CN120060766A - High heating efficiency aluminum-based coated hot-formed steel sheet and hot-formed part having excellent phosphating property - Google Patents
High heating efficiency aluminum-based coated hot-formed steel sheet and hot-formed part having excellent phosphating property Download PDFInfo
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- CN120060766A CN120060766A CN202510184101.7A CN202510184101A CN120060766A CN 120060766 A CN120060766 A CN 120060766A CN 202510184101 A CN202510184101 A CN 202510184101A CN 120060766 A CN120060766 A CN 120060766A
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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
- C23C2/12—Aluminium or alloys based thereon
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C21/00—Alloys based on aluminium
- C22C21/02—Alloys based on aluminium with silicon as the next major constituent
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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
- C23C2/34—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
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- Mechanical Engineering (AREA)
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- Coating With Molten Metal (AREA)
Abstract
The invention discloses an aluminum-based coating hot-formed steel plate with high heating efficiency and a hot-formed part with excellent phosphating property, wherein at least one surface of the aluminum-based coating hot-formed steel plate sequentially comprises a steel substrate, an aluminum alloy coating and an Fe coating from the substrate to the top, the aluminum alloy coating comprises 8.0-12.0% of Si, less than or equal to 2.0% of Fe and the balance of aluminum and unavoidable impurities, the Fe coating contains 0.1-2.0 g/m 2 of Fe by weight, preferably 0.1-1.0 g/m 2 of Fe by weight, the aluminum-based coating hot-formed steel plate has high heating efficiency in the hot-press forming process, and has good phosphating property, the coating has sacrificial anode protection effect on a substrate and good corrosion resistance after painting.
Description
Technical Field
The invention belongs to the technical field of hot forming steel, and particularly relates to an aluminum-series coating hot forming steel plate with high heating efficiency and a hot forming part with excellent phosphating property.
Background
Because of the light weight and corrosion resistance requirements, automotive parts are heavily hot formed steel with high strength coatings. Among coated hot-formed steels, aluminum-based coated hot-formed steel sheets are widely used.
The parts of the vehicle body need to be phosphated to form a phosphated film to ensure adhesion between the paint and the substrate. However, aluminum silicon plated hot formed steel may form dense aluminum silicon oxides on the hot formed surface, the presence of which makes it difficult to phosphorylate during the coating process.
It is desirable to shorten the heating time in the furnace as much as possible in view of productivity and energy saving and emission reduction. However, in view of coating, a high heating rate may lead to insufficient alloying and a decrease in adhesion and corrosion resistance after hot forming.
There are known techniques for partially improving the heating efficiency of aluminum-based plated hot-formed steel, such as chinese patent CN103492606a, chinese patent CN106164184A, chinese patent CN 116219271a, by applying a substance having higher heat absorption efficiency than aluminum alloy to the surface of a steel sheet. However, these methods for improving heating efficiency cannot solve the technical problems of incapacitation of phosphating after thermoforming and low corrosion resistance after painting, because these substances volatilize during thermoforming and do not contribute to the subsequent phosphating process.
It is also known that there are solutions aimed at improving the phosphating properties of aluminium-silicon coatings, as disclosed in chinese patent CN105829578a for press hardening steel sheets comprising an aluminium-based coating and a ZnO coating. As another example, chinese patent CN107250414a discloses a steel sheet coated with an aluminum-based coating and further comprising a second zinc coating, having the effect of improving the phosphate surface treatment. However, the ZnO coatings and zinc coatings in these patents do not have the technical effect of improving heating efficiency.
In summary, a technical scheme for simultaneously improving the phosphating property and the heating efficiency of the aluminum-silicon coating hot forming steel is lacking at present.
Disclosure of Invention
In order to solve the technical problems, the invention provides an aluminum-based coating hot-formed steel plate and a preparation method thereof, wherein the aluminum-based coating hot-formed steel plate has high heating efficiency in the hot-press forming process, good phosphating property after hot-press forming and sacrificial anode protection effect of a coating on a substrate.
The invention also provides a hot-formed part, which is prepared by heating and heat-preserving the aluminum-series coated hot-formed steel plate and hot stamping the hot-formed steel plate, and has good phosphating property and good corrosion resistance after painting.
The technical scheme adopted by the invention is as follows:
An aluminum-based coating hot-formed steel plate, which comprises a steel substrate, an aluminum alloy coating and an Fe coating from the substrate to the top in sequence;
the aluminum alloy coating comprises 8.0-12.0% of Si, less than or equal to 2.0% of Fe and the balance of aluminum and unavoidable impurities in percentage by mass;
The Fe coating contains 0.1 to 2.0g/m 2 wt% Fe, preferably 0.1 to 1.0g/m 2 wt% Fe, based on the Fe content.
Further, the Fe coating layer does not contain any metals other than Fe, except for unavoidable impurities.
The Fe coating is one or more of Fe, fe oxide or hydrate thereof, fe halogen compound or hydrate thereof, fe organic acid salt compound or hydrate thereof, fe carbonate compound or hydrate thereof.
Further, an anti-rust oil layer is also covered on the Fe coating. The purpose of the coating of the rust preventive oil is to temporarily prevent rust and to prevent the scratch of the plating layer at blanking, and since it is decomposed at the time of thermoforming, the coating amount thereof does not affect the technical effect of the present invention, and the adhesion amount of the rust preventive oil is preferably 0.5 to 2g/m 2.
The Fe-containing coating is formed by plating Fe on the aluminum alloy coating in a chemical plating, electroplating or vacuum plating mode.
The Fe-containing coating layer is attached by a Fe compound layer formed by contacting an aluminum plating plate with a solution containing Fe ions.
The Fe-containing coating is formed by applying a powder or colloidal solution containing an Fe oxide, an Fe hydroxide, an Fe carbonate compound, or an Fe organic acid salt compound to the aluminum alloy plating. In this embodiment, a binder such as a resin may be used to enhance adhesion between the Fe compound and the aluminum alloy plating layer, but the selected resin should not contain silicon, phosphorus, and nitrogen elements, which are detrimental to the coating quality after thermoforming, and which may cause NO x gas emissions.
The invention also provides a preparation method of the aluminum-based coated hot-formed steel plate, which comprises the following steps of hot dip plating a hot rolled substrate or a cold rolled substrate, forming an aluminum alloy coating on the surface of the substrate, and then forming an Fe coating on the surface of at least one aluminum alloy coating.
The hot forming part is manufactured by heating and preserving heat, and then hot stamping the aluminum-based coated hot forming steel plate. At least one surface of the aluminum alloy coating and iron oxide are sequentially arranged from the steel substrate upwards, wherein the iron oxide is granular and distributed on the surface of the aluminum alloy coating in an area ratio of at least 50 percent.
The heating temperature of the heating and heat preservation is 840-1100 ℃, the heat preservation time is 2-5min for the plate material with the thickness of more than or equal to 1.4mm, and the heat preservation time is 1-2min for the plate material with the thickness of less than 1.4 mm. Due to the existence of the surface treatment layer Fe, the heat absorption efficiency of the plate is improved, the time required for heating to the austenitizing temperature is shorter, and the heating time of the heating process can be shortened by more than 1min compared with that of the conventional hot forming process. The heating furnace can adopt any atmosphere such as N 2 protective atmosphere, air and the like, and air is preferably adopted for the cost. When a protective atmosphere is used, part of the Fe may not be completely oxidized, but the oxide may still be sufficiently formed later in the course of the transfer of the ingot from the furnace to the die and hot stamping, so that the phosphating effect is not affected.
The temperature of the hot stamping is 500-700 ℃.
The aluminum-based plated hot-formed steel sheet of the present invention is not limited to the composition of the steel substrate, and is exemplified by 22MnB5, which has a chemical composition of ：0.20％≤C≤0.25％;0.15％≤Si≤0.35％;1.10％≤Mn≤1.40％;0％≤Cr≤0.30％;0％≤Mo≤0.35％;0％≤P≤0.025％;0％≤S≤0.005％;0.020％≤Ti≤0.060％;0.020％≤Al≤0.060％;0.002％≤B≤0.004％,% by weight and the balance of iron and unavoidable impurities derived from steel production, as a conventional practice.
In the aluminum-based coating hot-formed steel plate provided by the invention, in the components of the aluminum alloy coating, si can form an Fe-Al-Si inhibition layer on the surface of the steel plate, so that the formation of brittle phase Fe2Al5 can be effectively prevented, and the coating adhesion is improved. When the Si content is less than 8.0%, the Fe-Al alloy layer becomes thicker, the adhesiveness of the coating is reduced, and when the Si content is more than 12.0%, the surface quality of the coating is affected, and according to the conditions, the Si content in the aluminum alloy coating is controlled to be 8.0-12.0%.
The inventor realizes that the adhesion amount of Fe needs to be strictly limited based on the hard research to ensure that the Fe has better technical effects of improving the heating efficiency and the coating performance. When the attachment amount of Fe is more than 2.0g/m 2, although the heating efficiency and the weight of the phosphating film can be improved, the stripping width exceeds the standard in the corrosion test after painting, because the Fe plating layer forms a loose and thick oxide layer in the thermoforming, the phosphating film covers the loose oxide layer in the subsequent coating process, and the coating can be stripped from the iron oxide layer. When the amount of Fe attached is less than 0.1g/m 2, the coverage of the surface of the iron oxide formed during the hot forming is insufficient, and the effect of improving the heating efficiency and the phosphating ability is insufficient. The inventors have also found that Fe has a minimum paint peel width and a high heating rate at an adhesion amount of 0.1 to 1.0g/m 2.
Compared with the prior art, the invention has the following beneficial effects:
According to the invention, the Fe-containing coating is applied to the surface of the aluminum coating, so that the technical defect of poor phosphating performance of the traditional aluminum-silicon hot-formed part is overcome, the aluminum-silicon hot-formed part has excellent post-paint corrosion resistance, meanwhile, the heat absorption efficiency of aluminum-plated hot-formed steel in the hot forming process is improved, the hot forming heating time is shortened, and the method has the technical advantages of environmental protection and low cost.
Drawings
FIG. 1 is a schematic view showing the progress of the coating layer of an aluminum-based coated hot-formed steel sheet according to the present invention in each step.
Detailed Description
The present invention will be described in detail with reference to examples.
The chemical composition and weight percentages of the steel sheets used for the hot-dip forming of the coatings of examples 1 to 5 and comparative examples 1 to 5 below were as follows ：C 0.2252％,Mn 1.1735％,P 0.0126％,S 0.0009％,Si 0.2534％,Cr 0.180％,Al 0.0371％,Ti 0.0382％,B 0.0028％,Mo0.0017％,, the balance being iron and unavoidable impurities.
The steel sheets of the above examples and comparative examples were hot dip plated in a hot rolled state or an annealed state to obtain an aluminum alloy-plated steel sheet, for example, by hot rolling, pickling, hot dip plating, leveling to obtain a hot base aluminum alloy-plated steel sheet, or by hot rolling, pickling, cold rolling, cleaning, annealing, hot dip plating, leveling to obtain an aluminum alloy-plated steel sheet.
The aluminum alloy coating contains 8.0-12.0% by mass of Si, up to 2% by mass of Fe, and the balance of aluminum and unavoidable impurities.
The plating layer obtaining modes of each example and comparative example are described in detail below.
The aluminum alloy plated sheet in example 1 and comparative example 1 was obtained by hot rolling, pickling, cold rolling, cleaning, annealing, hot dip plating, and leveling to obtain an aluminum alloy plated steel sheet. After the above steps are completed, the aluminum alloy coating contains 8.0% by mass of Si,2.0% by mass of Fe, and the balance of aluminum and unavoidable impurities. The plate thickness is 1.2mm, the coating is coated on both sides with equal thickness, and the weight of each single-side coating is 40g/m 2.
Example 2, comparative example 2 an aluminum alloy plated sheet was obtained by hot rolling, pickling, hot dip plating, and leveling to obtain an aluminum alloy plated steel sheet. After the above steps are completed, the aluminum alloy coating contains 9.0% by mass of Si,1.0% by mass of Fe, and the balance of aluminum and unavoidable impurities. The thickness of the plate is 1.2mm, the coating is coated on both sides with equal thickness, and the weight of each single-side coating is 60g/m 2.
Example 3 and comparative example 3 an aluminum alloy plated sheet was obtained by hot rolling, pickling, cold rolling, cleaning, annealing, hot dip plating, and leveling. And obtaining the aluminum alloy coated steel plate. After the above steps are completed, the aluminum alloy coating contains 10.0% by mass of Si,1.5% by mass of Fe, and the balance of aluminum and unavoidable impurities. The plate thickness is 1.4mm, the coating is coated on both sides with equal thickness, and the weight of each single-side coating is 35g/m 2.
Example 4 and comparative example 4 an aluminum alloy plated sheet was obtained by hot rolling, pickling, cold rolling, cleaning, annealing, hot dip plating, and leveling. And obtaining the aluminum alloy coated steel plate. After the above steps are completed, the aluminum alloy coating contains 12% by mass of Si,2.0% by mass of Fe, and the balance of aluminum and unavoidable impurities. The thickness of the plate is 1.6mm, the coating is coated on both sides with equal thickness, and the weight of each single-side coating is 75g/m 2.
Example 5 and comparative example 5 an aluminum alloy plated sheet was obtained by hot rolling, pickling, cold rolling, cleaning, annealing, hot dip plating, and leveling. And obtaining the aluminum alloy coated steel plate. After the above steps are completed, the aluminum alloy coating contains 10% by mass of Si,1.5% by mass of Fe, and the balance of aluminum and unavoidable impurities. The thickness of the plate is 2.0mm, the coating is coated on both sides with equal thickness, and the weight of each single-side coating is 75g/m 2.
And (3) applying an Fe-containing coating on the Al alloy coating by any mode of chemical plating, electroplating, vacuum plating, roller coating, spraying and the like, and controlling the adhesion quantity of the Fe coating to be 0.1-2.0 g/m 2.
As a specific embodiment, the following steps for applying Fe coating layers of examples 1-3 and comparative examples 2-3 were:
(1) An emulsion was formulated having the following composition:
150g/L of ferroferric oxide powder with the particle size of 50 nm;
200g/L polyacrylate;
50g/L ethanol;
5g/L dodecyl glucoside;
The balance being water.
(2) The emulsion is coated on the aluminum alloy plating layer.
(3) Heating to 200 ℃ and drying for 30s, and cooling to room temperature.
As a specific embodiment, the following steps of applying the Fe coating of examples 4, 5 and comparative examples 4, 5 are:
(1) Alkaline washing the surface of the aluminized silicon steel plate, removing greasy dirt, and washing with deionized water;
(2) A solution was formulated with the following ingredients:
80g/L ferrous chloride;
14g/L hydrofluoric acid;
5g/L sulfamic acid;
1g/L dodecyl glucoside;
The balance being water.
(3) And (3) at room temperature, immersing the aluminized silicon plate in the solution for 2-3 min.
(4) And washing the surface of the steel plate by deionized water, removing residual acid, and drying.
The rust preventive oil was used selectively to coat the aluminum alloy plating layer or the Fe coating layer, and the purpose of the coating rust preventive oil was to temporarily prevent rust and to prevent the plating layer from being scratched at blanking, and since it was decomposed at the time of thermoforming, the coating amount thereof did not affect the effect of the present invention, and the following examples and comparative examples were each coated with 1.5g/m 2 of quinine Ferrocoat N6130 type rust preventive oil. Each of the examples and comparative examples was coated with rust inhibitive oil.
The above coated steel sheet was subjected to performance evaluation according to the following method.
Measurement of time/s and heating rate from 20 ℃ to 900 ℃ the cut slabs were placed in a 900 ℃ box oven, the time required for heating to 900 ℃ was measured with a thermocouple, and the heating rate was calculated.
Heating total time, namely placing the cut sheet material into a 900 ℃ box furnace, taking 1min as a starting point, sequentially prolonging for 30s, then cooling in a flat plate die, grinding, mechanically polishing and picric acid etching a 10mm multiplied by plate thickness sample cut from the experimental steel subjected to die quenching, observing and measuring the original austenite grain size under an optical microscope to observe a martensitic structure, and taking the heating time for completely forming martensite as the heating total time.
Evaluation of pretreatment performance before coating:
Phosphating performance evaluation Using a degreasing agent for a two-component automobile of Shanghai Paka-Beijing Co., ltd., FC-L5000A (40 g/L)/FC-E2021 SB (16 g/L), the degreasing liquid temperature was 50 ℃, immersing the hot-formed steel sheet in the degreasing liquid for 2 minutes, and then taking out and rinsing with deionized water. After degreasing, phosphating was performed, and the resultant was subjected to surface conditioning for 30 seconds (immersion) using a PL-X surface conditioner (Shanghai Kaka-Beijing Co., ltd.), followed by ternary phosphating using Paka PB-3035 SB. The parameters of the phosphating solution are that the total acidity is 22.0pt, the free acidity is 1.0pt, the accelerator concentration is 2.0pt, the temperature is 35 ℃ and the time is 2min. After the pretreatment is finished, washing and drying, and then carrying out a phosphating film retest according to the GB/T9792-2003 standard.
The method for evaluating the corrosion resistance after coating comprises the steps of carrying out electrophoresis after pretreatment, and enabling the thickness of an electrophoresis dry film to reach 20+/-2 mu m by using an optimized process. The electrophoretic paint is of the type of Hunan Xiangjiang Guangxi paint HT8000C. And (3) carrying out scratch corrosion test after electrophoresis, scratching the paint by using a scratch knife, then placing the paint in a corrosion environment for 26 days, taking out the paint after test, removing floating rust, stripping a scratch area by using an adhesive tape, and taking the paint stripping width of the scratch area as an assessment index. The cyclic corrosion environment test method comprises 8h of normal temperature maintenance (25+/-3 ℃ C., 4 times of spraying saline solution respectively for 3min, wherein the saline solution comprises 0.9wt% of NaCl,0.1wt% of CaCl 2 and 0.0750.9wt% of NaHCO 3), 8h of damp heat (49+/-2 ℃ C., 100% RH), 8h of drying (60+/-2 ℃ C., 30% RH) and 26 cycles.
The adhesion amount of the Fe coating layer in the aluminum-based plated hot-formed steel sheet in each example and comparative example, and the evaluation results are shown in table 1.
Evaluation results:
compared with comparative example 1, example 1 significantly shortens the heating time by 20-900 ℃ and shortens the total heating time by 1min. And compared with comparative example 1, the pretreatment performance before coating of example 1 is remarkably improved, the pretreatment film weight is higher, and the corrosion resistance after electrophoretic coating is excellent.
The Fe adhesion amount of comparative example 2 was 0.05g/m 2, and the improvement in heating efficiency, phosphated film weight and paint peeling width was insufficient as compared with example 2.
Examples 3 and 4 have a closer heating rate than comparative examples 3 and 4, and the weight of the phosphated film is slightly increased by 3/4, while the paint peeling width after corrosion test is poorer by 3/4 compared with the comparative examples, which is caused by that more Fe oxide cannot be fully reacted with the phosphated solution to form a film.
Example 5 has a heating rate close to that of the phosphating film weight compared to comparative example 5, but comparative example 5 has a significantly increased paint peel width due to the fact that more Fe oxide fails to react completely with the phosphating solution to form a film.
Table 1 surface treatment methods and evaluation results of examples and comparative examples
The above detailed description of a high heating efficiency aluminum-based coated hot-formed steel sheet and a hot-formed part having excellent phosphating properties with reference to examples is illustrative and not restrictive, and several examples can be enumerated according to the defined scope, and therefore, variations and modifications are considered to fall within the scope of the present invention without departing from the general inventive concept.
Claims (10)
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| CN202510184101.7A CN120060766A (en) | 2025-02-19 | 2025-02-19 | High heating efficiency aluminum-based coated hot-formed steel sheet and hot-formed part having excellent phosphating property |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN120682679A (en) * | 2025-08-21 | 2025-09-23 | 马鞍山钢铁有限公司 | Aluminum-coated hot-formed steel plate with high heating efficiency and paint adhesion, manufacturing method and application thereof |
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2025
- 2025-02-19 CN CN202510184101.7A patent/CN120060766A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN120682679A (en) * | 2025-08-21 | 2025-09-23 | 马鞍山钢铁有限公司 | Aluminum-coated hot-formed steel plate with high heating efficiency and paint adhesion, manufacturing method and application thereof |
| CN120682679B (en) * | 2025-08-21 | 2025-11-21 | 马鞍山钢铁有限公司 | Aluminum-based coating hot-formed steel plate with high heating efficiency and paint adhesion, manufacturing method and application |
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