot-hardened steel part are as follows: the yield strength is more than or equal to 1100MPa, the tensile strength is more than or equal to 1300MPa, the elongation is more than or equal to 4 percent, and the bending angle is more than or equal to 55 degrees.
(5) The preparation method of the high corrosion resistant galvanized hot forming hardened steel comprises the following steps: iron-making, steel-making, continuous casting, hot rolling, acid pickling or/and acid rolling, and continuous annealing and galvanizing to obtain the galvanized hot forming hardened steel plate or the galvanized hot forming hardened steel coil.
Wherein, the key technological parameters of the continuous hot dipping are as follows: the temperature Ts of the steel plate in the zinc pot is as follows: 410-475 ℃, zinc liquid temperature Tz: hot dipping for 3-10 s at 420-475 ℃; the temperature of Ts and Tz meets the condition |. Ts-Tz |. Is less than or equal to 40 ℃; plating solution components (wt): 0.12 to 0.35 percent of Al, 0.005 to 0.06 percent of Fe, 0.08 to 3.2 percent of La and/or 0.12 to 5.0 percent of Ce, less than or equal to 3.0 percent of Si and Mn, less than or equal to 3.5 percent of Mg and Cr, and the balance of Zn and inevitable impurities.
(6) The preparation method of the high corrosion resistant galvanized hot forming hardened steel part is as follows.
And (3) blanking the galvanized hot-formed hardened steel plate or the galvanized hot-formed hardened steel coil by using pendulum shear, and preferably blanking by using a pendulum shear blanking mode to obtain a part blank with the size and the shape required by the manufacture of the final part. And deep processing the part blank to obtain a final part product. The deep processing process is as follows:
a) Cold-stamping preforming: cold stamping the part blank to perform; the total deformation of the parts in the deep processing process of the following step f); the cold stamping preforming accounts for 70-100% of the total deformation in the deep processing process; in order to ensure the size of the formed part, the cold-stamping preforming preferably accounts for 90 to 100% of the total deformation.
b) Trimming: and trimming the part blank subjected to cold stamping and preforming by adopting a blanking mode, wherein the trimming comprises punching, flanging, trimming and the like.
c) Austenitizing heat treatment: carrying out heat treatment on the part blank;
i) when the Mn content in the base plate of the galvanized formed hot-hardened steel plate is more than or equal to 0.42wt% and less than or equal to 3.0wt%, the following heating process is adopted:
(1) when the thickness T of the galvanized formed hot-hardened steel plate is more than or equal to 0.7mm and less than or equal to 1.4mm, the heat preservation temperature and time of the steel plate are limited within the range of ABCD; room temperature-T 1 The heating rate Vr in the temperature interval is controlled to be 3-7 ℃/s, T 1 The heating rate Vr from the temperature to the heat preservation temperature is controlled to be 6-18 ℃/s; wherein T is 1 The temperature range is 500-620 ℃; the ABCD range is a square frame range surrounded by points A, B, C and D as shown in FIG. 3; wherein, the temperature of the point A is 850 ℃ and is kept for 190s, the temperature of the point B is 850 ℃ and is kept for 750s, the temperature of the point C is 940 ℃ and is kept for 550s, and the temperature of the point D is 940 ℃ and is kept for 150s;
(2) when the thickness of the galvanized hot-hardened steel plate is more than 1.4mm and less than or equal to 2.5mm, the heating time of the steel plate is limited in the EFGH range; room temperature to T 1 The temperature heating rate Vr is controlled to be 3-7 ℃/s, T 1 The heating rate Vr from the temperature to the heat preservation temperature is controlled to be 6-18 ℃/s; wherein T is 1 The temperature range is 520-640 ℃; the EFGH range is shown in FIG. 4 and is a square range surrounded by points E, F, G and H; wherein, the temperature of 870 ℃ is 870 ℃ for 240s for the point E, 870 ℃ for 850s for the point F, 955 ℃ for 600s for the point G, 955 ℃ for 200s for the point H;
(3) when the thickness of the galvanized hot-hardened steel plate is more than 2.5mm and T is less than or equal to 4.0mm, the steel plateThe heating time is limited within the IJKL range; room temperature to T 1 The temperature heating rate Vr is controlled to be 3-7 ℃/s, T 1 The heating rate Vr of the temperature-heat preservation temperature is controlled to be 6-18 ℃/s; wherein T is 1 The temperature range is 540-660 ℃; the IJHK range is shown in fig. 5 and is a square range surrounded by the point I, the point J, the point K, and the point L; wherein the I point is 890 ℃ heat preservation for 270s, the J point is 890 ℃ heat preservation for 880s, the K point is 960 ℃ heat preservation for 630s, and the L point is 960 ℃ heat preservation for 230s.
II) when the Mn content in the base plate of the galvanized formed hot-hardened steel plate is more than 3.0wt% and less than or equal to 10.0wt%, adopting the following heating process:
(1) when the thickness T of the galvanized formed hot-hardened steel plate is more than or equal to 0.7mm and less than or equal to 1.4mm, the heat preservation temperature and the time of the steel plate are limited to A 1 B 1 C 1 D 1 Within the range; room temperature-T 1 The temperature heating rate Vr is controlled to be 3-7 ℃/s, T 1 The heating rate Vr from the temperature to the heat preservation temperature is controlled to be 6-18 ℃/s; wherein T is 1 The temperature range is 500-620 ℃; a is described 1 B 1 C 1 D 1 The range is shown in FIG. 6 as A 1 Dot, B 1 Dots, C 1 Point sum D 1 A square frame range surrounded by the dots; wherein, A 1 Point is 750 ℃ heat preservation for 200s and B 1 Point is 750 ℃ heat preservation 930s and C 1 Keeping the temperature at 840 ℃ for 630s, and keeping the temperature at 840 ℃ for 180s;
(2) when the thickness of the galvanized formed hot-hardened steel sheet is more than 1.4mm and T is less than or equal to 2.5mm, the heating time of the steel sheet is limited to E 1 F 1 G 1 H 1 Within the range; room temperature to T 1 The temperature heating rate Vr is controlled to be 3-7 ℃/s, T 1 The heating rate Vr from the temperature to the heat preservation temperature is controlled to be 6-18 ℃/s; wherein T is 1 The temperature range is 520-640 ℃; said E 1 F 1 G 1 H 1 The range is shown in FIG. 7 as E 1 Dot, F 1 Dot, G 1 Point sum H 1 A square frame range formed by point enclosure; wherein E is 1 The point is 770 ℃ heat preservation for 270s and F 1 The point is 770 ℃ heat preservation 980s, G 1 The point is 855 ℃ heat preservation 680s and H 1 Keeping the temperature at 855 ℃ for 230s;
(3) when forming by galvanizingT is more than 2.5mm and less than or equal to 4.0mm when the thickness of the hot-hardened steel plate is more than or equal to I, and the heating time of the steel plate is limited to I 1 J 1 K 1 L 1 Within the range; room temperature to T 1 The temperature heating rate Vr is controlled to be 3-7 ℃/s, T 1 The heating rate Vr from the temperature to the heat preservation temperature is controlled to be 6-18 ℃/s; wherein T is 1 The temperature range is 540-660 ℃; said I 1 J 1 K 1 L 1 The range is shown in FIG. 8 as I 1 Point, J 1 Dot, K 1 Point sum L 1 A square frame range surrounded by the dots; wherein, I 1 The temperature is 790 ℃ and the temperature is 330s and J 1 The temperature is 790 ℃ and the temperature is kept for 1010s and K 1 Point 870 ℃ heat preservation 710s and L 1 The spot was 870 ℃ for 260s.
d) Cooling and removing the oxidation layer: transferring the part blank subjected to heat treatment to a cooling device for cooling, and then removing an oxide layer; the cooling process comprises the following steps: and cooling the part blank by adopting a water cooling or air cooling mode at a cooling speed of 20-100 ℃/s until the temperature of the ferrite (F) or the bainite (B) which begins to precipitate is 10-20 ℃ higher than the temperature of the higher transformation point of the F phase or the B phase, and ensuring that the ferrite phase or the bainite phase is not precipitated before hot stamping.
The mechanism of action of this cooling step: after austenitizing heat treatment, the temperature difference between the zinc layer hot forming steel blank and the hot forming temperature reaches 300-400 ℃, if the traditional hot forming process is adopted, the production efficiency is reduced by air cooling in the stages of conveying belt and hot forming, and uneven cooling is caused by cooling in a die; according to the method, a water cooling or air cooling process is arranged after the blank is austenitized and heated, so that the subsequent hot stamping heat preservation time can be effectively shortened, the production efficiency is improved, and the uniformity of temperature control in the cooling process is improved; in addition, the process of obtaining air cooling by controlling water cooling can effectively remove loose Al on the surface of the zinc layer of the blank after high-temperature heating 2 O 3 、MgO、Cr 2 O 3 And the like.
e) Entering a mold: and transferring the cooled part blank to a die.
f) Shaping or low-temperature thermoforming: and (3) precisely shaping the shape of the part, or performing low-temperature thermal forming with small deformation on the part with a complex shape, and improving the forming precision of the part to obtain the finished product of the part. The low-temperature hot forming process and the shaping process are both as follows: when Mn in the substrate is less than or equal to 3.0wt%, the hot stamping temperature range is 450-760 ℃; when the content of Mn in the substrate is more than 3.0wt% and less than or equal to 10.0wt%, the hot stamping temperature ranges from 350 ℃ to 660 ℃; the pressure maintaining time is 4-8 s; the quenching cooling speed is more than or equal to 27 ℃/s, and is preferably between 27 and 60 ℃/s.
The present method the low temperature hot truing/forming quench is in comparison to the conventional hot forming process principle as shown in fig. 9; in the shaping or low-temperature hot forming process of the method: the part shape is precisely shaped, or the part with a complex shape is subjected to small deformation amount thermal forming, so that the part forming precision can be effectively improved. The hot forming temperature range of the low-temperature hot forming process is obviously 50-200 ℃ lower than that of the traditional hot forming process, which is mainly due to the following reasons: firstly, the thermal austenite of the substrate in the method has higher stability, has lower Ms, bs and Fs precipitation temperature which is shifted to the right, does not precipitate bainite, ferrite or martensite phase in the low-temperature hot forming process, and does not have brittleness caused by easy penetration of Zn into grain boundaries due to mixed crystals or multiphase structures; secondly, under the condition of lower temperature, the deformation is limited to be less than or equal to 20 percent of the total deformation of the part, even under the condition of no deformation, the hot forming is not easy to cause the generation of zinc layer cracks.
Examples 1 to 30: the high corrosion resistant galvanized hot formed hardened steel, the parts and the preparation method thereof are concretely described as follows.
(1) Galvanized hot-formed hardened steel sheets or coils were prepared by iron-making, steel-making, continuous casting, hot rolling, acid or acid rolling, continuous annealing and galvanizing processes, the substrate chemistry of which is described in table 1.
Table 1: substrate chemistry of various examples
In table 1, the balance is Fe and inevitable impurities; the steel grade of the comparative example was 22MnB5.
(2) The components of the plating solution for hot dip plating are shown in table 2, the hot dip plating process is shown in table 3, the structure of the zinc layer after hot dip plating is shown in table 4, and the mechanical properties of the hot dip plated zinc sheet after hot dip plating are shown in table 5; wherein the coating structure morphology of the hot dip coated steel plate of the example 4 is shown in figure 2.
Table 2: bath composition/wt% of each example
In table 2, the balance is Zn and inevitable impurities.
Table 3: hot dip plating Process of Each example
Table 4: the hot dip coating structure obtained in each example
In table 4, the balance of the average plating layer content is Zn and unavoidable impurities.
Table 5: mechanical Properties of galvanized Hot-formed hardened Steel sheets obtained in examples
(3) The cold stamping, austenitizing heat treatment, and pre-cooling processes of the examples are shown in table 6, the cooling and hot forming processes are shown in table 7, the plating structure of the parts is shown in table 8, and the mechanical properties of the parts are shown in table 9.
Table 6: examples Cold Forming and Austenitizing Heat treatment
In Table 6, the first heating rate is from room temperature to T 1 Heating rate in temperature range, the second heating rate is T 1 Temperature-holding temperature.
In table 6, examples 1, 2, 10, 11, and 12 correspond to fig. 3; examples 3, 4, 13, 14, 15 correspond to fig. 4; examples 5, 16, 17, 18, 19 correspond to fig. 5; examples 8, 9, 20, 21, 22 correspond to fig. 6; examples 23, 24, 25, 26, 27 correspond to fig. 7; examples 6, 7, 28, 29, 30 correspond to fig. 8.
Table 7: cooling and thermoforming process
Table 8: part plating layer structure
Table 9: mechanical properties of parts, electrode potential and plating state
Claims (7)
1. A high corrosion resistant galvanized hot-formed hardened steel is characterized in that: it comprises a substrate and a plating layer;
the substrate comprises the following components in percentage by mass: 0.12 to 0.35 percent of C, 0.08 to 2.12 percent of Si, 0.42 to 10.00 percent of Mn, 0.03 to 0.12 percent of Al, 0.02 to 0.65 percent of Cr, less than or equal to 1.12 percent of Mo, 0.02 to 0.25 percent of Nb + V + Tis, 0.0003 to 0.005 percent of B, less than or equal to 0.012 percent of S, less than or equal to 0.08 percent of P, and the balance of Fe and inevitable impurities;
the plating layer comprises the following components in percentage by mass: 0.15 to 0.45 percent of Al, 0.05 to 2.50 percent of Fe, 0.08 to 3.2 percent of La and/or 0.12 to 5.0 percent of Ce, less than or equal to 3.0 percent of Si and Mn, less than or equal to 3.5 percent of Mg and Cr, and the balance of Zn and inevitable impurities;
the plating layer comprises a zinc plating layer and a diffusion layer, wherein the diffusion layer contains a suppression layer; the thickness of the zinc coating is 6-20 μm, the zinc coating mainly comprises eta phase, and the zinc coating comprises the following components: 0.08 to 2.20 percent of solid-solution Fe, 0.08 to 0.45 percent of Al, 0.08 to 1.4 percent of La and/or 0.12 to 2.0 percent of Ce, less than or equal to 3.0 percent of Si + Mn, less than or equal to 3.5 percent of Mg + Cr, more than or equal to 1.1 percent of Si/Mn, more than or equal to 0.8 percent of Mg/Cr;
the thickness of the diffusion layer is 2-4 μm, the diffusion layer accounts for less than or equal to 40% of the thickness of the galvanized layer, the diffusion layer mainly comprises alpha Fe and gamma phase, the alpha Fe in the diffusion layer is more than or equal to 80%, and the average content of main solid solution elements is as follows: 0.34 to 1.45 percent of Al, 0.1 to 2.5 percent of La and/or 0.2 to 3.1 percent of Ce, less than or equal to 15.0 percent of Si and Mn, and less than or equal to 2.4 percent of Mg and Cr;
the thickness of the inhibition layer is 100-200 nm, the thickness of the inhibition layer accounts for 5-10% of the thickness of the diffusion layer, and the inhibition layer is mainly Fe 2 Al 5 。
2. The method for producing a highly corrosion-resistant galvanized hot-formed hardened steel according to claim 1, characterized by: hot dip coating the hardened steel sheet; the plating solution comprises the following components in percentage by mass: 0.12 to 0.35 percent of Al, 0.005 to 0.06 percent of Fe0, 0.08 to 3.2 percent of La and/or 0.12 to 5.0 percent of Ce, less than or equal to 3.0 percent of Si and Mn, less than or equal to 3.5 percent of Mg and Cr, more than or equal to 1.1 percent of Si/Mn, more than or equal to 0.8 percent of Mg/Cr and the balance of Zn and inevitable impurities;
the hot dip plating process comprises the following steps: the temperature Ts 410-475 ℃ of the hardened steel plate in a zinc pot, the temperature Tz 420-475 ℃ of the plating solution and the hot dipping time 3-10 s; the temperature of Ts and Tz meets the condition | Ts-Tz |. Is less than or equal to 40 ℃.
3. A highly corrosion-resistant galvanized hot-formed hardened steel part prepared from the highly corrosion-resistant galvanized hot-formed hardened steel of claim 1, characterized in that: it comprises a substrate and a plating layer; the coating comprises a surface oxidation layer, a Zn-Fe alloy matrix layer and a diffusion layer from the outer surface to the substrate in sequence;
the surface oxide layer is mainly composed of Al 2 O 3 、MgO、MnO、SiO 2 、ZnO、CeO、La 2 O 3 Is 1.0-2.0 μm thick, particle size is less than 3 μm, and surface oxide layer depth is less than 2 μm;
the Zn-Fe alloy matrix layer consists of alpha Fe, a gamma phase and a master alloy phase, and the master alloy phase comprises Zn x Si y Fe z 、Zn x Mn y Fe z 、ZnMg 2 (ii) a The Zn-Fe alloy matrix layer contains 40 to 70 weight percent of Fe and 20 weight percent of Zn50wt% and a thickness of 10-35 μm.
4. A method for producing a highly corrosion-resistant galvanized hot-formed hardened steel part as claimed in claim 3, characterized in that: cold stamping, preforming, trimming and austenitizing heat treatment are carried out on the galvanized hot-formed hardened steel; transferring to a cooling device, cooling and removing an oxidation layer; and then transferring the blank to a mold for shaping or low-temperature thermal forming.
5. The method for preparing a highly corrosion-resistant galvanized hot-formed hardened steel part according to claim 4, characterized in that the cooling and deoxidation process is: and reducing the temperature of the blank to be 10-20 ℃ above the precipitation temperature of ferrite or bainite by adopting a water cooling or air cooling mode.
6. The method for preparing a highly corrosion-resistant galvanized hot-formed hardened steel part according to claim 4, characterized in that the reshaping or low-temperature hot-forming process is: the pressure maintaining time is 4-8 s, and the quenching cooling speed is more than or equal to 27 ℃/s; when Mn in the substrate is less than or equal to 3.0wt%, the hot stamping temperature ranges from 450 ℃ to 760 ℃; when the Mn content in the substrate is more than 3.0wt% and less than or equal to 10.0wt%, the hot stamping temperature range is 350-660 ℃.
7. The method for preparing a highly corrosion-resistant galvanized hot-formed hardened steel part according to claim 4, 5 or 6, characterized in that the austenitizing heat treatment process is:
i) when the Mn content in the base plate of the galvanized formed hot-hardened steel plate is more than or equal to 0.42wt% and less than or equal to 3.0wt%, the following heating process is adopted:
(1) when the thickness T of the galvanized formed hot-hardened steel plate is more than or equal to 0.7mm and less than or equal to 1.4mm, the heat preservation temperature and time of the steel plate are limited within the range of ABCD; room temperature-T 1 The heating rate Vr in the temperature range is controlled to be 3-7 ℃/s, T 1 The heating rate Vr from the temperature to the heat preservation temperature is controlled to be 6-18 ℃/s; wherein T is 1 The temperature range is 500-620 ℃; wherein, the temperature of the point A is kept at 850 ℃ for 190s, the temperature of the point B is kept at 850 ℃ for 750s, the temperature of the point C is kept at 940 ℃ for 550s, and the temperature of the point D is kept at 940 ℃ for 150s;
(2) when the thickness of the galvanized hot-hardened steel plate is more than 1.4mm and less than or equal to 2.5mm, the heating time of the steel plate is limited in the EFGH range; room temperature to T 1 The temperature heating rate Vr is controlled to be 3-7 ℃/s, T 1 The heating rate Vr from the temperature to the heat preservation temperature is controlled to be 6-18 ℃/s; wherein T is 1 The temperature range is 520-640 ℃; wherein, the temperature of 870 ℃ is 870 ℃ for 240s for the point E, 870 ℃ for 850s for the point F, 955 ℃ for 600s for the point G, 955 ℃ for 200s for the point H;
(3) when the thickness T of the galvanized formed hot-hardened steel plate is more than 2.5mm and less than or equal to 4.0mm, the heating time of the steel plate is limited in the IJKL range; room temperature to T 1 The temperature heating rate Vr is controlled to be 3-7 ℃/s, T 1 The heating rate Vr of the temperature-heat preservation temperature is controlled to be 6-18 ℃/s; wherein T is 1 The temperature range is 540-660 ℃; wherein the I point is 890 ℃ heat preservation for 270s, the J point is 890 ℃ heat preservation for 880s, the K point is 960 ℃ heat preservation for 630s, and the L point is 960 ℃ heat preservation for 230s;
II) when the Mn content in the base plate of the galvanized formed hot-hardened steel plate is more than 3.0wt% and less than or equal to 10.0wt%, adopting the following heating process:
(1) when the thickness T of the galvanized hot-hardened steel plate is more than or equal to 0.7mm and less than or equal to 1.4mm, the heat preservation temperature and the time of the steel plate are limited to A 1 B 1 C 1 D 1 Within the range; room temperature-T 1 The temperature heating rate Vr is controlled to be 3-7 ℃/s, T 1 The heating rate Vr from the temperature to the heat preservation temperature is controlled to be 6-18 ℃/s; wherein T is 1 The temperature range is 500-620 ℃; wherein A is 1 The point is that the temperature is kept at 750 ℃ for 200s and B 1 Point is 750 ℃ heat preservation 930s and C 1 Point 840 ℃ heat preservation 630s and D 1 Keeping the temperature at 840 ℃ for 180s;
(2) when the thickness of the galvanized formed hot-hardened steel sheet is more than 1.4mm and T is less than or equal to 2.5mm, the heating time of the steel sheet is limited to E 1 F 1 G 1 H 1 Within the range; room temperature to T 1 The temperature heating rate Vr is controlled to be 3-7 ℃/s, T 1 The heating rate Vr from the temperature to the heat preservation temperature is controlled to be 6-18 ℃/s; wherein T is 1 The temperature range is 520-640 ℃; wherein E is 1 The point is 770 ℃ heat preservation for 270s and F 1 The point is 770 ℃ heat preservation 980s and G 1 The point is 855 ℃ heat preservation 680s and H 1 Point 855 ℃ heat preservation 230s；
(3) When the thickness of the galvanized formed hot-hardened steel sheet is more than 2.5mm and T is less than or equal to 4.0mm, the heating time of the steel sheet is limited to I 1 J 1 K 1 L 1 Within the range; room temperature to T 1 The temperature heating rate Vr is controlled to be 3-7 ℃/s, T 1 The heating rate Vr from the temperature to the heat preservation temperature is controlled to be 6-18 ℃/s; wherein T is 1 The temperature range is 540-660 ℃; wherein, I 1 The temperature is 790 ℃ and the temperature is 330s and J 1 The temperature is 790 ℃ and the temperature is kept for 1010s and K 1 Point 870 ℃ heat preservation 710s and L 1 The spot was 870 ℃ for 260s.
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