EP3484632B1 - Substrate with anti-corrosion system - Google Patents

Description

The invention relates to a substrate with an anti-corrosion system, the anti-corrosion system being arranged on the surface of the substrate and a plasma polymer layer with specific lower limits of the modulus of elasticity and specific maxima of the Si 2p peak, and between the substrate and the plasma polymer layer a zone with opposite Substrate enriched anti-corrosion elements includes.

The invention also relates to the use of the corrosion protection system described above to achieve corrosion protection and a method for producing a substrate with a corrosion protection system.

Corrosion protection is an important technical task, because corrosion destroys assets and causes machine downtimes in production processes. Therefore, there are a wide variety of methods to equip surfaces with corrosion-inhibiting properties. These primarily include passive corrosion protection methods such as painting or the use of galvanic methods. Surfaces are, for example, anodised, galvanized, burnished, chromated or phosphated. In the case of stainless steel, for example, attempts are often made to strengthen the passivating surface by using wet-chemical processes (electrochemical processes). In addition to passive corrosion protection methods, there are also some active methods in which, for example, coatings can release corrosion-inhibiting substances in the event of a defect.

Due to special requirements for the anti-corrosion layer, such as good heat transfer in heat exchangers called) or high precision when imaging the surface structure to be protected (edges, embossing, etc.) there is a need for thin-film

Anti-corrosion layers (≤ 10 µm and in particular ≤ 2.5 µm), which change the surface to be protected as little as possible, enable good thermal heat transfer, do not emit any heavy metals and do not subject the entire substrate to excessive heat (≤ 100°C) during coating, in order to thereby not promoting diffusion processes. This requirement can be met, for example, with plasma polymer anti-corrosion layers, which are typically applied in a layer thickness range of 10 to 5000 nm, preferably using a cold process. In addition, the plasma polymer coating process is fundamentally suitable for penetrating narrow structures, such as those often found in heat exchangers, or for maintaining the accuracy of fit of the component. Alternatively, e.g. sol-gel coatings or thin layers of paint can also be selected.

For use in applications such as heat exchangers, materials such as high-alloy stainless steel or titanium are often used to ensure high corrosion resistance to strong acids or alkalis. In exceptional cases, even plastics are used, which, however, involve limitations in heat transfer.

Stainless steels are initially divided into 4 different groups based on their microstructure: austenite, ferrite, duplex and martensite. Stainless steels contain 12 to 26% by weight chromium and 6 to 25% by weight nickel [L. Wegrelius]. Other elements can be added to the steel to modify its properties.

The addition of chromium and molybdenum increases corrosion resistance. In the case of stainless steel, the above quantity is sufficient for a protective layer (passivation) to form under the influence of air and moisture. In general, it can be stated that an increasing chromium and molybdenum content increases the corrosion resistance.

In the application of heavy corrosion protection (corrosion protection classes C5 and C6), it is often no longer possible to use somewhat cheaper materials due to their lack of corrosion stability. Therefore, the task was to identify a coating process that can remedy this deficiency at low cost.

One possibility to modify the surface in order to achieve increased corrosion resistance is laser surface treatment.

In JP01242787 describes how stainless steel or Inconel is machined with a laser to form a corrosion-resistant oxide layer. JP08104949 aims in a similar direction but focuses on austenitic steels.

RU 2287414 and KR 964574 use the effect of laser treatment to achieve a colored design of steel or other metallic materials through oxide formation. The latter application also makes use of the possibility of applying acrylic material or polycarbonate before the laser treatment in order to produce a transparent protective layer.

CN 104911329 uses the laser treatment of stainless steel to generate a super hydrophobic corrosion resistant surface. The surface is processed in such a way that a corresponding microstructure is created in the metal surface.

It is also known that the surface of steel or stainless steel can also be changed by heat treatment. In Birte Kämmerer's dissertation "Dependence of corrosion resistance on the chemical surface composition of chromium steels" (https://opus.bibliothek.uniaugsburg.de/opus4/frontdoor/index/index/docld/2191, library catalogue: opus.bibliothek. uni-augsburg.de) it is shown that the tempering causes more iron to reach the surface. Kämmer summarizes her result as follows: "The corrosion resistance initially decreases with increasing aging temperature, since the iron content in the top layer increases significantly with increasing aging temperature. This trend reaches its extreme at 400°C and leads to a further increase in aging temperature improved corrosion resistance." The goal of creating significantly improved corrosion protection is never achieved in a sufficiently satisfactory manner.

It can thus be stated that it is well known that the corrosion resistance of chromium-containing steels can be changed by specific treatment (heat input). As a rule, heat treatments degrade corrosion resistance.

The surface treatment of metallic materials by means of lasers, in particular with lasers in the near-IR range at λ = 1064 nm, enables a temperature input close to the surface and thus a material modification in the area close to the surface without changing the component more deeply. The temperature input can be so great for a short time (in the ns range) that the entire material or just individual alloy components, depending on the ablation threshold, sublimates directly and is thus removed become. Alternatively, the diffusion of special elements of the alloy to the surface can also be stimulated. The laser interaction depth is typically in the range of a few to a few µm.

Tests show that laser treatment alone increases the corrosion resistance of stainless steel, but it still does not achieve the corrosion resistance desired for the application. For example, a laser-treated stainless steel (1.4404) is still attacked by 25% hydrochloric acid at 35°C. After less than 1 hour, extensive corrosion is already visually recognizable. It is therefore an object of the present invention to provide solutions which can ensure further improved corrosion resistance, in particular for heat exchanger applications.

For many applications, an improvement in the anti-corrosion properties compared to the prior art is desirable. This applies in particular to resistance to the long-term use of strong alkalis and acids in heat exchanger applications. From the EN 102013219337 B3 a plasma polymer anti-corrosion layer is known. Experiments have shown that the anti-corrosion coating described there does not have the desired resistance, for example on alloyed high-grade steel. Rather, the coating quickly detaches from the surface in many areas. Apparently it was not possible to find suitable pre-treatments under the plasma technical boundary conditions (for applying the anti-corrosion layer) in order to build up the layer adhesion sufficiently.

Furthermore describes the DE 102013219331 B3 a plasma-polymer solid, in particular a plasma-polymer layer, which has an extraordinarily high modulus of elasticity for a given C/O ratio. The DE 102013219331 B3 also relates to a solid comprising a substrate and a plasma polymer layer applied to this substrate and the use of a plasma polymer layer as a separating layer in a mold and also the use of such a layer to improve the cleanability of a solid with water.

In the DE 102013210176 B3 primarily describes a method for coating magnesium or a magnesium alloy, in which a surface section (A) of the substrate is heated by means of a laser in an atmosphere containing at least one source of carbon and one source of oxygen, preferably at least CO2, so that a layer (B) containing magnesium oxide and magnesium carbonate is formed on the surface portion (A) of the substrate.

Also describes the DE 102009007100 A1 a flat steel product comprises a metallic coating applied to a base layer of steel material, the main component of the coating being zinc. Three layers are embossed into the metallic coating, two of which are partially alloyed with one another. The coating is optionally coated with a plasma polymer layer.

Finally describes the EP 1722006 A1 describes a process for anticorrosive surface treatment of liquid containers, consisting in depositing at least one anticorrosive layer on the internal surface of a liquid container. At least one anti-corrosion layer is deposited by plasma deposition using the container as a reaction chamber.

It was therefore the object of the invention to describe a way by which it is possible to inexpensively equip stainless steels with corrosion protection that is significantly improved beyond the material class, so that such materials can be used in the area of higher corrosion protection classes. In particular, it was desirable that the anti-corrosion protection according to the invention could be applied to surfaces effectively, over a large area and/or inexpensively. It was particularly preferred that the corrosion-resistant surface according to the invention changes as little as possible in strong acids and alkalis, but that a permanent protective effect can be ensured.

mit

• x = C/O Verhältnis ermittelt mittels XPS
• E = E-Modul [GPa]
• x ≥ 0,5 und ≤ 2,0, bevorzugt x ≥ 0,5 und ≤ 1,8

wobei auf der Oberfläche der Schicht gemessen mittel XPS für das Maximum des Si 2p - Peaks gilt: für E-Modul < 10 GPa: 102,5 - 102,8 eV für E-Modul 10-20 GPa: 102,7 - 103,1 eV und bevorzugt für für E-Modul > 20 GPa: > 103,0 eV
und (ii) zwischen der plasmapolymeren Schicht und dem Substrat eine Zone mit gegenüber dem Substrat angereicherten Korrosionsschutzelementen ausgewählt aus der Gruppe bestehend aus Cr, Mn, Mo, Si und Ti, wobei die Zone mit gegenüber dem Substrat angereicherten Korrosionsschutzelementen durch eine Modifikation des Substratmaterials ohne Hinzufügen weiteren Materials mittels einer Laserbehandlung und/oder mittels Elektronenstrahlbehandlung hergestellt oder herstellbar ist. Folglich stellt die Zone mit angereicherten Korrosionsschutzelementen insbesondere auch eine Zone dar, bei der Elemente wie Fe, C, N, Ni, und P abgereichert sind.This object is achieved by a substrate with an anti-corrosion system, the substrate being made of steel and the anti-corrosion system being arranged on the surface of the substrate and (i) comprising a plasma polymer layer for which the lower limit of the modulus of elasticity of the coating is given by the following function (1) is determined: $$\mathrm{E}=25-31.5*\mathrm{x}+13.5*{\mathrm{x}}^2-1.85*{\mathrm{x}}^3$$

with

• x = C/O ratio determined using XPS
• E = modulus of elasticity [GPa]
• x ≥ 0.5 and ≤ 2.0, preferably x ≥ 0.5 and ≤ 1.8

where on the surface of the layer measured by means of XPS for the maximum of the Si 2p peak applies: for Young's modulus < 10 GPa: 102.5 - 102.8eV for modulus of elasticity 10-20 GPa: 102.7 - 103.1 eV and preferred for for modulus of elasticity > 20 GPa: > 103.0eV
and (ii) between the plasma polymeric layer and the substrate a zone with anti-corrosion elements enriched in relation to the substrate selected from the group consisting of Cr, Mn, Mo, Si and Ti, the zone with anti-corrosion elements enriched in relation to the substrate being formed by a modification of the substrate material without Adding further material is produced or can be produced by means of a laser treatment and/or by means of electron beam treatment. Consequently, the zone with enriched anti-corrosion elements also represents a zone in which elements such as Fe, C, N, Ni and P are depleted.

A "zone of enriched anti-corrosion elements" in the sense of the present text is either a layer with clear layer boundaries to the substrate or the area in which there is a gradient with an increasing concentration of anti-corrosion elements, starting from the concentration of anti-corrosion elements in the substrate. Such a zone is not a plasma polymer layer and is produced or can be produced according to the invention by modifying the substrate material without adding further material.

Anti-corrosion elements within the meaning of the present text are chromium, manganese, molybdenum, silicon and titanium, with preferred anti-corrosion elements being chromium, molybdenum and manganese. Preferably, "enriched compared to the substrate" means that the sum of the anti-corrosion elements is enriched compared to the sum of the anti-corrosion elements in the substrate (amount of substance in each case), preferably by at least ≥ 2 at%, more preferably ≥ 5 at%, based on the sum of the in the substrate or the sum of the elements contained in the transition zone. In case of doubt, the corrosion protection elements enriched in the substrate or in the zone compared to the substrate are determined using EDX, as described in measurement example 3.

Conversely, the reduction of elements susceptible to corrosion, in particular Fe from the zone with enriched anti-corrosion elements, is preferred. "Reduction" is to be understood with the same as well as the same preferred differences as for "enrichment", with the sign converted, of course.

Plasma polymers differ from classic polymers in that during their production, a fragmentation of usually gaseous precursors takes place. Accordingly, in contrast to classical polymers, plasma polymers do not show any regular repetitive subunits, even if - depending on the manufacturing process - a short-range order cannot be ruled out.

The modulus of elasticity of the coating within the meaning of the present invention is determined using the method described in measurement example 1.

In case of doubt, the C/O ratio is determined using XPS (x-ray photoelectron spectroscopy) according to measurement example 2. The same also applies to shifting the maximum of the Si 2p peak.

As already described above, the plasma polymer layer is already known as an anti-corrosion layer, but exhibits insufficient adhesion, particularly when used on steel. For the description of the plasma polymeric layer to be used according to the invention, reference is also made to DE 10 2013 219 337 B3 referred.

Surprisingly, it has now been found that a combination of the aforementioned plasma polymeric layer with an enrichment of the corrosion protection elements mentioned improves the adhesion of the plasma polymeric layer on substrates, in particular on ferrous substrates and especially on stainless steel substrates, to an unexpected extent and thus a synergetic effect within the scope of corrosion protection can be achieved.

The corrosion-increasing effect is also particularly surprising because the plasma polymer layers described and to be used according to the invention are not adequate barrier layers for water molecules or chloride ions. In addition, technical flaws in the coating must always be expected, so that corrosive substances, at least locally, reach the interface between the coating and the substrate.

oder $$\mathrm{\sigma }\left(\mathrm{p}\right)=\mathrm{1,2}$$

je nachdem welcher Wert der Funktionen (2) und (2a) der größere ist,
mit

• σ(p) = polarer Anteil der Oberflächenenergie [mN/m]
• E = E-Modul [GPa]
• für E = 0,75 - 12,4, bevorzugt 1,0 - 12,4, weiter bevorzugt 1,25 - 12,4
  und/oder
• die Oberflächenenergie der Oberfläche der plasmapolymeren Schicht hinsichtlich ihrer Obergrenze durch folgende Funktion (3) bestimmt ist: $$\mathrm{\sigma }=\mathrm{0,9}*\mathrm{E}+\mathrm{21,7}$$
  
• und die Oberflächenenergie der Oberfläche der plasmapolymeren Schicht hinsichtlich ihrer Untergrenze bevorzugt durch folgende Funktion (4) bestimmt ist: $$\mathrm{\sigma }=\mathrm{0,25}*\mathrm{E}+\mathrm{22,25}$$
  
  mit
  • σ = Oberflächenenergie [mN/m]
  • E = E-Modul [GPa].

A substrate according to the invention with an anti-corrosion system is preferred, the maximum polar component of the surface energy of the surface of the plasma polymer layer being determined by the following functions (2) or (2a): $$\mathrm{\sigma }\left(\mathrm{p}\right)=0.28*\mathrm{E}+0.106$$

or $$\mathrm{\sigma }\left(\mathrm{p}\right)=1.2$$

depending on which value of the functions (2) and (2a) is the larger,
with

• σ(p) = polar part of the surface energy [mN/m]
• E = modulus of elasticity [GPa]
• for E = 0.75 - 12.4, preferably 1.0 - 12.4, more preferably 1.25 - 12.4
  and or
• the surface energy of the surface of the plasma polymer layer is determined with regard to its upper limit by the following function (3): $$\mathrm{\sigma }=0.9*\mathrm{E}+21.7$$
  
• and the lower limit of the surface energy of the surface of the plasma polymer layer is preferably determined by the following function (4): $$\mathrm{\sigma }=0.25*\mathrm{E}+22.25$$
  
  with
  • σ = surface energy [mN/m]
  • E = Young's modulus [GPa].

In case of doubt, the surface energy and the polar component of the surface energy are determined according to measurement example 3.

Here, too, it has unexpectedly turned out that the improvement in corrosion protection resulting from the combination according to the invention of corrosion protection elements enriched in relation to the substrate and the plasma polymer layer to be used according to the invention is particularly evident at the surface energies mentioned or the polar components of the surface energies.

To achieve the mentioned surface energies is also on the DE 10 2013 219 337 B3 referred.

Reference is also made to the preferred compositions of the layer to be used according to the invention, which are described in the patent specification mentioned and are hereby incorporated by reference into the present application.

A preferred substrate according to the invention with an anti-corrosion system is one in which the zone with anti-corrosion elements that are enriched in relation to the substrate has an enrichment gradient of the anti-corrosion elements that increases away from the substrate.

Such a substrate or the corresponding zone with anti-corrosion elements enriched in relation to the substrate is accessible via a number of enrichment methods that are to be used with preference (see also below), and on the other hand it allows a particular degree of improvement in adhesion of the plasma polymeric layer to be used according to the invention.

It is a substrate according to the invention with an anti-corrosion system, in which the zone with anti-corrosion elements enriched compared to the substrate is produced or can be produced by means of laser treatment and/or by means of electron beam treatment. According to the invention, methods are presented in which no material is added to produce the enrichment of the anti-corrosion elements.

It is particularly preferred that the zone with anti-corrosion elements enriched compared to the substrate was produced by means of a laser treatment.

Surprisingly, the adhesion behavior of the plasma polymer layer to be used could be significantly improved, in particular by the laser surface modification. The inventors were able to observe, without being bound by this theory, that in the case of steel surfaces in particular, the iron content in ferrous substrates such as steel or stainless steel is significantly reduced by the preferred method for creating a zone with anti-corrosion elements that are enriched compared to the substrate, especially by laser treatment , so that in the case of a chromium-containing steel, for example, a chromium-enriched oxide on the surface remains. It was not foreseeable that such a surface offers such an improved adhesion base compared to the plasma-polymer anti-corrosion layer to be used according to the invention.

More detailed examinations of the laser pre-treatment on (chromium) alloyed stainless steels show a material change of two sizes in particular. While the accumulation of chromium-containing oxides towards the material surface (i.e. away from the substrate) occurs primarily in a layer thickness range of over 10 nm, preferably over 15 nm, particularly preferably in the range of 15 - 20 nm (this then corresponds to the thickness of the zone opposite corrosion protection elements enriched in the substrate) (see Fig. 3a)), only a change in the grain boundary structure of the substrate takes place in a deeper region of a few µm, preferably in a region of up to 2 µm (see Fig. 3b)).

Due to the small thickness of the first zone of a few to several tens of nanometers, the laser-treated surface can have an interference-related color appearance that depends on the layer thickness in this area, the layer composition and the actual substrate material. The additional application of the plasma polymer coating can lead to a further change in the interference color. In a non-limiting example of the invention, the laser treatment according to example 1 below leads to an interference color with a golden to golden brown hue.

• Verwendung eines gepulsten Lasers mit einer Pulsdauer im ns-Bereich und einer Energiedichte auf der Substratoberfläche von mindestens 100 mJ/cm². Bevorzugt wird ein Laser mit einer Wellenlänge im Nahen und Mittleren IR-Bereich (0,7 µm bis 10,6 µm) verwendet, besonders bevorzugt mit einer Wellenlänge von 1064 nm.

In order to carry out laser pretreatments preferred according to the invention, the following is recommended:

• Use of a pulsed laser with a pulse duration in the ns range and an energy density on the substrate surface of at least 100 mJ/cm ² . A laser with a wavelength in the near and middle IR range (0.7 μm to 10.6 μm) is preferably used, particularly preferably with a wavelength of 1064 nm.

An improvement in the corrosion protection within the meaning of the present invention is present at least when the action of strong acids results in a slower surface change compared to the uncoated state, for example due to the formation of corrosion products typical of the alloy. As a quick test, it is preferable to test the coated surface with 25% HCl at 35°C over a period of 15 to 60 minutes and to compare it with an uncoated surface of the same type of material that has been exposed to the same load. An improvement The surface resistance to acids or alkalis is present if the test described shows a surface change slowed down by the coating according to the invention, preferably already visible to the naked eye.

A substrate according to the invention with an anti-corrosion system is preferred, the zone with anti-corrosion elements enriched in relation to the substrate comprising ≧12 atom %, preferably ≧15 atom %, particularly preferably ≧20 atom % of anti-corrosion elements, measured using XPS. (This always means the sum of the above-mentioned anti-corrosion elements, preferably the preferred anti-corrosion elements, based on the total number of atoms recorded with EDX (measurement example 3)).

It is a substrate according to the invention with a corrosion protection system, the substrate consisting of steel and more preferably of stainless steel, preferably measured by EDX (measurement example 3)

Steel in the sense of the present text is a metallic alloy which consists primarily of iron. According to DIN EN 10020:2000-07, the iron alloy has a carbon content of < 2.06% (a limited number of chromium steels can also have a higher carbon content).

According to EN 10020, stainless steel in the sense of this text is a steel with a special degree of purity, eg with a low sulfur and phosphorus content. Alloyed high-grade steels, in particular chromium, chromium-nickel, chromium-molybdenum and titanium steel, are of particular interest, also within the meaning of this application. As an example of such stainless steels the materials X5CrNi18-10, X5CrNiMo17-12-2 and X2CrNiMo17-12-2 should be mentioned.

Preference is given to a substrate according to the invention with a corrosion protection system selected from the group consisting of heat exchangers, heat exchangers, medical devices or tools, fittings for e.g. furniture, vehicles or trailers, pull-out units e.g. for ovens, kitchens or furniture; Decorative and functional elements for means of transport, e.g. decorative strips, railings, components for (sea)water desalination or filtration systems and chemical exhaust air purification, such as housing or piping, components for flue gas systems and seawater use.

Part of the invention is also the use of a corrosion protection system defined above to achieve corrosion protection on a substrate described above, wherein the substrate consists of steel and more preferably stainless steel and more preferably represents one of the types of substrates that are explicitly described above.

1. a) Bereitstellen eines Substrates, wobei das Substrat aus Stahl besteht, bevorzugt wie oben als bevorzugt beschrieben,
2. b) Erzeugen einer Zone mit gegenüber dem Substrat angereicherten Korrosionsschutzelementen, bevorzugt wie weiter oben als bevorzugt definiert, wobei die Zone mit gegenüber dem Substrat angereicherten Korrosionsschutzelementen durch eine Modifikation des Substratmaterials ohne Hinzufügen weiteren Materials mittels einer Laserbehandlung und/oder mittels Elektronenstrahlbehandlung hergestellt oder herstellbar ist, und
3. c) Abscheiden einer wie oben definierten plasmapolymeren Schicht.

Part of the invention is also a method for producing a substrate according to the invention with a corrosion protection system, comprising the steps:

1. a) providing a substrate, wherein the substrate consists of steel, preferably as described above as preferred,
2. b) Creating a zone with anti-corrosion elements enriched in relation to the substrate, preferably as defined above as preferred, the zone with anti-corrosion elements enriched in relation to the substrate being produced or producible by modifying the substrate material without adding further material by means of a laser treatment and/or by means of electron beam treatment , and
3. c) depositing a plasma polymeric layer as defined above.

It is particularly preferred within the meaning of the method according to the invention that one of the preferred treatment variants is used in step b), very particularly that a laser treatment is included or that step b) consists of a laser treatment. The invention is explained in more detail below using examples:

measurement examples Measurement example 1: Young's modulus:

Nanoindentation is a testing technique that uses a fine diamond tip (three-sided pyramid [Berkovich], radius a few 100nm) to measure the hardness of surface coatings can be determined. Contrary to the macroscopic determination of hardness (such as Vickers hardness), the remaining indentation trough imprinted by a normal force is not measured, but a penetration depth-dependent cross-sectional area of the nanoindentor is assumed. This depth-dependent cross-sectional area is determined using a reference sample with a known hardness (usually fused silica).

During the application of the normal force, nanoindentation uses a sensitive deflection sensor (capacitive plates), with which the penetration depth can be precisely measured as the normal force increases and decreases again - quite differently from the classic procedure. The normal force versus indentation depth curve indicates the in situ stiffness of the specimen during the initial phase of unloading. The modulus of elasticity and the hardness of the sample can be determined using the cross-sectional area of the nanoindentor known from the reference sample. The maximum test force for nanoindentation is usually below 15 mN.

A rule of thumb of 10% of the coating thickness is used to measure the pure properties of the coating without being influenced by the substrate. Deeper penetration curves include an influence of the substrate used. With increasing penetration depths of more than 10% of the layer thickness, the measured values for modulus of elasticity and hardness gradually approach those of the substrate. The evaluation described using this measurement method is named after Oliver & Pharr [ WC Oliver, GM Pharr, An improved technique for determining hardness and elastic modulus using load and displacement sensing indentation experiments, J. Material Res. (1992) Vol. 7, No. 6, 1564-1583 ].

The so-called multiple loading and unloading method, or multi-indentation method for short, is used to make it easier to vary the penetration depths for different loads. In this case, debits and credits are made segment by segment at a fixed point. The local maximum loads are continuously increased. In this way, depth-dependent values of the modulus of elasticity and hardness can be determined at the fixed point. In addition, for statistical purposes, various unaffected points on the sample are also approached and tested on a measuring field. By comparing single indentation and multiple indentation methods, Schiffmann & Küster have proven that there are only very small deviations between the values determined by the two methods [ KI Schiffmann, RLA Küster; Comparison of Hardness and Young's Modulus by Single Indentation and Multiple Unloading Indentation. In: Journal of Metallurgy 95 (2004) 5, 311-316 ]. For compensation longer holding times are proposed to prevent creep effects of the piezo scanner [ KI Schiffmann, RLA Küster; Comparison of Hardness and Young's Modulus by Single Indentation and Multiple Unloading Indentation. In: Journal of Metallurgy 95 (2004) 5, 311-316 ].

Accordingly, a maximum of 0.055 mN was measured for samples from exemplary embodiment 2 with 10 multi-indents per point. The multi-indents have local force maxima, which were then reduced to 20% of the force. These unloading curves were evaluated in the form of a 98 to 40% tangent. 10 measurement points were tested for statistics and homogeneity. The distance between the measuring points was 50 µm in order to avoid influences such as plastic deformation of the layer to be tested due to previous measurements. The layer thickness was 1839 nm. To comply with the rule of thumb for the penetration depth of max. 10% of the layer thickness, the relief curves for the multi-indents in the example shown are permissible for the evaluation up to a maximum force of 0.055 mN. In the case of lower layer thicknesses, the associated max. local force must be observed in order not to exceed the 10% rule.

A Universal Material Tester (UMT) with Nano-Head (NH2) nano-indentation module from CETR (now under Bruker AXS S.A.S.) with appropriate vibration damping technology (minus k) was used in a thermal and acoustic insulation chamber for the nano-indentation of the exemplary embodiments.

According to the multi-indentation method, for example, samples which were produced according to exemplary embodiment 1 were measured with 10 multi-indents per point with a maximum of 0.055 mN. The multi-indents have local force maxima, which were then reduced to 20% of the force. These unloading curves were evaluated in the form of a 98 to 40% tangent. 10 measurement points were tested for statistics and homogeneity. The distance between the measuring points was 50 µm in order to avoid influences such as plastic deformation of the layer to be tested due to previous measurements. The layer thickness was 2017 nm. To comply with the rule of thumb for the penetration depth of max. 10% of the layer thickness, the relief curves for the multi-indents in the example shown are permissible for the evaluation up to a maximum force of 0.055 mN. In the case of lower layer thicknesses, the associated max. local force must be observed in order not to exceed the 10% rule.

The maximum force for the penetration depth and the corresponding relief curve is ≦0.055 mN here in case of doubt, it is preferably ≦0.020 mN with layer thicknesses of ≦1000 nm in case of doubt.

Measurement example 2: XPS measurements:

The XPS measurements are used to determine substance amount ratios for the layers according to the invention. To do this, proceed as follows:
The XPS investigations were carried out with a VG 220i-XL system (from VG Scienta). Parameters: Magnetic lens mode, acceptance angle of the photoelectrons 0°, monochromatized AIK _α excitation, constant analyzer energy mode (CAE) with 70 eV pass energy in overview spectra and 20 eV in energetically high-resolution line spectra, analysis area: 0.65 mm ø, the neutralization of electrical non-conductive samples is done with low-energy electrons (4 eV). The detection sensitivity of the method is element-specific and is around 0.1 at%, ie around 1000 ppm. To compensate for charging effects, the C1s main photoemission line to be assigned to the CC species is set to 285 eV in the evaluation, which means that the positions of the other photolines shift accordingly.

The XPS spectrometer was set up in accordance with ASTM standard E902-94. ASTM standard E 1078 - 90 was used with regard to sample handling before and during analysis. The ASTM E 996-94 and E995-95 standards were used to process the measurement data obtained. Applicable documents are the references named in the standards.

With the help of this procedure, both the elementary compositions and the Si 2p peak shifts are obtained (see Fig 1 ) as shown in Table 1.

Measurement example 3: surface energy:

The surface energy is determined in accordance with DIN 55660-2 of December 2011 using a G2 contact angle measuring device from Krüss. Water, diiodomethane and ethylene glycol with a high degree of purity are used as test liquids. The test liquids have the following characteristics: Water surface energy: 72.8 mN/m, polar component: 51.0 mN/m diiodomethane surface energy: 50.8 mN/m, polar part: 0.0 mN/m ethylene glycol surface energy: 47.7 mN/m, polar part: 16.8 mN/m

The measuring method used is the dynamic measurement (advancing contact angle), in which the contact angle is determined during the liquid supply. In case of doubt, the baseline is set manually, horizontally in the middle between the tip of the syringe and the mirror image. The needle spacing is set to approx. 2 mm. Before the measurement, the surface is cleaned with acetone if necessary (one time very light wiping with acetone and a lint-free cloth) to reduce the risk of incorrect measurements.

The amount of test liquid used is 6 µl with a dosing rate of 11.76 µl/min. The actual measurement starts after 5 s, this corresponds to a feed volume of approx. 1 µl. 3 drops are applied per liquid. The respective results are averaged.

The evaluation of the contact angle as well as the surface energy and the polar component of the surface energy was carried out using the software "Drop Shape Analysis (DSA) for Windows" (Version 1.91.0.2) from the Krüss company. Polynomial method 2 was used to determine the contact angle. The evaluation for surface energies up to 30 mN/m was based on Wu [ S. Wu, Calculation of interfacial tension in polymer systems, Journal of Polymer Science, Part C: Polymer Symposia (1971), Vol. 34, Issue 1, 19-30 ] and for surface energies above 30 mN/m according to Owens-Wendt-Rabel-Kaelble. The evaluation was carried out without error weighting.

The values given in Table 1 for the surface energy and its polar component were obtained.

This deficiency could be remedied by the laser surface modification according to the invention. This significantly reduces the iron content in the steel surface, so that essentially in the case of chromium-containing steel, a chromium-enriched oxide remains. Surprisingly, such a surface provides a much better adhesion base for a plasma-polymer anti-corrosion layer DE102013219337B3 This makes it possible to combine the laser pre-treatment with a plasma polymer anti-corrosion layer with regard to the anti-corrosion effect.

Measurement example 4: EDX measurement:

Energy dispersive X-ray spectroscopy (EDX) is a method for elementary material characterization. The sample to be examined is energetically excited by means of a primary electron beam of uniform energy. The sample relaxes by element-specific X-ray radiation is emitted, which can be analyzed with a suitable detector.

The element analysis typically takes place from an atomic number of 6 (carbon), so that organic substances can be identified. However, quantitative statements with a small error can be difficult for light elements. The reason for this lies in a thin protective layer ("window") in front of the EDX detector, which ensures that the necessary vacuum is maintained in the detector, even if the sample chamber is ventilated (such as in a scanning electron microscope when changing samples). Unfortunately, however, this protective layer absorbs the low-energy X-rays from light elements, making quantification difficult. Depending on the window material used, elements from atomic number 11 (sodium, beryllium windows) or 6 (C, polymer-based thin windows) can be detected and analyzed. In systems in which the sample space is not ventilated (e.g. in a transmission electron microscope), windowless detectors can also be used and even elements up to atomic number 3 (lithium) can be examined.

However, spatially resolved measurements (with a lateral resolution of up to 1-2 nm) are only possible if the primary electron beam is sufficiently focused and the sample to be examined is prepared so thinly that the propagation of the primary electron beam in the sample is from the focal point outgoing is largely suppressed. The second point is important because X-rays are emitted from the entire propagation area of the electron beam in the sample (so-called excitation bulb). The shape and characteristics of this excitation bulb depend primarily on the energy of the primary electrons (the higher, the more extended and deeper) and the sample thickness (the thicker, the better the excitation bulb can develop fully) of the sample. Very thin samples that are examined with high primary electron energy are ideal. These two requirements are met, for example, when examining samples in the transmission electron microscope (TEM). Here, the sample thickness is usually less than 100nm, which prevents the excitation bulb from spreading, and the energy of the primary electron beam is several hundred keV, resulting in the primary electron beam hardly expanding when passing through the sample. Investigations in a scanning electron microscope (SEM), on the other hand, have the problem that thick samples with lower primary electron energy are usually examined here. The low energy of the electrons causes the primary electron beam to rapidly fan out below the sample surface, and the thickness of the sample allows the excitation bulb to fully express itself. At a typical primary electron energy in the SEM of 20keV, the expansion of the excitation bulb can be roughly estimated at 1µm in all spatial directions (analytical resolution) regardless of whether the primary electron beam was focused to 1nm for the analysis (typical resolution of modern SEMs). The expansion of the excitation bulb thus blurs the lateral resolution of the SEM.

In this measurement example, a sample thin section (a TEM lamella) with a final sample thickness of less than 100 nm is first produced using the focused ion beam method (FIB). In order to preserve the actual surface quality and chemistry, a protective layer of carbon and platinum is first applied in the corresponding area using EBID ("electron beam induced deposition") and IBID ("ion beam induced deposition").

This is followed by the EDX examination in the TEM. In this case, a Tecnai TF-20 S-Twin G ² transmission electron microscope from FEI (Hillsboro, Oregon) was used. The microscope was used in the raster mode STEM ("scanning transmission electron microscopy") with a spot size of about 1-2nm. The detector used was an EDAX r-TEM EDX detector with S-UTW window ("super ultrathin window"), the resolution of which is 136eV.

The Figure 4a represents a line profile on the surface of an electropolished 1.4404 steel surface (after laser treatment). The starting point (position 0 nm) is marked with a cross in the STEM image in FIG Figure 4a marked.

Figure 4b and 4c represent the measurement results.

A line profile created using EDX measurements (see Figure 4a ) of an electropolished 1.4404 steel sample before laser treatment shows only a thin oxide layer directly on the surface (approx. 5 nm, dark area in the middle of the Figure 4a ). In deeper layers (from the surface about 70 nm into the bulk material, to the left) the iron content decreases slightly to about 40 at-%, while the carbon content increases to about 30 at-%. Above the oxide layer there is a clear increase in the carbon and platinum signals, which can be attributed to the protective layer required for the FIB preparation.

In contrast, the sample that was additionally subjected to a laser treatment with parameter 2 from exemplary embodiment 1 shows significant changes. The oxide layer thickness has increased to approx. 16 nm as a result of the treatment. located in the oxide almost no iron, no molybdenum, no silicon and no nickel (only in the bulk area) anymore. In contrast, chromium and manganese are significantly enriched together with oxygen. Corresponding oxides have formed. These promote the corrosion stability and the adhesion of the subsequently applied plasma polymer coating.

The Figure 5a represents a line profile on the surface of an electropolished 1.4404 steel surface (after laser treatment). The starting point (position 0 nm) is marked with a cross in the Figure 5a marked.

The Figure 5b and 5c represent the measurement results.

In case of doubt, proportions of elements are always determined as in this measurement example.

exemplary embodiments Example 1:

The stainless steel used (X2CrNiMo17-12-2; 1.4404, V4A) is one of the common corrosion-resistant types of stainless steel. Due to its molybdenum content, it is characterized by high resistance to non-oxidizing acids and media containing halogens. In addition, this material is easy to process and can be used at temperatures of up to 550°C. In terms of corrosion resistance (especially in the presence of chlorides), this material is also significantly better than, for example, the frequently used stainless steel X5CrNi18-10, 1.4301 (V2A) due to the addition of molybdenum.

In natural environmental media and industrial areas with moderate chlorine and salt concentrations, as well as in the food and pharmaceutical industries, 1.4404 stainless steel shows excellent corrosion resistance. Due to the low carbon content, the material is resistant to intergranular corrosion according to DIN EN ISO 3651 Part 2.

However, stainless steel 1.4404 is not seawater resistant. It is therefore initially unsuitable for high-end corrosion protection applications. This is confirmed by the following Table 1 with laboratory tests (optimal specimen) from the manufacturer Deutsche Edelstahlwerke. [Material data sheet Acidur 4404 from Deutsche Edelstahlwerke, 16/10/2015 2015-0016] Table 1: Corrosion properties of 1.4404 means of attack concentration temperature resistance NaCl Saturated 20°C Danger of pitting corrosion seawater Saturated 20°C Danger of pitting corrosion Steam 400°C resistant nitric acid 7% 20°C resistant sulfuric acid 1% 20°C resistant formic acid 10% 20°C resistant

According to the invention, the material is first subjected to a laser treatment, with it being proposed, but not prescribed, for further surface optimization to first smooth the workpiece surface by means of electropolishing. This can generally be preferred within the meaning of the invention.

A CL250 device from Clean-Lasersysteme GmbH with a power of the beam source of 250 W is used for the laser treatment. The diode-pumped Nd:YAG laser (short for neodymium-doped yttrium-aluminum-garnet as active medium) emits infrared radiation with a wavelength of 1064 nm kHz and minimum pulse lengths of 80 to 200 ns. The resulting maximum pulse energy of this system is 21 mJ.

• Parameter 1: Leistung: 250 W, Pulsfolgefrequenz: 12 kHz, Pulsdauer: 100 ns, scannend in x-Richtung, Scangeschwindigkeit: 2050 mm/s, Überlapp: 75 %, Fluenz: 5 J/cm², Wiederholungen: 2
• Parameter 2: Leistung: 165 W, Pulsfolgefrequenz: 12 kHz, Pulsdauer: 100 ns, Scangeschwindigkeit: 2050 mm/s, Überlapp: 75 %, Fluenz: 3,8 J/cm², Wiederholungen: 2, scannend jeweils in x- und y-Richtung

The laser parameters used were:

• Parameter 1: Power: 250 W, pulse repetition frequency: 12 kHz, pulse duration: 100 ns, scanning in x-direction, scanning speed: 2050 mm/s, overlap: 75 %, fluence: 5 J/cm ² , repetitions: 2
• Parameter 2: Power: 165 W, pulse repetition frequency: 12 kHz, pulse duration: 100 ns, scanning speed: 2050 mm/s, overlap: 75%, fluence: 3.8 J/cm ² , repetitions: 2, scanning in x and y direction

The samples, which had changed color as a result of the laser treatment (slight gold colouration), were then reapplied with a plasma polymer anti-corrosion layer to be used according to the invention DE102013219337 Mistake. A plasma polymerisation system with a volume of approx. 1m ³ was used for this purpose. The system is characterized by its large electrode area of approx. 3m ² , which corresponds approximately to the area of the electrical ground. The samples were placed in radio frequency contact with the electrode. A working pressure of 0.018 mbar was set in the system with the working gases hexamethyldisiloxane and oxygen, after the surface had been pre-cleaned with pure oxygen. A radio frequency power of 1200 W was coupled into the electrodes. The gases were used in a 2:1 ratio for a total of 135 sccm. The layer thickness produced was 0.55 μm, the modulus of elasticity 1.3 GPa, the surface energy 23.5 mN/m with a polar component according to Wu of 0.85 mN/m.

The effectiveness of the anti-corrosion layer was checked by a test over a period of up to 16 hours in 25% hydrochloric acid at 35°C. This test did not allow to distinguish between the laser parameters 1 + 2. The results are presented in Table 2 and therefore do not differentiate the laser treatments: Table 2: Corrosion result after HCl test according to processing condition editing corrosion pattern without, only electropolished Extensive corrosion attack after just 0.5 hours. laser treated Slight surface corrosion attack already after 1 hour. plasma coated Spontaneous layer detachment in large areas. Areas with residual coating without findings, otherwise extensive corrosion attack. Laser treated and plasma coated No corrosive attack and no layer detachment recognizable. Very few technical flaws with pitting corrosion, without layer infiltration after 16 hours.

Example 2:

For a further test of the effectiveness of the anti-corrosion layer, a stainless steel 1.4404 is subjected to a laser treatment in accordance with example 1. A CL100 device from Clean-Lasersysteme GmbH with a power of the beam source of 100 W is used for the laser treatment. The diode-pumped Nd:AG laser emits laser radiation with a wavelength of 1064 nm, a pulse repetition frequency of 100 to 200 kHz and a pulse length of 80 ns (with a pulse energy of 1 mJ). The resulting maximum pulse energy of the system is 12.7 J/cm ² .

• Parameter 3: Leistung: 20 W; Pulsfolgefrequenz: 200 kHz; Pulsdauer: ~ 100 ns; Scangeschwindigkeit: 2000 mm/s; Überlapp: 90 %; Fluenz: 1,3 J/cm²; Wiederholungen 3
• Parameter 4: Leistung: 25 W; Pulsfolgefrequenz: 200 kHz; Pulsdauer: ~100 ns; Scangeschwindigkeit: 2500 mm/s; Überlapp: 87,5; Fluenz: 1,6 J/cm²; Wiederholungen 8
• Parameter 5: Leistung: 30 W; Pulsfolgefrequenz: 200 kHz; Pulsdauer: ~100 ns; Scangeschwindigkeit: 3000 mm/s; Überlapp: 85 %; Fluenz: 1,9 J/cm²; Wiederholungen 8

The laser parameters used were:

• Parameter 3: Power: 20W; pulse repetition frequency: 200 kHz; pulse duration: ~ 100 ns; Scan speed: 2000mm/s; overlap: 90%; Fluence: 1.3 J/cm ² ; repetitions 3
• Parameter 4: Power: 25W; pulse repetition frequency: 200 kHz; pulse duration: ~100 ns; Scan speed: 2500mm/s; Overlap: 87.5; Fluence: 1.6 J/cm ² ; repetitions 8
• Parameter 5: Power: 30W; pulse repetition frequency: 200 kHz; pulse duration: ~100 ns; Scan speed: 3000mm/s; overlap: 85%; Fluence: 1.9 J/cm ² ; repetitions 8

Subsequently, the samples whose color had changed as a result of the laser treatment (predominantly bluish for parameter 3/golden to golden brown coloration for parameters 4 and 5) were reapplied with a plasma polymer anti-corrosion layer to be used according to the invention DE102013219337 provided (according to the procedure described and the coating in Example 1). The layer thickness produced was 0.55 μm, the modulus of elasticity 1.3 GPa, the surface energy 23.5 mN/m with a polar component according to Wu of 0.85 mN/m.

The effectiveness of the anti-corrosion layer was tested by means of a test over a period of 2 hours in a 35° C., 30% solution of iron(III) chloride hexahydrate (FeCl ₃ *6H ₂ O) in water. In this case, an untreated stainless steel sample was used as a comparison. The optical and microscopic characterization of the individual samples allowed the effectiveness of the different laser parameters to be characterized (Table 3). Table 3: Corrosion result after HCl test according to processing condition editing corrosion pattern without, only electropolished Severe pitting corrosion after only a short exposure time (deep holes) Laser treated: parameter 3 Local, small pitting corrosion with resulting layer under-migration Laser treated: Parameter 4: Larger number of strongly localized corrosion attacks with little evidence of strata infiltration Laser treated: parameter 5 No corrosive attack and no layer detachment recognizable. Very few technical flaws with pitting corrosion

Example 3:

In this example, energy dispersive X-ray spectroscopy (EDX) was carried out in cross section on TEM lamellae (TEM: transmission electron microscope) produced by means of the preparation with a focused ion beam (FIB). Due to the small sample thickness, this analysis allows the layer structure in the surface area to be determined with a spatial resolution of approx. 1.5 nanometers (nm).

First of all, the elemental composition was determined at different points near the surface, with the oxygen content decreasing with increasing distance from the surface.

Stainless steel 1.4404 electropolished

Table 4 in at% Area C O si Cr Mn feet no Mon 1 0.0 10.3 0.8 16.3 1.4 62.0 8.4 0.8 2 0.0 9.6 0.7 16.9 1.5 61.7 8.7 1.0 3 0.0 8.7 0.3 17.1 1.6 62.6 8.7 0.9 Average 0.0 9.5 0.6 16.7 1.5 62.1 8.6 0.9

The further investigations showed, cf. Fig. 1a ) - b) that the surface of the only electropolished sample is provided with a very thin oxide layer (approx. 5 nm). Otherwise, the iron content drops slightly in the subsequent, approx. 70 nm thick layer to about 40 at-%, whereas the carbon content increases accordingly to about 30 at-%.

In contrast, the sample that was additionally subjected to the laser treatment shows changes (cf. Figure 2a ) - c.)).

The oxide layer thickness has increased to approx. 16 nm as a result of the treatment. The oxide contains almost no iron, no molybdenum, no silicon and no nickel (only in the near-bulk area). In contrast, chromium and manganese are significantly enriched together with oxygen. Corresponding oxides have formed. These promote the corrosion stability and apparently also the adhesion of the plasma polymer layer to be used.

Example 4:

In this example, various surfaces of stainless steel 1.4404 (electropolished; electropolished and laser-treated as in example 1 and example 3, electropolished and laser-treated (parameters 1 and 2)) were examined using XPS spectroscopy. The surface composition was as follows (Table 5): Table 5: XPS surface composition of differently treated surfaces of the material 1.4404 Electropolished Laser treatment parameters 2 Laser treatment parameters 1 elements at-% at-% at-% no 1.6 0.0 0.0 feet 9.3 3.3 3.3 Mn 0.0 4.1 3.0 Cr 10.0 18.1 20.5 O 39.4 50.8 50.8 N 5.4 0.4 0.4 Approx 1.5 0.2 0.3 C 30.0 14.9 16.4 Mon 0.7 0.0 0.0 S 0.2 0.3 0.2 P 1.3 0.0 0.0 si 0.5 7.9 5.0 pb 0.1 0.0 0.0

As was to be expected on the basis of the EDX investigations, an increase in the chromium and manganese content can also be seen here, with a more powerful laser treatment (Parameter 1) further increases the chromium content. However, there are also differences to the EDX examination, since only the top 10 nm are examined using XPS. The surface has a reduced nickel and carbon content, but an increased silicon content. According to the invention, the iron content is significantly reduced for both laser settings.

The examination of the individual element peaks shows that there are almost no more metallic atoms, but that the laser treatment has increased the ratio of chromium + manganese oxide to iron and iron oxide from around 2.6 to 6.7 (parameter 2 treatment) or 7 ,1 for the parameters 1 treatment changed.

The result can be interpreted in such a way that the laser treatment in particular reduces the proportion of iron, nickel and molybdenum close to the surface. At the same time, the remaining elements (particularly chromium and manganese) are oxidized. The oxide layer thickness increases significantly. Since the heat input is very low and is only limited to the surface, no iron migrates from the bulk area. There is a clear depletion of iron oxide near the surface.

Claims (10)

1. Substrate having an anticorrosion system, wherein the substrate consists of steel and the anticorrosion system is disposed on the surface of the substrate and (i) comprises a plasma-polymeric layer for which the lower limit of the modulus of elasticity of the coating is determined by the following function (1): $$\mathrm{E}=25-31.5*\mathrm{x}+13.5*{\mathrm{x}}^2-1.85*{\mathrm{x}}^3$$

   

   with

   x = C/O ratio ascertained by XPS

   E = modulus of elasticity [GPa]

   for x ≥ 0.5 and ≤ 2.0

   wherein the maximum of the Si 2p peak on the surface of the layer measured by XPS is as follows: for modulus of elasticity < 10 GPa: 102.5-102.8 eV for modulus of elasticity 10-20 GPa: 102.7-103.1 eV and preferably for modulus of elasticity > 20 GPa: > 103.0 eV, characterized in that
   (ii) there is a zone between the plasma-polymeric layer and the substrate that comprises anticorrosion elements enriched relative to the substrate and selected from the group consisting of Cr, Ni, Mo, Mn, Nb, Cu, Si and Ti, where the zone having anticorrosion elements enriched relative to the substrate is produced or producible by a modification of the substrate material without addition of further material by means of a laser treatment and/or by means of electron beam treatment.
2. Substrate having an anticorrosion system according to Claim 1, wherein the maximum polar component of the surface energy of the surface of the plasma-polymeric layer is determined by the following functions (2) or (2a) : $$\mathrm{\sigma }\left(\mathrm{p}\right)=0.28*\mathrm{E}+0.106$$

   

   or $$\mathrm{\sigma }\left(\mathrm{p}\right)=1.2$$

   

   according to which value of the functions (2) and (2a) is the greater,
   with

   σ(p) = polar component of surface energy [mN/m]

   E = modulus of elasticity [GPa]

   for E = 0.75-12.4
   and/or

   the surface energy of the surface of the plasma-polymeric layer, with regard to its upper limit, is determined by the following function (3): $$\mathrm{\sigma }=0.9*\mathrm{E}+21.7$$

   

   and the surface energy of the surface of the plasma-polymeric layer, with regard to its lower limit, is preferably determined by the following function (4): $$\mathrm{\sigma }=0.25*\mathrm{E}+22.25$$

   

   with

   σ = surface energy [mN/m]

   E = modulus of elasticity [GPa].
3. Substrate having an anticorrosion system according to Claim 1 or 2, wherein the zone having anticorrosion elements enriched relative to the substrate has a rising enrichment gradient of the anticorrosion elements moving away from the substrate.
4. Substrate having an anticorrosion system according to Claim 3, wherein the zone having anticorrosion elements enriched relative to the substrate is produced or producible by means of a laser treatment.
5. Substrate having an anticorrosion system according to any of the preceding claims, wherein the zone having anticorrosion elements enriched relative to the substrate comprises ≥ 12 atom%, preferably ≥ 15 atom%, more preferably ≥ 20 atom%, of anticorrosion elements, measured by XPS.
6. Substrate having an anticorrosion system according to any of the preceding claims, wherein the substrate consists of stainless steel.
7. Substrate having an anticorrosion system according to any of the preceding claims, selected from the group consisting of heat exchanger, heat transferrer, automobile wheel rim, medical device or tool, coating for furniture, pull-out unit, for example for baking ovens, kitchens or furniture; decorative and functional elements for modes of transport, for example decorative strips, guardrails, components for (sea)water desalination or filtration plants and chemical output air cleaning, for example housings or pipework, components for flue gas systems and use in seawater.
8. Use of an anticorrosion system as defined in any of Claims 1 to 5 for achieving protection from corrosion for a substrate according to any of Claims 1, 6 and 7.
9. Method of producing a substrate having an anticorrosion system according to any of Claims 1 to 7, comprising the steps of:

   a) providing a substrate, where the substrate consists of steel,

   b) generating a zone having anticorrosion elements enriched relative to the substrate as defined in any of Claims 1 or 3 to 5, where the zone having anticorrosion elements enriched relative to the substrate is produced or producible by a modification of the substrate material without addition of further material by means of a laser treatment and/or by means of electron beam treatment, and

   c) depositing a plasma-polymeric layer as defined in either of Claims 1 and 2.
10. Method according to Claim 9, wherein step b) comprises or consists of a laser treatment.

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