EP4247992A1

EP4247992A1 - Steel material and method for production thereof

Info

Publication number: EP4247992A1
Application number: EP21816016.6A
Authority: EP
Inventors: Florian Gerstner; Andreas Sommer; Siegfried Kolnberger; Thomas Kurz
Original assignee: Voestalpine Stahl GmbH
Current assignee: Voestalpine Stahl GmbH
Priority date: 2020-11-19
Filing date: 2021-11-18
Publication date: 2023-09-27
Also published as: WO2022106561A1; DE102020130543A1; CN116507752A; US20240002965A1

Abstract

The invention relates to a steel material for the production of high- or super-high-strength components with a tensile strength Rm > 1600 MPa, more particularly > 1800 MPa and more particularly > 2000 MPa, the steel material being a boron-manganese steel which has a carbon content of > 0.30 mass %, the steel material being hot rolled, or hot rolled and cold rolled, to a strip having a thickness of 0.5 to 3 mm, the strip having a thin coating of zinc or an alloy on the basis of zinc with a weight of the coating mass of < 50 g/m2 for each strip side of the steel strip.

Description

Steel material and method for its manufacture

The invention relates to a steel material and a method for its production.

It is known, in particular in automobile bodies, to form structural components and in particular structural components which form the passenger compartment or load-bearing components from high-strength steel grades. The use of high-strength steel grades or high-strength steel components has the advantage that with very high strength, these components can be designed with a comparatively small wall thickness, which in turn reduces the vehicle weight and thus the fuel consumption.

Efforts to achieve this in body construction by hardening components have been known since the mid-1980s.

In order to produce such high-strength steel components, two methods have prevailed in the prior art, namely press hardening and hot stamping developed by the applicant.

What both processes have in common is that quenching at a rate above the critical hardening rate influences the steel structure that forms in such a way that the steel becomes very hard.

In the case of press hardening, a plate made of a suitably hardenable steel is heated to a temperature that is so high that the steel structure is partially or completely transformed into austenite. This transformation usually takes place above the austenite transformation temperature A _c 3 . This A _c 3 temperature depends on the steel material and its alloy composition and is usually between 720 and 920°C. A steel blank heated in this way is then transferred to a forming tool, in which case it retains its austenitic state, and is brought into the shape of the desired component in this forming tool with one or more forming strokes. The forming tool is so cold that when you touch the austenitic blank during forming and then the component obtained by forming, the heat is dissipated so quickly from the steel into the forming tool that the critical hardening speed is exceeded. This converts the structure of the steel from an austenitic structure to a predominantly or completely martensitic structure.

A certain carbon content of the steel is necessary for this martensite transformation, with the hardening effect, to put it very simply, increasing with the higher the carbon content. The hardening effect is based on the fact that, to put it simply, the austenite lattice can dissolve carbon better than the martensite lattice that forms, so that lattice strains or carbide precipitations occur in the martensite lattice, which lead to a distortion of the lattice, which causes the high hardness.

Another way of creating such hardened components is the already mentioned form hardening. The physical requirements and the metallurgical requirements of the steel are basically the same as in press hardening. However, in the case of hot stamping, the component is first cold formed in a conventional forming process. The usual shaping process for steel is deep drawing, for which five-stage press lines are often used, in which such a component is formed into the finished component with five forming strokes. The multiple press strokes mean that more complex components can be achieved than would be possible with press hardening, since there is only one press stroke available for forming and hardening, since after the first forming stroke the component is hardened to such an extent that it is practically impossible to bend can be reshaped more.

During hot stamping, the finished formed component is heated to such an extent that the steel reaches its austenitic state and is transferred to a hot stamping tool in the austenitic state. The form hardening tool is 0.2% larger than the target geometry of the finished component. It is particularly advantageous if, during the hot stamping process, the component is dimensioned in all three spatial directions after cold forming in such a way that it has exactly the size of the desired component in all three spatial directions after heating up due to thermal expansion and, above all, when it is placed in the hot stamping tool exactly the size that is also specified by the form hardening tool. The heated component then fits perfectly into the hardening mold, is placed in it and the hardening mold closes and clamps the hot component on all sides. The form hardening The tool is also cold, so the heat is dissipated from the steel into the tool, also at a rate above the hardening critical rate.

Thus, the austenitic structure is also converted into a martensitic structure during form hardening, with the hardening effect already described.

The press hardening process is also referred to as a direct process because it hardens and forms directly. The form hardening process is also referred to as an indirect process because the hardening no longer carries out any shaping or at least only minor shaping or calibration.

To ensure that the critical hardening speed is exceeded, which is usually between 20 and 25 Kelvin per second and is usually significantly exceeded by the tools, the tools can usually be cooled and, for example, have liquid cooling.

With the methods mentioned, components can be achieved which achieve tensile strengths R _m of more than 1600 MPa and in particular more than 1800 MPa and even up to or more than 2000 MPa.

The materials have different designations depending on the manufacturer, but are generally referred to in the prior art as, for example, PHS1500 for grades that can develop a tensile strength of 1500 MPa during press or form hardening or PHS2000 for grades that have a tensile strength of 2000 MPa and be able to train more.

In addition, it has long been known to design such components with a metallic anti-corrosion coating. The fundamental need for a metallic anti-corrosion coating resulted from essentially two requirements. One requirement is that the metallic anti-corrosion coating should prevent superficial oxidation and scaling of the material during heating. The second, more important effect is that press-hardened or form-hardened components with a corresponding metallic coating fit better into the overall corrosion protection concept of the vehicle, especially automobiles. Initially, only aluminium-based metallic anti-corrosion coatings were used because it was assumed that only these could withstand the high-temperature process of heating up to the hardening temperature. A special selection of chemicals later made it possible to use metallic anti-corrosion coatings based on zinc, which can be better integrated into a fully galvanized body than aluminium-coated sheets, which can (but do not have to) lead to contact corrosion.

Metallic anti-corrosion layers are often identified by abbreviations for the materials used, with the abbreviation AS usually standing for aluminum silicon layers, while the abbreviation Z applies to zinc layers or zinc-based layers produced by means of hot dip and ZF stands for zinc layers, which after hot dip coating are treated by a subsequent heat treatment step diffusion-related alloy with the underlying sheet steel, so-called galvannealing layers. These are distinguished by the fact that usually up to 15%, preferably between 8% and 14%, of iron are diffused into the zinc layer. ZE stands for zinc-based layers which were applied using an electrolytic process.

In addition, it is customary to put a number after this abbreviation, which indicates the coating weight in grams per m ² . A Z140 coating therefore means that it is a zinc coating applied by hot dipping with a total of 140 g per m ² layer coating on both sides of the strip. This means that with Z140, 70 g Zn per m ² is applied to each side of the strip.

In the prior art, so-called boron-manganese steels are used as steel materials, i.e. steels alloyed with boron and manganese. One of these steels is, for example, the most widely used 22MnB5, where the number 22 indicates the carbon content, i.e. 0.22% carbon.

However, other grades are also known, in particular to achieve very high strength, such as 34MnB5, where the carbon content - for the reasons already mentioned - is higher, namely 0.34%. In addition to the 34MnB5, variants with a higher boron alloy such as a 34MnB7 or 34MnB8 are also possible.

In the prior art it has been found that the materials with a higher carbon content, which are particularly suitable for developing tensile strengths of over 2000 MPa after press or die hardening.

Particularly high-strength grades, ie grades that can achieve tensile strengths of over 2000 MPa, are currently processed either uncoated or provided with an aluminium-silicon coating. These ultra-high strength steel grades can often, but not always, have certain problems related to hydrogen uptake during austenitization heating. Therefore, with such materials, especially special high-carbon materials, the furnace atmosphere is specially adjusted and, in particular, works with a very low dew point.

The object of the invention is to create a steel material which can be produced in a simpler and improved manner, in particular as a high-strength steel material with tensile strengths of more than 2000 MPa.

The object is achieved with a steel material having the features of claim 1.

Advantageous developments are identified in the dependent claims.

The steel material of the present invention is a quench-hardenable steel material composed of a boron-manganese steel having a high carbon content.

In particular, the steel material is a material containing more than 0.30% carbon and in particular a 34MnB5 type steel.

A composition of the steel material according to the invention is as follows, all data being in mass percentages:

Carbon (C) 0.30-0.60 Manganese (Mn) 0.5-3.0 Aluminum (Al) 0.01-0.30 Silicon (Si) 0.01-0.5 Chromium (Cr) 0. 01-1 .0 Titanium (Ti) 0.01-0.08 Niobium (Nb) 0.001-0.06 Nitrogen (N) < 0.02 Boron (B) 0.002-0.02 Phosphorus (P) < 0.015 Sulfur ( S) < 0.01 Molybdenum (Mo) < 1

The remainder is iron and unavoidable impurities from the smelting process.

A particularly preferred composition of the steel material can be composed as follows, with all data being in percent by mass:

Carbon (C) 0.32-0.38 Manganese (Mn) 0.8-1.5 Aluminum (AI) 0.025-0.20 Silicon (Si) 0.01-0.5 Chromium (Cr) 0.01-0.25 Titanium (Ti) 0.025-0, 08 Niobium (Nb) 0.001-0.06 Nitrogen (N) < 0.006 Boron (B) 0.002-0.008 Phosphorus (P) < 0.012

Sulfur (S) < 0.002 Molybdenum (Mo) < 1

The remainder is iron and unavoidable impurities from the smelting process.

The steel material can be particularly distinguished if the following condition is met: (AI - 0.02) / (15.4 * N) + Ti / (3.25 * N) + Nb / (13.3 * N) >= 1

In this case, the ratio of aluminum, titanium and niobium in relation to nitrogen is advantageously adjusted in order to activate the boron as effectively as possible in the steel material as a hardening element and to be able to achieve correspondingly high tensile strength values.

According to the invention, the material is covered with a thin layer of zinc alloy, contrary to common practice with galvanized hardenable steels and expert knowledge. According to the invention, however, the zinc alloy coating is extremely thin and is <7 μm per strip side, preferably <6 μm per strip side. This corresponds, for example, to a layer ZF80 (approx. 35 g/m ² Zn per hinge side).

Contrary to professional considerations, no thick layer of zinc was applied, since cathodic protection against corrosion is not the priority.

According to the invention, it was found that even such a thin zinc alloy layer evens out the heating behavior of the steel in the furnace over the surface of the strip. In the case of uncoated sheet steel, the heating behavior can vary locally due to uneven oil distribution. In addition, due to production-related inhomogeneities, the oxide adhesion can develop locally with different strengths and thus the effect of cleaning or conditioning processes, in particular wheel blasting, can have different local effects. Furthermore, compared to uncoated high-strength sheet steel, it is advantageous that processing is more cost-effective, despite the thin zinc layer can be produced without protective gas, especially existing plants can be used in a good way. Surprisingly, significantly improved formability and significantly reduced tool wear have resulted. The processing is also less expensive than sheets coated with aluminium-silicon layers and it was surprisingly found that heating up takes place more quickly than sheets coated with aluminium-silicon, so that the minimum furnace dwell time is significantly reduced. This is attributed to the fact that the emissivity is significantly better right from the start and it is not necessary to react through the layers or it can be carried out much more quickly.

Therefore, a coating weight of less than 50 g/m ² , in particular less than 45 g/m ² , particularly preferably less than 40 g/m ² , can advantageously offer reduced friction and thus reduced wear. On the other hand or in addition, the coating weight can be greater than 20 g/m ² , in particular greater than 25 g/m ² , particularly preferably greater than 30 g/m ² , in order to even out the heating behavior even further and to further positively influence the formation of the oxide layer.

In addition, compared to aluminium-silicon-coated steels, it is advantageous that there are apparently no hydrogen problems, because no dew point control is required in the furnace and no dry air injection is required either. Tests have shown that the hydrogen loading after the furnace process, i.e. after austenitization, is significantly lower. Another very surprising effect that occurred is that materials of this type, which were previously poorly suited for adhesive connections, are now easily possible with the material according to the invention. The material with the particularly thin zinc layer is ideally suited for adhesive connections. Even at very low test temperatures, this compound shows no local delamination. In addition, the sheets have significantly improved weldability compared to uncoated and untreated sheets and compared to aluminium-silicon-coated sheets. Compared to thick zinc coatings, it was found that the heating rate is also higher here, with the zinc coating being so thin that no embrittlement occurs through contact of austenite with liquid zinc phases, the so-called Liquid Metal Embrittlement (LME).

Surprisingly, it was found that with direct forming, i.e. press hardening, despite the low zinc layer, the friction values in the tool are just as good as with a significantly thicker zinc layer, for example Z140 or Z200, despite the thin layer. In the indirect process, i.e. hot stamping, in contrast to AlSi, very good formability without delamination could also be observed. In addition, the hydrogen loading was also significantly lower here than with an uncoated or with an AlSi material. The invention thus relates to a steel material for the production of high-strength or ultra-high-strength components with a tensile strength R _m > 1600 MPa, in particular > 1800 MPa and in particular > 2000 MPa, the steel material being a boron-manganese steel which has a carbon content > 0, 30 M-%, the steel material being hot-rolled or hot-rolled and cold-rolled into a strip with a thickness of 0.5 to 3 mm, the strip having a thin coating of zinc or a zinc-based alloy with a coating weight of <50 g/m ² per strip side of the steel strip.

Furthermore, the invention relates to a steel material, the steel material having the following alloy

Composition has (all data in % by mass):

Carbon (C) 0.30-0.60 Manganese (Mn) 0.5-3.0 Aluminum (Al) 0.01-0.30 Silicon (Si) 0.01-0.5 Chromium (Cr) 0. 01-1 .0 Titanium (Ti) 0.01-0.08 Niobium (Nb) 0.001-0.06 Nitrogen (N) < 0.02 Boron (B) 0.002-0.02 Phosphorus (P) < 0.015 Sulfur ( S) < 0.010 molybdenum (Mo) < 1

The remainder is iron and impurities caused by the smelting process.

In an advantageous further development, the steel material has the following alloy composition (all data in % by mass):

Carbon (C) 0.32-0.38 Manganese (Mn) 0.8-1.5 Aluminum (Al) 0.025-0.20 Silicon (Si) 0.01-0.5 Chromium (Cr) 0.01- 0.25 Titanium (Ti) 0.025-0.08 Niobium (Nb) 0.001-0.06 Nitrogen (N) < 0.006 Boron (B) 0.002-0.008 Phosphorus (P) < 0.012 Sulfur (S) < 0.002 Molybdenum (Mo) < 1

The remainder is iron and impurities caused by the smelting process.

In an advantageous development, the steel material fulfills the following condition (in % by mass) (Al - 0.02) / (15.4 * N) + Ti / (3.25 * N) + Nb / (13.3 * N) >= 1

In another advantageous development, the layer weight is <45 g/m ² , in particular <40 g/m ² , particularly preferably <30 g/m ² per side of the steel strip

In an advantageous development, the coating consists of zinc or an alloy based on zinc, or is a coating that is converted into a zinc-iron layer on the steel strip by a temperature treatment.

The invention also relates to a method for producing a steel material, wherein a melt for a boron-manganese steel with a carbon content> 0.3% by mass is melted and then cast, the slab obtained being hot-rolled or hot-rolled and cold-rolled to form a To obtain steel strip with a thickness of 0.5 to 3 mm, the steel strip thus obtained being coated with a coating of zinc or an alloy based on zinc using a galvanizing process, the coating having a coating weight of <50 g/m ² per has hinge side.

In a further development, the zinc layer is converted into a zinc-iron layer with a proportion of 8 to 18% by mass of iron, preferably 10 to 15% by mass of iron, by a heat treatment following the galvanizing.

In an advantageous embodiment, the zinc layer is deposited by hot dip coating (hot-dip galvanizing), electrolytic galvanizing or a PVD process.

In an advantageous development, in addition to zinc, the coating can contain other elements such as aluminum, magnesium, nickel, chromium, tin, iron or a mixture of these, which are deposited together. The sum of these elements can be less than 25% by mass, preferably less than 15% by mass, particularly preferably less than 5% by mass. This means that the coating contains at least 75% by mass of zinc.

In addition, the invention relates to a method for producing components, in particular hardened components, from steel material, one of the aforementioned steel materials according to the invention being press-hardened or form-hardened. In a further development, the steel material is heated to a temperature between 700 and 950°C for the purpose of austenitization, optionally maintained at this temperature until it has reached a desired degree of austenitization and then hardened, with the material either being completely deformed before heating or shaped after heating.

The invention is explained with reference to a drawing, the only figure of which shows a comparison of the different properties of different comparison materials.

The numbers 1 to 4 each show material with a tensile strength of around 1500 MPa and different types of coating. AlSi stands for well-known coatings made of aluminum silicon, also known as llsibor. Uncoated stands for bare material, i.e. uncoated. The press hardening process used is also indicated in brackets, with ind standing for the indirect process and dir for the direct hot forming process. The designation pc stands for a well-known pre-cooling process in which the steel blank is cooled to a temperature of 400°C to 650°C before forming.

Numbers 5 to 8 show corresponding material with a tensile strength of around 2000 MPa, again with different types of coating.

All examples from 1 to 8 are not according to the invention but are known materials from the prior art.

In the columns next to the designation, the individual mechanical values are assessed and assessed according to their suitability. A - indicates a poor suitability, a 0 an average suitability, a + a good suitability and a ++ an excellent suitability. The designation na stands for values that are not used, for example a coefficient of friction for the indirect process is not applicable.

The steel material according to the invention is a blasting material made from a high-carbon or higher-carbon boron-manganese steel, in particular a steel with more than 0.30% by mass of carbon and in particular a 34MnB5. The examples according to the invention are designated as number 9 and number 10 in FIG.

This material has been melted according to the usual analysis of a 34MnB8 and continuously cast and then hot-rolled and, if desired, cold-rolled. The steel material has a thickness of 0.5 to 3 mm as a strip or sheet and thus also the blanks cut out of it.

For further processing, the hot-rolled or optionally hot and cold-rolled steel material is provided with a zinc coating or a coating with an alloy based on zinc or a zinc-iron layer.

Electrolytic galvanizing, galvanizing using the PVD process or hot-dip galvanizing can be used for galvanizing.

In all three cases, the zinc layer on both sides of the strip is set to <7 μm, more preferably <6 μm.

If desired, the zinc layer (Z/FVZ) on the steel strip can be converted into a zinc-iron layer (ZF) by heating to temperatures between 400 and 600°C.

For further processing into components, sections, so-called blanks, are cut out of this sheet steel strip. For processing in the press hardening process, i.e. in the direct process, the blanks are placed in a furnace and passed through the furnace and heated above the austenitization temperature (A _c 3) in the furnace and, if necessary, kept at this temperature until a desired degree of austenitization, in particular a complete austenitization has taken place.

The blanks austenitized in this way are then removed and placed in a forming tool in which the blanks are formed with a single stroke and simultaneously quenched by the cold tool and thereby hardened.

For the indirect process, the blanks are fed to a particularly single-stage or multi-stage forming process and formed there into the desired component, with the degree of forming usually increasing with each forming stroke and the products being transferred between the individual forming stations. The trimming preferably takes place in the course of the forming.

After the last forming station, ie when the forming is as far as desired, ie a finished component has been achieved, the components are fed to a furnace and austenitized in the furnace and removed after the desired degree of austenitization and a Abandoned form hardening tool in which the component is clamped by the flow of the forming tool and thereby quenched and hardened.

The usual continuous furnaces are suitable as furnaces, which are usually adapted to their corresponding cycle rates of the process.

Components produced in this way are compared with other components in FIG. The two lowest materials here are materials according to the invention which have a very high strength class, namely more than 2000 MPa tensile strength R _m . It can be seen that the corrosion protection is less effective compared to thicker zinc layers, but corrosion protection is not the primary task of the thin zinc layer. Above all, the material has significantly less problematic behavior in the furnace than high-strength steel grades that are coated with aluminum silicon (Al-Si) or not (uncoated), since no protective gas atmosphere and no dew point control are necessary and the furnace process window is larger. With the material according to the invention, the risk of absorbing hydrogen in the PHS furnace is significantly lower than with an AlSi-coated material, and the risk of absorbing hydrogen in the course of welding, cutting, phosphating, cathodic dip painting or possible corrosion is significantly lower than with thicker ones zinc layers. It is surprising that the material can be glued much better than all other materials and is therefore almost predestined for applications in which a glued structure is used and also offers the possibility of using very high-strength steel grades.

The advantage of the invention is that a steel material is created that has improved heating behavior in the furnace, which allows a shorter residence time in the furnace and thus higher cycle rates.

In addition, the material is less sensitive to hydrogen deposits than normal galvanized material or aluminium-silicon-coated material with a comparable tensile strength, both during austenitizing and in other process steps.

In addition, surprisingly, the thin zinc layer can also ensure the same low coefficients of friction during forming as significantly thicker coatings.

Claims

Expectations

1 . Steel material for the production of high-strength or ultra-high-strength components with a tensile strength R _m > 1600 MPa, in particular > 1800 MPa and in particular > 2000 MPa, the steel material being a boron-manganese steel with a carbon content > 0.30% by mass , wherein the steel material is hot-rolled or hot-rolled and cold-rolled into a strip with a thickness of 0.5 to 3 mm, the strip having a thin coating of zinc or a zinc-based alloy with a coating weight of <50 g/m ² per strip side of the steel strip.

2. Steel material according to claim 1, characterized in that the steel material has the following alloy composition (all figures in % by mass):

The remainder is iron and impurities caused by the smelting process.

3. Steel material according to claim 1 or 2, characterized in that the steel material has the following alloy composition (all figures in % by mass):

Carbon (C) 0.32-0.38 Manganese (Mn) 0.8-1.5 Aluminum (Al) 0.025-0.20 Silicon (Si) 0.01-0.5 Chromium (Cr) 0.01- 0.25 Titanium (Ti) 0.025-0.08 Niobium (Nb) 0.001-0.06 Nitrogen (N) < 0.006 Boron (B) 0.002-0.008 Phosphorus (P) < 0.012 Sulfur (S) < 0.002

Molybdenum (Mo) < 1

The remainder is iron and impurities caused by the smelting process.

4. Steel material according to any one of the preceding claims, characterized in that the steel material satisfies the following condition (in mass %)

(AI - 0.02) / (15.4 * N) + Ti / (3.25 * N) + Nb / (13.3 * N) >= 1

5. Steel material according to one of the preceding claims, characterized in that the coating weight is <45 g/m ² , in particular <40 g/m ² , for each side of the steel strip.

6. Steel material according to one of the preceding claims, characterized in that the coating weight is >20 g/m ² , in particular >30 g/m ² per side of the steel strip.

7. Steel material according to one of the preceding claims, characterized in that the coating of zinc or an alloy based on zinc on the steel strip is converted into a zinc-iron layer by a temperature treatment.

8. A method for producing a steel material according to any one of the preceding claims, characterized in that a melt for a boron-manganese steel with a carbon content> 0.3% by mass is melted and then cast, the slab obtained being hot-rolled or hot-rolled and cold-rolling to obtain a steel strip with a thickness of 0.5 to 3 mm, the steel strip thus obtained being coated with zinc or a zinc-based alloy, the coating having a coating weight of <50 g/m ² per has hinge side.

9. The method according to claim 7, characterized in that the zinc layer is converted into a zinc-iron layer with a proportion of 8 to 18, preferably 10 to 15% by mass of iron by a heat treatment following the galvanizing,

10. The method according to claim 7 or 8, characterized in that the zinc layer is deposited by means of hot-dip coating (hot-dip galvanizing), electrolytic galvanizing or a PVD process. 15 The method according to any one of claims 7 to 9, characterized in that the coating contains zinc as well as other elements such as aluminum, magnesium, nickel, chromium, tin, iron or a mixture thereof, which are deposited together and the sum of these other elements is smaller 25% by mass, preferably less than 15% by mass, particularly preferably less than 5% by mass. Method for producing components, in particular hardened components, from steel material, characterized in that a steel material according to one of Claims 1 to 6 is press-hardened or form-hardened. Method according to Claim 11, characterized in that the steel material is heated to a temperature between 700 and 950°C for the purpose of austenitizing, is optionally maintained at the temperature until it has reached a desired degree of austenitization and is then hardened, the material being either has been completely transformed before heating, or is transformed after heating.