EP4200457A1

EP4200457A1 - Component with integrated aluminum diffusion layer and aluminum oxide layer

Info

Publication number: EP4200457A1
Application number: EP22758146.9A
Authority: EP
Inventors: Ali SOLIMANI
Original assignee: Kamax Holding GmbH and Co KG
Current assignee: Kamax Holding GmbH and Co KG
Priority date: 2021-07-20
Filing date: 2022-07-20
Publication date: 2023-06-28
Also published as: DE102021118766A1; US20240271285A1; MX2024000832A; WO2023001869A1; CN117677727A

Abstract

The invention relates to a component with a part (1) which is made of low-alloy steel and/or heat-treatable steel. The part (1) is at least partly coated with an aluminum diffusion layer (10), and an aluminum oxide layer (14) is applied onto the aluminum diffusion layer (10). The layer thickness of the aluminum diffusion layer (10) equals 1 – 200 µm, and the aluminum diffusion layer (10) has an aluminum content of 10 wt.% above the aluminum content of the steel, based on the total weight of the aluminum diffusion layer, up to a maximum concentration, wherein the aluminum content in the aluminum diffusion layer (10) continuously increases from 10 wt.% to the maximum concentration in the direction of the boundary surface (12) between the aluminum diffusion layer (10) and the aluminum oxide layer (14), said maximum concentration equaling 11 – 60 wt.%.

Description

Component with integrated aluminum diffusion layer and

aluminum oxide layer

The invention relates to a component with a component made of heat-treated steel and/or a low-alloy steel, in which the component is provided with an aluminum diffusion layer and an aluminum oxide layer. In particular, the invention can also relate to a fastener, such as a screw or a nut, which has a component made of heat-treated steel and/or a low-alloy steel, which is provided with an aluminum diffusion layer and an aluminum oxide layer.

Metal components, particularly high-strength and ultra-high-strength components made from heat-treatable and/or low-alloy steel, are susceptible to hydrogen embrittlement. Hydrogen embrittlement is caused by the penetration of hydrogen into the metal structure of the components and leads to the formation of intergranular cracks when the components are stressed. This phenomenon is called hydrogen-induced stress corrosion cracking.

The object of the present invention is to reduce hydrogen embrittlement and thus the tendency to hydrogen-induced stress corrosion cracking in steel components.

This object is achieved with a component with a component made of heat-treated steel and/or a low-alloy steel according to claim 1, with a fastening means according to claim 2, with a manufacturing method a component according to claim 8 and with a use according to claim 11. Further features, embodiments and advantages result from the dependent claims, the description and the figures.

One aspect of the invention relates to a component with a component made of heat-treated steel and/or a low-alloy steel, the component being at least partially coated with an aluminum diffusion layer and an aluminum oxide layer being applied to the aluminum diffusion layer, the layer thickness of the aluminum diffusion layer being 1-200 μm, preferably 2-100 μm, particularly preferably 3-20 μm, the aluminum diffusion layer having an aluminum content, based on the total weight of the aluminum diffusion layer, of 10% by weight above the aluminum content of the steel up to a maximum concentration, the aluminum content in the aluminum diffusion layer being in toward an interface between the aluminum diffusion layer and the aluminum oxide layer from 10% by weight above the aluminum content of the steel to the maximum concentration, and the maximum concentration is 11 - 60% by weight.

Another aspect of the invention can relate to a component with a component made of heat-treated steel and/or a low-alloy steel, the component being a fastener, the component made of steel having and/or forming a threaded area, the component, in particular in the threaded area, at least is partially coated with an aluminum diffusion layer and an aluminum oxide layer is applied to the aluminum diffusion layer, the layer thickness of the aluminum diffusion layer being 1-200 μm, preferably 2-100 μm, the aluminum diffusion layer having an aluminum content, based on the total weight of the aluminum diffusion layer, of 10 wt. -% above the aluminum content of the steel up to a maximum concentration, the aluminum content in the aluminum diffusion layer towards an interface between the aluminum diffusion layer and the aluminum oxide layer being 10% by weight above the aluminum content of the steel increases up to the maximum concentration, and the maximum concentration is 11-60% by weight. The fastener is expediently a screw, in particular a high-strength or even an ultra-high-strength screw, or a nut, in particular a high-strength or even an ultra-high-strength nut.

Another aspect of the invention relates to a method for producing a component with a component made of heat-treated steel and/or a low-alloy steel, comprising the steps: a) providing a component with a component made of heat-treated steel and/or a low-alloy steel, b) applying an aluminum diffusion layer with a layer thickness of 1 - 200 pm on the component at a temperature of 400 to 1100 °C in an inert gas atmosphere, c) heating the component to 700 to 1000 °C in an oxygen-containing atmosphere for at least 10 minutes, creating an aluminum oxide layer on the aluminum diffusion layer is produced.

A further aspect of the invention relates to the use of the component according to the invention to reduce hydrogen embrittlement.

The aluminum diffusion layer according to the invention in combination with the aluminum oxide layer surprisingly acts as a very effective barrier against the penetration of hydrogen by diffusion on components made of heat-treated steel and/or low-alloy steel and thereby increases the resistance of the components to hydrogen-induced stress corrosion. The diffusion process and thus the formation of the aluminum diffusion layer also improves the adhesion of the aluminum layer to the steel, since the aluminum layer grows together with the steel of the component, so to speak.

Especially with fasteners made of low-alloy steels, which usually have or are exposed to high and often dynamic axial stress, reducing hydrogen-induced stress corrosion is particularly advantageous and desirable, because these fasteners, which can be screws or nuts, for example, are essential for many assemblies. For example, the failure of a fastener, in particular a high-strength or ultra-high-strength screw, can have drastic consequences for man or machine, such as an engine head screw, a bridge screw, a cylinder head screw, a chassis screw and/or a battery fastening screw. The invention can therefore also relate to a vehicle, an engine, in particular a cylinder head, a chassis arrangement or a battery arrangement with a component, in particular a fastening means, with the aluminum diffusion layer according to the invention or a building, in particular such as a bridge, or a vehicle.

Advantageously, the steel component is coated with the aluminum diffusion layer in areas of increased stress and/or areas adjacent to areas of increased stress, particularly in areas of a thread, under a head, e.g., a screw, notches or grooves. Areas with an increased notch effect are in particular areas which have a notch effect factor of more than 1.1, preferably more than 1.4, particularly preferably more than 1.9 and most preferably more than 2.1. In an area of a thread, a groove or under a (screw) head or in the transition to the screw head, an area with an increased notch effect within the meaning of the invention can therefore advantageously be seen. Below an area adjacent to an area with an increased notch effect, an area can be seen which is spaced a maximum of 10 mm, preferably a maximum of 5 mm and particularly preferably a maximum of 2 mm, from the area with an increased notch effect. Alternatively, an area adjacent to an area with an increased notch effect can also be present if this is at a maximum distance of 10%, preferably a maximum of 5%, particularly preferably a maximum of 2%, of the largest main dimension of the steel component from the area with an increased notch effect.

All known aluminum coating processes and aluminating processes are suitable for producing the aluminum diffusion layer, provided the processes can be carried out at a temperature in the range from 400 to 1100° C., so that an aluminum diffusion layer can be produced. Those are preferred Hot-dip aluminizing, Chemical Vapor Deposition (CVD) and the slip process. Chemical vapor deposition (CVD) is particularly preferred.

Due to the increased temperature of 400 to 1100 °C in an inert gas atmosphere, the aluminum diffuses into the iron lattice of the steel, which creates the aluminum diffusion layer. In particular, the aluminum can react with the iron to form an intermetallic phase (so-called aluminide phase). Of course, in addition to the iron, any alloying components of the steel also diffuse into the aluminum-containing layer. The aluminum diffusion layer has a concentration gradient in which the aluminum concentration increases toward the surface of the aluminum diffusion layer. After the production of the aluminum oxide layer, this surface is the interface between the aluminum diffusion layer and the aluminum oxide layer. The iron concentration decreases in the same direction. Furthermore, the concentration of any alloying components of the steel decreases in this direction. The surface and/or the interface is in particular that area which delimits the aluminum diffusion layer distally opposite or facing away from the steel component.

In the subsequent heating step of the component in an oxygen-containing atmosphere, the aluminum oxidizes on the surface and forms an aluminum oxide layer on the aluminum diffusion layer (oxidation step). This aluminum oxide layer acts as an additional hydrogen barrier and also serves as protection against corrosion. The surface of the aluminum oxide layer can itself in turn be coated and/or the surface can be, for example, a free surface which is not coated. In other words, the surface can be exposed or covered by a coating and/or by another component.

For the purposes of the invention, the aluminum diffusion layer is defined as the area of the component made of heat-treated steel or low-alloy steel that has an aluminum content, based on the total weight of the aluminum diffusion layer, of 10% by weight above the aluminum content of the steel up to one Maximum concentration, the maximum concentration being 10-60% by weight aluminum. For example, if the steel used does not contain aluminum, the aluminum diffusion layer is the layer that has an aluminum content of 10% by weight up to the maximum concentration of aluminum. In this case, for a steel without aluminum content, the aluminum concentration in the aluminum diffusion layer is between 10 and 60% by weight.

If the steel of the constituent part of the component is an alloyed steel with an aluminum content of, for example, 1% by weight, the aluminum content in the aluminum diffusion layer is 11% by weight up to the maximum concentration. If the maximum concentration at the surface is 60% by weight, the

Aluminum content in the aluminum diffusion layer at 11 - 60% by weight.

The aluminum oxide layer is preferably formed in direct contact with the aluminum diffusion layer. In other words, as already described in particular, there is no further layer between the aluminum oxide layer and the aluminum diffusion layer. Advantageously, at least 90%, particularly preferably at least 95% and particularly preferably at least 99% of the aluminum diffusion layer, or its interface, is covered by the aluminum oxide layer. In this way, a particularly good and extensive shielding of the diffusion layer can be achieved.

A component made of heat-treated steel or low-alloy steel within the meaning of the invention can be understood in particular as meaning that at least part of the component, ie a volume area, is made of heat-treated steel or low-alloy steel. A tempered steel is a steel that is given or has high tensile strength and fatigue strength through tempering, in particular in the form of hardening and/or tempering. It is particularly preferred if the weight of the component consists of at least 80%, preferably at least 90%, and particularly preferably at least 95%, made of heat-treated steel or low-alloy steel or is formed by the component made of heat-treated steel or low-alloy steel. As a result, a particularly good mechanical strength of the component, in particular of the fastening means, can be achieved. Is particularly preferred it to increase mechanical strength when the steel component is in one piece or in multiple pieces. “In one piece” can in particular be understood to mean that at least the one-piece part has been created in a primary shaping process and/or is coherent.

In the context of the invention, “coated” with an aluminum diffusion layer is understood to mean that the component made of steel has an aluminum diffusion layer on the outside in cross section. This means in particular that the component made of steel is bordered in at least one spatial direction by a firmly adhering layer of shapeless material, which is an aluminum diffusion layer. Advantageously, the coating can correspond to DIN 8580 - in particular in the version applicable on May 1, 2021. .

According to the invention, the thickness of the aluminum diffusion layer is 1-200 μm, preferably 2-100 μm, particularly preferably 3-50 μm and most preferably 3-20 μm. The lower thicknesses of the preferred embodiments of the aluminum diffusion layer are advantageous in particular in the case of precisely fitting components. The aluminum oxide layer is preferably applied directly to the aluminum diffusion layer. This means that there is no further layer between the aluminum diffusion layer and the aluminum oxide layer.

The production of the aluminum oxide layer is determined, among other things, by the duration and temperature of the heating step in an oxygen-containing atmosphere (oxidation step). The thickness of the aluminum oxide layer is preferably 1-5000 nm (nanometers), preferably 100-2000 nm, particularly preferably 500-1000 nm. A particularly effective barrier against the penetration of hydrogen and thus a particularly effective reduction in hydrogen embrittlement is achieved with these layer thicknesses.

The "layer thickness" of the aluminum diffusion layer and the aluminum oxide layer is understood to mean the average layer thickness if the upper or lower side is uneven. At least three will do this Measurements of the layer thickness are made, preferably 6 to 8 measurements, and the arithmetic mean of the measured values is determined.

The barrier effect against the penetration of hydrogen is achieved with the present invention through the combination of an aluminum diffusion layer and an aluminum oxide layer. A ratio of the layer thickness of the aluminum diffusion layer to the layer thickness of the aluminum oxide layer of 0.2-2,000,000, more preferably 0.5 to 2000, has proven to be advantageous on the low-alloy and/or heat-treated steel and a durable, barrier and corrosion-resistant aluminum oxide layer.

The maximum concentration of aluminum in the aluminum diffusion layer is 11-60% by weight. Preference is given to 11-50% by weight, particularly preferably 11-35% by weight, more preferably 12-35% by weight, even more preferably 15-35% by weight, in particular 18-30% by weight. These maximum concentrations of aluminum in the aluminum diffusion layer lead to a pronounced formation of iron aluminide phases (FeAl) which are particularly effective in preventing hydrogen embrittlement.

The proportion of aluminum in the aluminum diffusion layer increases towards the interface between the aluminum diffusion layer and the aluminum oxide layer. The increase occurs from 10% by weight above the aluminum content of the steel up to the maximum concentration, for example 11-60% by weight. Preferably, the aluminum content in the

Aluminum diffusion layer perpendicular to the direction of the interface between the aluminum diffusion layer and the aluminum oxide layer. Furthermore, it is preferable that the proportion of aluminum in the aluminum diffusion layer increases perpendicularly in the direction of the interface between the aluminum diffusion layer and the aluminum oxide layer. Intermetallic phases preferably form in the aluminum diffusion layer, which preferably contain intermetallic iron are aluminide phases (FeAl). These are preferably formed by setting the maximum concentration of the aluminum in the aluminum diffusion layer in the preferred ranges, eg 11-50% by weight, particularly preferably 11-35% by weight, more preferably 12-35% by weight more preferably 15-35% by weight, in particular 18-30% by weight, maximum concentration of the aluminum in the aluminum diffusion layer.

In a preferred embodiment of the invention, the control of the Al activity can be adjusted depending on the coating process during the production of the aluminum diffusion layer, eg. Al powder can be mixed with Si in the slurry process in order to reduce the Al activity or in the CVD process the ratio of the so-called pack mixture (filler AI2O3 e.g. 85% by weight, plus activator containing halogen (e.g. 6% ), such as NH4Cl, and e.g. 9% Al powder). These processes lead to increased formation of intermetallic phases, which are preferably intermetallic iron aluminide phases (FeAl).

The aluminum oxide layer can at least partially form the surface of the component. In order to further adapt the surface of the component to the respective application, it is preferable for another layer to be applied to the aluminum oxide layer, preferably selected from a wear protection layer and a sliding layer. Phosphate layers and zinc flakes are preferred, particularly when the component is a fastener, advantageously a screw or a bolt. These layers are particularly advantageous with regard to improving the friction properties.

The steel of the constituent part of the component is a low-alloy steel and/or quenched and tempered steel. In the context of the invention, a low-alloy steel is understood to mean a steel whose total proportion of alloying elements does not exceed 5% by weight, in particular the alloying elements Cr, Mo, V, Ni, Mn, Al, B and Ti, based on the total weight of the steel . The term low-alloy steel within the meaning of the invention thus also includes unalloyed steels and micro-alloyed steels. In the context of the invention, an unalloyed steel is a steel understood, which contains up to 0.8% by weight of carbon and less than 1% by weight of manganese, based on the total weight of the steel.

In a preferred embodiment of the invention, the low-alloy steel of the part of the component, which can also be an unalloyed steel, is preferably a high-strength or ultra-high-strength steel. In particular, it can be a low-alloy, tempered steel. Low-alloy steels can be tempered particularly well and at the same time or alternatively provide a particularly high degree of strength, so that the advantages achieved by the invention, in particular with regard to hydrogen embrittlement, can be used or achieved particularly well here.

In a preferred embodiment of the invention, the microstructure of the steel component in the component is at least predominantly martensitic, bainitic and/or dual-phase (residual austenite, ferrite and/or martensite). The structure of the steel component in the component is preferably at least 80% by weight, in particular at least 90% by weight, martensitic, bainitic and/or dual-phase (residual austenite, ferrite and/or martensite), based in each case on the total weight of the component from steel. This structure gives the component according to the invention particularly high strength and toughness. These structures can be exposed to high and often dynamic axial stress, so that the reduction in hydrogen embrittlement is particularly advantageous for them. The microstructure in the aluminum diffusion layer can differ from the microstructure of the remaining steel component (the so-called base material). The elemental distribution in the aluminum diffusion layer is advantageously characterized by a high concentration of two elements, namely iron and aluminum. Depending on the composition of the steel component, the other alloying elements can be present as dissolved elements or as intermetallic precipitations in the aluminum diffusion layer.

The component according to the invention is preferably a high-strength or ultra-high-strength component, in particular with strengths of more than 1000 MPa above 1200 MPa, more preferably above 1400 MPa and most preferably above 1600 MPa. Preferred high-strength and ultra-high-strength components are high-strength or ultra-high-strength screws or fasteners, springs, leaf springs, plate springs and chain drives, formed components and/or structural components. Further or alternatively preferred is the component according to the invention, in particular the high-strength or ultra-high-strength component, preferably a welded component, an additively manufactured component or a case-hardened component. Particularly in the case of welded components, a high level of hydrogen embrittlement can occur as a result of welding, so that the invention can be used particularly well here. In the case of a case-hardened component, the component is additionally case-hardened for production, in particular by carburizing, nitrating or nitrocarburizing. The component is then provided with the aluminum diffusion layer, as described here.

A formed component is to be understood in particular as a component which has been formed by means of a forming step, in particular a cold forming process. Especially in the case of a formed component, in particular a cold-formed component, it is particularly advantageous to avoid brittleness, in particular hydrogen embrittlement, because a formed component already has a certain degree of brittleness due to the accumulated forest dislocations. A structural component within the meaning of the invention is present in particular when the component is a load-bearing component. This structural component has, in particular, two load introduction sections, which advantageously have load introduction structures, such as mounting recesses or openings, and a transmission area arranged between the load introduction sections, which can transfer a load, in particular a bending load, from one load introduction section to the other load introduction section and/or or transmits. Advantageously, at least one, preferably all, load application sections and/or the transmission area is equipped with the aluminum diffusion layer according to the invention. Forming the component in such a way that the steel has a strength of more than 1000 MPa, preferably more than 1200 MPa, particularly preferably more than 1400 MPa and particularly preferably more than 1600 MPa, is straight particularly advantageous since hydrogen embrittlement is becoming increasingly important in these strength classes, so that the invention can demonstrate its advantages precisely in the case of these strengths.

In a preferred embodiment, the invention relates to a component with a component made of heat-treated steel and/or a low-alloy steel, the component being a fastener, the component having and/or forming a threaded area and/or a shank area, the component at least partially in particular in the thread area and/or shaft area, is coated with an aluminum diffusion layer and an aluminum oxide layer is applied to the aluminum diffusion layer, the layer thickness of the aluminum diffusion layer being 1-200 μm, the aluminum diffusion layer having an aluminum content, based on the total weight of the aluminum diffusion layer, of 10 wt % above the aluminum content of the steel up to a maximum concentration, the aluminum content in the aluminum diffusion layer exceeding 10% by weight towards an interface between the aluminum diffusion layer and the aluminum oxide layer the aluminum content of the steel increases up to the maximum concentration, and the maximum concentration is 11 - 60% by weight, the component being a high-strength or ultra-high-strength component.

The fastening means according to the invention can in particular be non-positive fastening means such as screws, bolts or nuts. Force-locking fastening means are characterized in particular by the fact that they have a threaded section for bracing or fastening, in particular with an external thread or an internal thread. For example, the threaded section can therefore be an external thread or an internal thread. Advantageously, this threaded section is incorporated in a part of the fastener, which is made of steel. In other words, the steel component may have a threaded portion which with the may be coated with the aluminum diffusion layer set forth above and below. In particular, at least three, preferably at least five, and particularly preferably all thread turns of the threaded section are expediently coated with the aluminum diffusion layer. At least the distal end threads are advantageously those threads which are coated with the aluminum diffusion layer. The end threads are, in particular, the threads which form one end of the threaded section or form the end regions of the threaded section or the end of the thread. Alternatively or additionally preferably, the aluminum diffusion layer can also be present in a shaft area. The shank area is in particular an area of the fastening means which lies between the head, in particular the screw head, and the threaded section of the fastening means and mechanically connects them to one another. The shank region can preferably be designed without a thread and/or be designed as a cylindrical section. The diameter of the shank can be less than or equal to the thread diameter in the threaded section. By applying or forming an aluminum diffusion layer--as described above and below--in the shaft area, the mechanical properties of the fastening means can be positively influenced there according to the invention. The screws are advantageously high-strength or ultra-high-strength screws.

The component made of steel in the component according to the invention is at least partially coated with an aluminum diffusion layer, ie the component is partially or completely coated with an aluminum diffusion layer.

In a particularly preferred embodiment of the invention, the component is a high-strength or ultra-high-strength screw. A high-strength bolt is a bolt with a tensile strength of at least 800 MPa. High-strength screws are, for example, screws in strength classes 8.8, 10.9 and 12.9. In particular, the strength classes of the invention correspond to ISO 898-1 in the version valid in January 2021. Among an ultra-high strength bolt, a bolt with tensile strength is particularly important of at least 1200 MPa and/or advantageously of 1400 MPa. Examples of ultra-high-strength screws are screws in strength classes 12.8, 12.9, 14.8, 14.9, 15.8, 15.9, 16.8, 16.9, 17.8 and 12.8U, 12.9U, 14.8U, 14.9U, 15.8U, 15.9U, 16.8U, 17.8U. A high-strength bolt is a bolt that is at least high-strength, but can also be ultra-high-strength. It is preferably a high-strength or ultra-high-strength screw with a strength of more than 1000 MPa. Particular preference is given to the part of the component or screw that has the aluminum diffusion layer, the shank and/or the threaded area of the screw, because it is here that strong dynamic loads occur when the screw is in operation, which makes the screw more vulnerable Increase hydrogen embrittlement, which can be prevented or at least significantly reduced by the invention. The screw can have a head with tool engagement surfaces, these tool engagement surfaces in particular forming an internal or external hexagon with one another. It is particularly preferred if the entire screw is coated with the aluminum diffusion layer.

The invention also relates to a method for producing the component according to the invention. The method according to the invention for producing a component with a component made of heat-treated steel and/or a low-alloy steel comprises the steps: a) providing a component with a component made of heat-treated steel and/or a low-alloy steel, b) applying an aluminum diffusion layer with a layer thickness of 1 - 200 pm on the component at a temperature of 400 to 1100 °C in an inert gas atmosphere, c) heating the component to 700 to 1000 °C in an oxygen-containing atmosphere for at least 10 minutes, whereby an aluminum oxide layer is produced on the aluminum diffusion layer.

The temperature in step b) is preferably 800-1000.degree. In heating step c), heating is preferably carried out for at least 15 minutes, preferably at least 20 minutes and particularly preferably for at least 30 minutes. Further, it is preferred that the heating takes place for 10-600 minutes, more preferably for 15-400 minutes and most preferably for 20-180 minutes. The heating in step c) takes place at 700-1000.degree. C. for the specified periods of time, preferably at 800-1000.degree. C., particularly preferably at 820-980.degree.

The aluminum diffusion layer is preferably applied by applying an aluminum layer which then forms an aluminum diffusion layer at the temperature of step b), preferably a temperature of 400 to 1100° C.

The method according to the invention for producing a component with a component made of heat-treated steel and/or a low-alloy steel thus comprises the steps: a) providing a component with a component made of heat-treated steel and/or a low-alloy steel, b) applying an aluminum layer on the component at a temperature of 400 to 1100 °C in an inert gas atmosphere, with an aluminum diffusion layer with a layer thickness of 1 - 200 pm being formed on the component, c) heating the component to 700 to 1000 °C in an oxygen-containing atmosphere for at least 10 minutes , whereby an aluminum oxide layer is formed on the aluminum diffusion layer.

In the context of the invention, an inert gas atmosphere is understood as meaning an atmosphere of a gas or gas mixture which is inert towards the aluminum of the aluminum diffusion layer. It is preferably a gas atmosphere which contains less than 1% by volume of gases which are reactive towards aluminum, in particular contains less than 1% by volume of oxygen. The inert gas atmosphere particularly preferably comprises more than 99% by volume of nitrogen, hydrogen and/or noble gases, for example argon, argon and nitrogen, or nitrogen and hydrogen, for example nitrogen and 5-10% H2.

A preferred embodiment of the invention relates to a method for producing a component, the component being a high-strength or ultra-high-strength component, comprising the steps of: a) providing a component, the component being a high-strength or ultra-high-strength component, which is a fastener that has and/or forms a threaded area and/or a shank area, with a component made of heat-treated steel and/or a low-alloy steel, b) applying an aluminum diffusion layer with a layer thickness of 1-200 μm to the component, in particular in the threaded area and/or shank area a temperature of 400 to 1100°C in an inert gas atmosphere, c) heating the component to 700 to 1000°C in an oxygen-containing atmosphere for at least 10 minutes, whereby an aluminum oxide layer is produced on the aluminum diffusion layer.

After the heating step c), further steps can follow, in particular an annealing step d). Alternatively or additionally preferably, however, the tempering step can also take place during and/or at the same time or together with the heating step c). In other words, the tempering and the heating/oxidation can be carried out together in one step. As a result, the aluminum oxide layer can be produced particularly quickly and inexpensively. For example, martensitic tempering (preferably by quenching in oil, air and/or water) or bainitising (preferably in a salt bath) can take place. Martensitic quenching or bainitising is carried out under the usual conditions.

The heating step c) can thus be a separately carried out heating step, for example in a furnace, or the heating step can take place during the tempering step of the component, for example at the austenitization of the steel. The heating step preferably takes place during the annealing of the component.

In a preferred embodiment of the invention, the method for producing the component according to the invention therefore comprises the steps: a) providing a component with a component made of heat-treated steel and/or a low-alloy steel, b) applying an aluminum diffusion layer with a layer thickness of 1-200 gm the component at a temperature of 400 to 1100 °C in an inert gas atmosphere, c) heating the component to 700 to 1000 °C while annealing the component in an oxygen-containing atmosphere for at least 10 minutes, thereby producing an aluminum oxide layer on the aluminum diffusion layer.

The above steps a), b) and c) are performed in this order.

The invention also relates to the use of the component according to the invention to avoid or reduce hydrogen embrittlement. The use preferably includes the use of the preferred components described to avoid or reduce hydrogen embrittlement, for example a fastening means with a threaded area and/or shank area. This relates in particular to the reduction or avoidance of hydrogen embrittlement in the component due to hydrogen that can penetrate from the outside, for example when the component is used as intended. This can be the case, for example, when using the component according to the invention, for example a fastener, in a corrosive environment. The aluminum diffusion layer according to the invention in combination with the aluminum oxide layer then particularly effectively protects the component from hydrogen embrittlement by reducing or preventing the penetration of hydrogen into the component. A preferred embodiment of the invention relates to the use of the component according to the invention, in particular the fastening means, in a fuel cell or a battery arrangement. In the case of fuel cells or batteries, a relatively large amount of hydrogen is often produced and here the aluminum diffusion layer according to the invention in combination with the aluminum oxide layer can prevent hydrogen embrittlement with particular advantage.

The invention also relates to a battery arrangement and/or fuel cell, comprising a component according to the invention, in particular a fastening means according to the invention. Here, the advantages described above of avoiding hydrogen embrittlement are achieved particularly effectively due to the relatively high amounts of hydrogen that are produced in battery assemblies or fuel cells.

The advantageous configurations of the method according to the invention described above are also advantageous for this preferred method, in particular the preferred and particularly preferred layer thicknesses, temperatures, heating times and/or advantageous components etc.

Before the heating step c), the microstructure of the steel component can be ferritic, ferritic-pearlitic, bainitic, GKZ annealed or a mixed microstructure. After tempering step d), the microstructure of the component can, in a preferred embodiment, be martensitic, bainitic or ferritic-martensitic or dual-phase (residual austenite, ferrite and/or martensite).

The invention also relates to a component with a component made of steel, obtainable by the method according to the invention. Advantageously, the component and/or the component made of steel can also have the aforementioned features with regard to the method.

It goes without saying that the features mentioned above and those to be explained below can be used not only in the specified combinations, but also in other combinations or on their own, without the leave the scope of the present invention. The stated advantages of features or combinations of several features are only examples and can have an alternative or cumulative effect. The combination of features of different embodiments of the invention or features of different patent claims is possible in deviation from the selected back-references of the patent claims.

Measuring method for determining layer thickness:

The layer thickness of the aluminum diffusion layer is preferably measured with a micrometer, for example using the method according to ASTM C664-10 (as published 2020, Test Method A). For this purpose, the thickness of the component is essentially measured before and after coating with the aluminum diffusion layer, and the layer thickness results from the difference.

The thickness of the aluminum diffusion layer can also be determined by first measuring the thickness of the component after coating with the aluminum diffusion layer. Subsequently, the aluminum diffusion layer is removed, for example by grinding, and the composition of the material is analyzed, for example by chemical analysis of the removed material or chemical analysis of the remaining surface material. For example, wet-chemical methods, atomic force microscopy (AFM) or energy-dispersive X-ray spectroscopy (EDS, EDX, EDXS or XEDS) can be used as analysis methods. Material is removed as long as the removed material has an aluminum content of at least 10% by weight above the aluminum content of the steel, based on the total weight of the aluminum diffusion layer. After removal of the aluminum diffusion layer, the aluminum content of the steel on the surface of the component is just below 10% by weight above the aluminum content of the steel and the thickness of the component is measured again with a micrometer. The difference gives the thickness of the aluminum diffusion layer. Alternatively, the thickness of the aluminum diffusion layer can be determined using the procedure outlined in ASTM C664-10 (as amended in 2020, Test Method B). For this purpose, the layer thickness is essentially determined in the cross section with the aid of an optical microscope. It is also possible to determine the layer thickness of the aluminum diffusion layer in a cross-section using energy-dispersive X-ray spectroscopy (EDS, EDX, EDXS or XEDS). The thickness of the aluminum oxide layer can be determined using scanning electron microscopy.

A component with an aluminum diffusion layer is manufactured by manufacturing the component from the substrate material steel using axial cold forging. The starting material is fed to the forming machine in the form of a coil of wire. The formed product has the geometry of a screw. An aluminum diffusion layer is then applied. After the coating has been applied, the component is heated in an oxygen-containing atmosphere and austenitized for 30 minutes at a temperature of 850°C for tempering.

To set the desired microstructure and the mechanical properties of the component, quenching is carried out immediately after austenitizing. A suitable microstructure is set during the quenching process. Within the diffusion layer, the material produced converts according to its local Al concentration. The resulting component had a tensile strength of 1600 MPa - 1650 MPa.

Experimental assessment of the influence of the aluminum diffusion layer on hydrogen-induced stress corrosion cracking:

The phenomenon of hydrogen-induced stress corrosion cracking in high-strength steel materials generally requires three external influencing factors. These are:

1. Material with a susceptibility to hydrogen-induced stress corrosion cracking 2. Flee mechanical tensile or bending stresses in the component

3. Hydrogen supply in the area

A test setup in which the other two factors are reproduced in a reproducible manner is therefore suitable for evaluating the material behavior with regard to hydrogen-induced stress corrosion cracking. The test setup according to DIN EN ISO 7539-7 is therefore used for the assessment.

The evaluation according to DIN EN ISO 7539-7 Chapter 7.3 according to "Integral of the nominal stress/strain curve" has proven to be particularly precise. In any case, the system consisting of the above-mentioned influencing factors in the state without hydrogen supply in the environment is always compared with the system with hydrogen supply in the environment for characterization. After evaluating the characteristic value of the "integral of the nominal stress/strain curve", a value for the total deformation energy absorbed by the component results for each of the two states. Using the formula

Wßh (deformation energy with H loading) W _Bu (deformation energy without H loading) the so-called FIE value is determined from the two determined deformation energies. The FIE value can range from 0 to 1. A value of FIE=0 means no influence on the material properties, while HE=1 means failure under hydrogen without loading (the latter is a theoretical extreme value and not possible in reality).

To characterize the screws with an integrated aluminum diffusion layer, the reference value without hydrogen exposure W _BU is determined. This is based on the mean of three samples with a

Elongation rate of 0.0067 1/s determined in the instrumented tensile/compression testing machine. The screws according to the invention showed no significant drop in strength after exposure to hydrogen, whereas screws not coated according to the invention showed such a drop.

Further advantages and features of the present invention result from the following description with reference to the figures. Individual features of the illustrated embodiments can also be used in other embodiments, unless this has been expressly excluded. It shows: FIG. 1 a component according to the invention

FIG. 1 shows a component according to the invention. The component has a component 1 made of low-alloy steel and/or heat-treated steel. The component can in particular be a fastener or a spring. The component 1 is at least partially coated with an aluminum diffusion layer 10, the layer thickness of the aluminum diffusion layer being 1 to 200 μm. The arrow in the aluminum diffusion layer 10 in FIG. 1 indicates the decrease in the concentration of aluminum in the aluminum diffusion layer 10 and the direction of thickness, in which the thickness of the aluminum diffusion layer 10 can be determined in particular. On the aluminum diffusion layer 10, an aluminum oxide layer 14 is applied. The aluminum diffusion layer is delimited by the interface 12 between the aluminum diffusion layer 10 and the aluminum oxide layer 14 distally opposite the component 1 made of steel. This surface 16 of the aluminum oxide layer 14 can itself in turn be coated.

Claims

patent claims

Component with a component (1) made of heat-treated steel and/or a low-alloy steel, the component (1) being at least partially coated with an aluminum diffusion layer (10) and an aluminum oxide layer (14) being applied to the aluminum diffusion layer (10), wherein the layer thickness of the aluminum diffusion layer (10) is 1 - 200 gm, the aluminum diffusion layer (10) having an aluminum content, based on the total weight of the aluminum diffusion layer, of 10% by weight above the aluminum content of the steel up to a maximum concentration, the aluminum content being in of the aluminum diffusion layer (10) increases in the direction of an interface (12) between the aluminum diffusion layer (10) and the aluminum oxide layer (14) from 10% by weight above the aluminum content of the steel to the maximum concentration, and the maximum concentration is 11 - 60% by weight amounts to.

Component with a component (1) made of heat-treated steel and/or low-alloy steel, the component being a fastener, the component (1) having and/or forming a threaded area, the component (1) at least partially, in particular in the threaded area , is coated with an aluminum diffusion layer (10) and an aluminum oxide layer (14) is applied to the aluminum diffusion layer (10), the layer thickness of the aluminum diffusion layer (10) being 1-200 gm, the aluminum diffusion layer (10) having an aluminum content, based on the total weight of the aluminum diffusion layer, from 10% by weight above the aluminum content of the steel up to a maximum concentration, the aluminum content in the aluminum diffusion layer (10) towards an interface (12) between the aluminum diffusion layer (10) and the aluminum oxide layer (14) of 10% by weight above the aluminum content of the Steel increases to the maximum concentration, and the maximum concentration is 11-60% by weight.

3. Component according to one of the preceding claims, characterized in that the aluminum oxide layer (14) is applied directly to the aluminum diffusion layer (10).

4. Component according to one of the preceding claims, characterized in that the layer thickness of the aluminum diffusion layer (10) is 2-100 μm and/or the layer thickness of the aluminum oxide layer (14) is 100-2000 nm.

5. Component according to one of the preceding claims, characterized in that the aluminum diffusion layer (10) has intermetallic phases, preferably intermetallic iron aluminide phases (FeAl).

6. Component according to one of the preceding claims, characterized in that the component is a high-strength or ultra-high-strength component, preferably selected from the group consisting of screws, springs, leaf springs, disc springs and chain drives.

7. Component according to one of the preceding claims, characterized in that the low-alloy steel is unalloyed steel.

8. Method for manufacturing a component according to one of the preceding ones

Claims, comprising the steps: a) providing a component with a component (1) made of heat-treated steel and/or a low-alloy steel, b) applying an aluminum diffusion layer (10) with a layer thickness of 1-200 pm on the component (1) at a temperature from 400 to 1100 °C in an inert gas atmosphere, c) heating the component to 700 to 1000°C in an oxygen-containing atmosphere for at least 10 minutes, whereby an aluminum oxide layer (14) is produced on the aluminum diffusion layer (10).

9. The method according to claim 8, characterized in that the heating in

Step c) takes place during the tempering of the component.

10. Component with a component made of steel, in which the component is at least partially coated with an aluminum diffusion layer (10) and an aluminum oxide layer (14) is applied to the aluminum diffusion layer (10), obtainable by a method according to claim 8 or 9.

11. Use of a component according to any one of claims 1 to 7 or 10 for reducing hydrogen embrittlement.

12. Use according to claim 11 in a battery arrangement and/or fuel cell.

13. Battery arrangement or fuel cell, comprising a component, in particular fastening means, according to any one of claims 1-7 or 10.