WO2024028641A1

WO2024028641A1 - Steel sheet having excellent corrosion properties after press hardening and method for manufacturing the same

Info

Publication number: WO2024028641A1
Application number: PCT/IB2022/057250
Authority: WO
Inventors: Maxime BROSSARD; Tiago MACHADO AMORIM; Pascale FELTIN
Original assignee: Arcelormittal
Priority date: 2022-08-04
Filing date: 2022-08-04
Publication date: 2024-02-08
Also published as: WO2024028760A1

Abstract

A steel sheet, coated with a metallic coating comprising, by weight percent, from 6.0 to 10.0 % of zinc, from 1.1 to 4.0 % of silicon, from 1.1 to 8.0 % of magnesium, up to 3.0% of iron, optional elements chosen from Pb, Ni, Zr, or Hf, the content by weight of each element being less than 0.3%, optionally up to 100 ppm of Calcium and unavoidable impurities up to 0.02 %, the balance being aluminum.

Description

Steel sheet having excellent corrosion properties after press hardening and method for manufacturing the same

The present invention relates to a method for the manufacture of hardened parts starting from a steel sheet coated with a metallic coating. The part has good characteristics with respect to cosmetic corrosion resistance after painting. The invention is particularly well suited for the manufacture of automotive vehicles.

In recent years the use of coated steels in hot-stamping processes for the shaping of parts has become important, especially in the automotive industry. Fabrication of such parts may include the following main steps:

- Coating of a steel sheets, by hot dipping

- Trimming or cutting for obtaining blanks

- Heating the blanks in order to obtain alloying of the steel substrate with the coating, as well as the austenitizing of the steel

- Press hardening of the part in order to obtain a predominantly martensitic structure.

Thanks to an alloying of the coating with the steel substrate, which has the effect of creating intermetallic alloys with high melting temperature, the blanks having such coating may be heated in a temperature range where austenitizing of the metallic substrate takes place, allowing further hardening by quenching.

Hardened parts can be coated with zinc-based coating or aluminum-based coating.

Zinc-based coatings are generally used because they allow a protection against corrosion thanks to barrier protection and cathodic protection. Sacrificial cathodic protection is based on the fact that zinc is a metal less noble that steel. Thus, if corrosion occurs, zinc is consumed preferentially to steel.

However, when press hardening process is performed on such zinc coated steel sheets, for example by hot-stamping, microcracks are observed in steel which spread from the coating. Additionally, the step of painting of hardened parts coated with zinc necessitates sanding operations before phosphatizing due to the presence of a weak layer of oxides at the part surface.

Aluminum-based coatings have a good aptitude for painting. They allow for a protection by barrier effect and can be welded. However, they do not allow for a cathodic protection or they have a very low cathodic protection.

The purpose of the present invention is to provide a coated steel sheet providing cathodic protection and a suitable method for manufacturing a press hardened part with a good corrosion performance after phosphatizing without prior sanding operations.

This is achieved by the steel sheet of claims 1 to 4.

Another object of the invention is the manufacturing method of claims 5 and 6.

The invention also covers press hardened parts coated with a metallic coating having an oxide layer on top of the coating according to claims 7 to 11 .

A final object of the invention is the use of such a coated part for the manufacture of an automotive vehicle according to claims 12 to 14.

Other characteristics and advantages of the invention will become apparent from the following detailed description of the invention.

To illustrate the invention, various embodiments and trials of non-limiting examples will be described, particularly with reference to the following figures obtained by scanning electron microscopy with a magnification of x 500:

- figure 1 illustrates the homogeneous distribution observed by cross-section of the metallic coating after heat-treatment (at 900°C for 6 minutes) on a 1 .5 mm thick steel sheet with a coating comprising 8 % by weight of zinc, according to the invention.

- figure 2 illustrates the inhomogeneous distribution observed by cross-section of the metallic coating after heat-treatment (at 900°C for 6 minutes) on a 1 .5 mm thick steel sheet, with a coating comprising 15 % by weight of zinc, not according to the invention. The invention relates to a steel sheet coated with a metallic coating comprising, by weight, from 6.0 to 10.0 % of zinc, from 1 .1 to 7.0 % of silicon, from 1.1 to 8.0 % of magnesium, up to 3.0% of iron, and unavoidable impurities up to 0.02 %, the balance being aluminum.

Preferably, the coating comprises, in weight percent, from 2.0 to 4.0 % of silicon and from 1.1 to 4.0 % of magnesium, advantageously from 1.5 to 2.5 % of magnesium.

Preferably, the coating comprises, in weight percent, from 7.5 to 9.0 % of zinc.

Optionally, the coating comprises additional elements chosen from Ni, Zr, Hf, Sr, Sb, Pb, Ti, Ca, Mn, Sn, La, Ce, Cr, or Bi, the content by weight of each additional element being inferior to 0.3 wt.%. In a preferred embodiment, up to 100 ppm of calcium is added.

Finally, the coating may contain unavoidable impurities up to 0.02 %, preferably up to 0.01 %.

The steel sheet according to the invention can be manufactured by hot dip galvanizing in a bath, the temperature of which is set from 600 to 700°C, preferably from 620 to 650°C.

The coating weight is set during the wiping process by gas knives in a range from 50 to 500 g/m², possibly from 80 to 150 g/m² and preferably from 100 and 120 g/m² for the sum of both sides of the steel sheet.

Before being coated, the steel sheet according to the invention can be obtained by hot rolling and optionally cold rolling depending on the desired thickness, which can be for example between 0.5 and 3.0 mm.

The steel substrate to be coated can have any appropriate composition, depending on the final properties required. When the steel is used for presshardening, its composition is preferably as described below.

The coated steel sheet according to the invention can notably be used in a press hardening method. In particular, it can be used in the frame of a method of manufacturing of a press hardened part according to the invention.

This method according to the invention comprises the following steps:

A) the provision of a coated steel sheet according to the invention, B) the cutting of the coated steel sheet to obtain a blank,

C) the thermal treatment of the blank at a temperature between 840 and 950°C to obtain a fully austenitic microstructure in the steel,

D) the transfer of the blank into a press tool,

E) the press-hardening of the blank to obtain a part,

F) the cooling of the part obtained at step E) in order to obtain a press- hardened part.

In step A, any steel can be advantageously used in the frame of the invention. However, in case steel having high mechanical strength is needed, in particular for parts of structure of automotive vehicle, steel having a tensile resistance superior to 500MPa, advantageously between 500 and 2000MPa before or after heattreatment, can be used. The weight composition of steel sheet is preferably as follows: 0.03% < C < 0.50% ; 0.3% < Mn < 3.0% ; 0.05% < Si < 0.8% ; 0.015% < Ti

< 0.2% ; 0.005% < Al < 0.1 % ; 0% < Cr < 2.50% ; 0% < S < 0.05% ; 0% < P< 0.1 % ; 0% < B < 0.010% ; 0% < Ni < 2.5% ; 0% < Mo < 0.7% ; 0% < Nb < 0.15% ; 0% < N

< 0.015% ; 0% < Cu < 0.15% ; 0% < Ca < 0.01 % ; 0% < W < 0.35%, the balance being iron and unavoidable impurities from the manufacture of steel.

For example, the steel sheet is 22MnB5 with the following weight composition: 0.20% < C < 0.25%; 0.15% < Si < 0.35%; 1.10% < Mn < 1.40%; 0% < Cr < 0.30%; 0.020% < Ti < 0.060%; 0.020% < Al < 0.060%; 0.002% < B < 0.004%, the remainder being iron and unavoidable impurities from the manufacture of steel.

In another embodiment, the steel sheet has the following weight composition: 0.24% < C < 0.38%; 0.40% < Mn < 3%; 0.10% < Si < 0.70%; 0.015% < Al < 0.070%; Cr < 2%; 0.25% < Ni < 2%; 0.015% < Ti < 0.10%; Nb < 0.060%; 0.0005% < B < 0.0040%; the remainder being iron and unavoidable impurities resulting from the manufacture of steel.

Alternatively, the steel sheet can have the following weight composition: 0.30% < C < 0.40%; 0.5% < Mn < 1.0%; 0.40% < Si < 0.80%; 0.1 % < Cr < 0.4%; 0.1 % < Mo < 0.5%; 0.01 % < Nb < 0.1 %; 0.01 % < Al < 0.1 %; 0.008% < Ti < 0.003%; 0.0005% < B < 0.003%; 0.0% < P < 0.02%; 0.0% < Ca < 0.001 %; 0.0% < S < 0.004 %; 0.0% < N < 0.005 %, the remainder being iron and unavoidable impurities resulting from the manufacture of steel. In another embodiment, the steel sheet has the following weight composition: 0.040% < C < 0.100%; 0.80% < Mn < 2.00%; 0% < Si < 0.30%; 0% < S < 0.005%; 0% < P < 0.030%; 0.010% < Al < 0.070%; 0.015% < Nb < 0.100%; 0.030% < Ti < 0.080%; 0% < N < 0.009%; 0% < Cu < 0.100%; 0% < Ni < 0.100%; 0% < Cr < 0.100%; 0% < Mo < 0.100%, the balance being iron and unavoidable impurities from the manufacture of steel.

In another embodiment, the steel sheet has the following weight composition: 0.06% < C < 0.1 %, 1 % < Mn < 2%, Si < 0.5%, Al <0.1 %, 0.02% < Cr < 0.1 %, 0.02%

< Nb < 0.1 %, 0.0003% < B < 0.01 %, N < 0.01 %, S < 0.003%, P < 0.020% less than 0,1 % of Cu, Ni and Mo, the remainder being iron and unavoidable impurities resulting from the manufacture of steel.

In another embodiment, the steel sheet has the following weight composition: 0.015% < C < 0.25%; 0.5% < Mn < 1.8%; 0.1 % < Si < 1.25%; 0.01 % < Al < 0.1 %; 0.1 % < Cr < 1 .0%; 0.01 % < Ti < 0.1 %; 0% < S < 0.01 %; 0.001 % < B < 0.004%; 0%

< P < 0.020%; 0% < N < 0.01 %; the balance being iron and unavoidable impurities from the manufacture of steel.

Alternatively, the steel sheet has the following weight composition: 0.2% < C

< 0.34%; 0.5% < Mn < 1 .24%; 0.5% < Si < 2.0%; 0% < S < 0.01 %; 0% < P < 0.020%; 0% < N < 0.01 %, the balance being iron and unavoidable impurities from the manufacture of steel.

The steel sheet is cut into a blank in step B. Said coated steel blank may have a thickness which is not uniform. This is the case of the so-called “tailored rolled blanks” which are obtained from cutting a sheet obtained by a process of rolling with an effort which is variable along the direction of the length of the sheet. Or this may be also the case of the so-called “tailored welded blanks” obtained by the welding of at least two sub-blanks of different thicknesses. In step C, a heat treatment of the blank is performed at a temperature from 800 to 970°C, preferably from 840 to 950°C. Said blank is maintained during a dwell time from 1 to 15 minutes. During the heat treatment before the press hardening, the coating forms an alloy layer having a high resistance to corrosion, abrasion, wear and fatigue.

In step D, after the heat treatment, the blank is then transferred to a presshardening tool.

In step E, the press-hardening takes place at a temperature from 600 to 830°C.

In step F, the part is cooled in the hot-forming tool or after the transfer to a specific cooling tool. The cooling rate is controlled depending on the steel composition, in such a way that the final microstructure after press hardening is consistent with the targeted mechanical properties. After press hardening, the part can be tempered to reach the targeted microstructure and mechanical properties.

In a preferred embodiment, the steel microstructure comprises, in terms of volume fraction, at least 95% of martensite.

In another embodiment, the steel microstructure comprises after press hardening, in terms of volume fraction, at least 50% of martensite and less than 40 % of bainite.

In another embodiment, the steel microstructure comprises after press hardening, in terms of volume fraction, from 5 to 20 % of martensite, up to 10 % of bainite and at least 75 % of equiaxed ferrite.

A coated part according to the invention is thus obtained by press hardening but is also achievable by any suitable combination of cold-stamping and press hardening.

The part obtained in step F is topped by a superficial oxide layer on its outer surface. This oxide layer comprises aluminum, zinc and magnesium from the coating and iron from the steel substrate. Iron has diffused through the coating during heat treatment. The thickness of said oxide layer can vary from 0.2 up to 3 pm, preferably from 0.3 to 1.5 pm. Oxidizable elements have their highest concentration at the vicinity of the surface. The proportion of each element can be obtained by Energy X-ray dispersive spectroscopy. It gives thus the composition of a layer having a thickness of 1 ,5 pm from the outer surface.

According to the invention, the superficial oxide layer comprises aluminum from 10 to 27 % by weight, preferably 17 to 24%.

According to the invention, the superficial oxide layer comprises zinc from 20 to 60 % by weight, preferably 25 to 50%.

According to the invention, the superficial oxide layer comprises magnesium from 5 to 10 % by weight.

According to the invention, the superficial oxide layer comprises iron from 10 to 28 % by weight, preferably 14 to 25%.

Without willing to be bound by any theory, it is believed that the corrosion performance after phosphating step is related to the zinc content in the superficial oxide layer having a depth of 1 .5 pm or less from the outer surface of the coating.

If there is less than 20 % in weight of zinc in this superficial oxide layer, the surface is mainly composed of aluminium oxide, which is not phosphatable. It is believed that zinc oxides are not covering enough the upper surface to ensure a proper layer of phosphate crystals after phosphatizing, resulting in a poor corrosion performance.

If there is more than 60 % in weight of zinc in this superficial layer, the surface becomes non-uniform, as can be seen on figure 2. It is believed that this heterogeneity leads then to poor corrosion performance.

This invention is notably relevant to manufacture any parts relevant for crash which are in wet areas. Specifically, the part can be a front rail, a seat cross member, a side sill member, a dash panel cross member, a front floor reinforcement, a rear floor cross member, a rear rail, a B-pillar, a door ring or a shotgun.

For automotive applications, the part is previously degreased and phosphated to ensure the adhesion of the other layers. Then, the part is dipped in an e-coating bath forming a layer by cataphoresis on the part. After the e-coating step, other paint layers can be deposited, for example, a primer coat of paint, a basecoat layer and a top-coat layer.

Usually, the thickness of the phosphate layer is from 1 to 2 pm and the thickness of the e-coating layer is between 15 and 25 pm, preferably inferior or equal to 20pm. The cataphoresis layer ensures an additional protection against corrosion

The invention will now be explained in trials carried out for information only. They are not limiting.

Examples

For all samples, steel sheets used are 22MnB5. The composition of the steel is as follows: C = 0.23 %; Mn = 1.2%; Si = 0.25%; %; Cr = 0.2%; Al = 0.04%; Ti = 0.04%; B = 0.003 %.

All coatings were deposited by hot-dip galvanization process. The hot dip bath temperature was set at 620 or 650°C.

Example 1 : Surface analysis:

Trials 1 to 14 were therefore prepared as follows: coated samples were cut into blanks. These blanks were then heated at a temperature of 900°C during a dwell time varying from 5 to 6 minutes. Blanks were transferred into a press tool and hot-stamped to obtain a part. Finally, the part was cooled to obtain a hardening by martensitic transformation. After press hardening and when observed with a microscope, trials 1 to 11 have a homogeneous coating distribution at the vicinity of the surface, as can be observed on figure 1. Trials 12 to 14, on the contrary, have an inhomogeneous coating distribution as can be seen on figure 2.

After heat treatment, trials were subjected to the EDX test to deliver their superficial composition of the outer layer having a thickness of 1.5 pm: surface analysis test is used to determine the weight percentage of elements on the surface. After heat treatment, the samples were analyzed using Energy X-ray dispersive spectroscopy (EDX) at 15 kV to determine the superficial atomic composition of the oxide layer. Results are gathered in table 1 .

Table 1 : Samples tested

Example 2: Corrosion test

A degreasing of the samples was then realized. It was followed by a phosphating step realized by dipping them into a bath solution comprising during 3 minutes at 50°C. The components of the phosphating bath are Gardobond® products from supplier Chemetall. Their concentrations are disclosed in table 2.

Table 2: Component concentrations in phosphating bath

The samples were then wiped with water and dried with hot air and finally stored in corrosion chambers for 12 cycles according to VDA 233-102 standard. All the samples according to the invention had less than 20% red rust in terms of surface percentage after these cycles. Results are gathered in table 3.

Table 3: Corrosion results

*Trials according to the invention, underlined values are not according to the invention.

Trials 1 , and 12 to 14, the steel sheet coating of which contains respectively 5 and 15 weight % of zinc, have also less than 20% or more than 60 weight % of zinc in the oxide layer after heat treatment. They show more than 20% of red rust in terms of area portion.

The trials according to the invention show less than 20% of red rust in terms of area portion.

Claims

CLAIMS A steel sheet, coated with a metallic coating comprising, by weight percent, from 6.0 to 10.0 % of zinc, from 1.1 to 4.0 % of silicon, from 1.1 to 8.0 % of magnesium, up to 3.0% of iron, optional elements chosen from Pb, Ni, Zr, or Hf, the content by weight of each element being less than 0.3%, optionally up to 100 ppm of Calcium and unavoidable impurities up to 0.02 %, the balance being aluminum. A steel sheet according to claim 1 , wherein said metallic coating comprises, by weight percent, from 7.5 to 9.0 % of zinc, 2.0 to 4.0% of silicon, 1 .1 to 4.0 % of magnesium, up to 3.0% of iron, and optional elements chosen from Pb, Ni, Zr, or Hf, the content by weight of each element being less than 0.3%, optionally up to 100 ppm of Calcium, and unavoidable impurities up to 0.01 %, the balance being aluminum. A steel sheet according to claims 1 or 2, wherein the coating weight of said metallic coating is from 50 to 500 g/m² for both sides of said steel sheet. A steel sheet according to claim 3, wherein the coating weight of said coating is from 80 to 150 g/m² for both sides of said steel sheet A method for the manufacture of a hardened part coated with an anti-corrosion coating comprising the following steps:

A) the provision of a coated steel sheet according to anyone of claims 1 to 4,

B) the cutting of the coated steel sheet to obtain a blank,

C) the thermal treatment of the blank at a temperature from 840 to 950°C to obtain a fully austenitic microstructure in the steel,

D) the transfer of the blank into a press tool,

E) the press hardening of the blank to obtain a part, F) the cooling of the part obtained at step E) in order to obtain a press-hardened part.

6. A method according to claim 5, wherein in step A) said coating comprises, by weight percent, from 7.5 to 9.0 % of zinc, 2.0 to 4.0% of silicon, 1 .1 to 4.0 % of magnesium, up to 3.0% of iron, and optional elements chosen from Pb, Ni, Zr, or Hf, the content by weight of each element being less than 0.3%, unavoidable impurities up to 0.01 %, and optionally up to 100 ppm of Calcium, the balance being aluminum.

7. A press-hardened coated steel part obtained by press-hardening of a coated steel sheet according to anyone of claims 1 to 4, said coating being topped by a superficial oxide layer on its outer surface, such oxide layer comprising from 20 to 60 % weight of zinc on a thickness of 1 .5 pm from the outer surface of the coated part.

8. A press-hardened coated steel part according to claim 7, wherein such oxide layer comprises from 25 to 50 % weight of zinc.

9. A press-hardened coated steel part according to claims 8 or 7, wherein the microstructure of said press-hardened part comprises, in terms of volume fraction, at least 95% of martensite.

10. A press-hardened coated steel part according to claims 7 or 8, wherein the microstructure of said press-hardened part comprises, in terms of volume fraction, at least 50% of martensite and less than 40 % of bainite.

11. A press-hardened coated steel part according to anyone of claims 7 or 8, wherein the microstructure of said press-hardened part comprises from 5 to 20 % of martensite, up to 10 % of bainite and at least 75 % of equiaxed ferrite. Use of a part according to any of claims 7 to 10 for the manufacture of an automotive vehicle. Use of a part according to claim 11 for the manufacture of parts located in wet area of an automotive vehicle. Use of a part according to claim 12 for the manufacture of at least one part chosen among: front rail, seat cross member, side sill member, dash panel cross member, front floor reinforcement, rear floor cross member, rear rail, B- pillar, door ring, shotgun.