DE102018009263A1 - Nanocontainer-containing coating for a body part, and body part with such a coating - Google Patents

Abstract

The invention relates to a coating (1) containing a nanocontainer (7) for a body part (3), the coating having a metal matrix (5), the metal matrix (5) having at least one element selected from the group consisting of Al, Co , Fe, Mg, Mn, Ni and Zn, characterized in that the coating has nanocontainers (7), the nanocontainers (7) being coated with at least one layer of at least one polymer, the at least one polymer being impregnated with at least one corrosion inhibitor , the proportion of the nanocontainers (7) in the coating (1) being at most 20% by weight, the proportion of the metal matrix (5) in the coating (1) being at least 70% by weight, and the nanocontainers (7) are embedded in the metal matrix (5).

Description

The invention relates to a nanocontainer-containing coating for a body part, and a body part with such a coating.

To improve the durability of body parts, in particular body parts made of steel, the body parts are provided with a corrosion protection coating for both cold formability and hot formability. In order to increase the corrosion resistance of body parts, in particular to ensure good corrosion protection properties, body parts are usually coated with a metallic coating. Hot-dip galvanized or electrolytically galvanized coatings have established themselves for body parts. These coatings offer cathodic corrosion protection due to the low corrosion potential based on a zinc-based layer compared to body parts without such a layer. In addition, such coatings can achieve good properties for the subsequent painting and joining processes. The advantage of zinc-based corrosion protection coatings is that they not only have a barrier effect, but also offer active corrosion protection for the body part. The coating behaves as a sacrificial anode and dissolves in front of the body part, since the corrosion potential of the coating is lower than that of the body part. However, zinc-based corrosion protection coatings also have disadvantages; For example, in the case of direct press hardening of zinc-based corrosion protection coatings, it is known that macro and micro cracks can occur due to liquid metal embrittlement (LME).

Numerous zinc alloys for coatings are known, for example from zinc-nickel, zinc-manganese, zinc-iron, zinc-aluminum, zinc-magnesium and zinc-aluminum-magnesium, which have better properties than pure zinc coatings.

Zinc-iron coatings, however, have only a low resistance to corrosion, since the corrosion potential of zinc-iron coatings is increased compared to pure zinc. Furthermore, the high iron content in the coating leads to higher risks of red rust formation on the surface of the coating, which affects the optical quality and also the long-term corrosion resistance of the body part. In the case of zinc-magnesium and zinc-aluminum-magnesium coatings, advantageous corrosion protection properties can be expected because of the formation of particularly stable corrosion products.

It is also known to adapt the properties of a component by using non-metallic components, for example by using polymers.

The German publication DE 10 2015 113 677 A1 discloses a metal matrix composite and a method for additively manufacturing a component from the metal matrix composite, wherein a metal powder is connected to filaments by melting.

The invention is therefore based on the object of providing a coating containing a nanocontainer for a body part, and a body part with such a coating, the disadvantages mentioned not occurring, and in particular an increase in corrosion protection being achieved.

The object is achieved by creating the subject matter of the independent claims. Advantageous refinements result from the subclaims.

The object is achieved in particular by creating a coating containing a nanocontainer for a body part, the coating having a metal matrix, the metal matrix having at least one element selected from the group consisting of Al, Co, Fe, Mg, Mn, Ni and The coating is characterized in that the coating has nanocontainers, the nanocontainers being coated with at least one layer of at least one polymer, the at least one polymer being impregnated with at least one corrosion inhibitor, the proportion of the nanocontainers in the coating being at most 20 % By weight (based on the total weight of the coating), the proportion of the metal matrix in the coating being at least 70% by weight (based on the total weight of the coating), and the nanocontainers being embedded in the metal matrix.

Nanocontainers are understood to mean in particular particles with a core and at least one layer made of at least one polymer, the at least one layer made of the at least one polymer preferably being arranged on the surface of the core, in particular the at least one layer made of the at least one polymer enclosing the core the nanoparticle completely. The core of the nanoparticles can preferably be designed in different forms. The nanoparticles can preferably be designed in different forms.

The nanocontainer-containing coating for a body part has advantages compared to the prior art. Advantageously the coating of the metal matrix and the nanocontainers increases the corrosion protection, in particular the local corrosion is reduced. The corrosion of the body part is advantageously reduced by the formation of stable corrosion products. This can improve the passivation behavior of the coating and increase the corrosion resistance. The coating advantageously achieves improved paint adhesion and / or improved phosphatability. A body part coated with the coating advantageously enables improved cold forming and / or hot forming, in particular by reducing macro and micro cracks. The coating advantageously enables a particularly thin coating, which leads to savings in costs and weight in the corrosion protection of the body part. The coating advantageously shows an improved temperature resistance in comparison to pure zinc coatings, in particular since phenomena of grain growth can be reduced or controlled. The coating advantageously exhibits reduced wear properties. The coating advantageously shows homogeneous corrosion. Advantageously, the corrosion of the coating at a certain pH value at least partially dissolves the nanoparticles, the corrosion inhibitor flowing to the surface of the coating and thereby reducing the corrosion.

A body part is understood to mean, in particular, a part of the body of a vehicle, preferably a passenger car, truck, bus, camper, construction vehicle, utility vehicle or else rail vehicle, boat, ship or aircraft.

According to a development of the invention, it is provided that the at least one polymer is selected from the group consisting of polyacrylic acid (PAA), polydiallyldimethylammonium chloride (PDAD), polyethylene oxide (PEO), polypropylene oxide (PPO), and polystyrene (PS).

The nanocontainers preferably have a proportion of the at least one polymer of at least 50% by weight, preferably at least 60% by weight, preferably at least 65% by weight, preferably at least 70% by weight, preferably at least 75% by weight, preferably at least 80% by weight, preferably at least 85% by weight, preferably at least 90% by weight, preferably at least 95% by weight, preferably at least 97% by weight , preferably of at least 98% by weight, or preferably of at least 99% by weight (based on the total weight of the nanocontainers).

The metal matrix preferably has a Zn content of at least 50% by weight, preferably at least 60% by weight, preferably at least 65% by weight, preferably at least 70% by weight, preferably at least 75% by weight, preferably at least 80% by weight, preferably at least 85% by weight, preferably at least 87% by weight, or preferably at least 90% by weight (based on the total weight of the metal matrix).

The metal matrix preferably has a Mn content of from 5% by weight to 40% by weight, preferably from 5% by weight to 30% by weight, preferably from 5% by weight to 25% by weight, preferably from 5% by weight to 20% by weight, preferably from 5% by weight to 15% by weight, preferably from 5% by weight to 10% by weight, preferably from 10% by weight to 40% by weight, preferably from 10% by weight to 30% by weight, preferably from 10% by weight to 25% by weight, preferably from 10% by weight to 20% by weight, preferably from 10% by weight to 15% by weight, preferably from 15% by weight to 40% by weight, preferably from 15% by weight to 30% by weight, preferably from 15% by weight to 20% by weight .-%, or preferably from 20 wt .-% to 25 wt .-% (based on the total weight of the metal matrix).

According to a development of the invention, it is provided that the corrosion inhibitor is benzotriazole and / or at least one nitrite, preferably sodium nitrite or calcium nitrite.

According to a development of the invention, it is provided that the metal matrix consists of Zn, or consists of Mn and Zn, the proportion of Mn in the metal matrix being at most 40% by weight, preferably 10% by weight to 25% by weight (based on the total weight of the metal matrix).

The proportion of at least one further element selected from the group consisting of Al, Co, Fe, Mg and Ni in the metal matrix is at least 0.1% by weight to at most 10% by weight (based on the total weight of the metal matrix). It is clear to the person skilled in the art that a metal matrix consisting of Zn, or consisting of Mn and Zn, can have technically caused impurities, in particular unavoidable impurities.

The metal matrix preferably has further elements, preferably sulfur, lead, copper, molybdenum, titanium and / or zirconium. Other components of the metal matrix can be production-related impurities, in particular unavoidable impurities. Unavoidable impurities preferably occur in a proportion of at most 0.2% by weight, preferably at most 0.1% by weight (based on the total weight of the metal matrix).

The coating preferably has at least 75% by weight of the metal matrix, preferably at least 80% by weight, preferably at least 85% by weight, preferably at least 90% by weight, preferably at least 95% by weight, preferably at least 97% by weight .-% (based on the total weight of the coating).

According to a development of the invention, it is provided that the nanocontainers have a core made of a hematite-based composition, preferably with at least one oxide selected from the group consisting of aluminum oxide, cerium oxide, chromium oxide, iron oxide, cobalt oxide, magnesium oxide, manganese oxide, molybdenum oxide, nickel oxide, Silicon oxide, titanium oxide, yttrium oxide, zinc oxide, tin oxide, and zirconium oxide. The nanocontainers preferably have a hematite-based composition with a core of zinc oxide, or manganese oxide and zinc oxide. A hematite-based composition is a composition based on Fe ₂ O ₃ .

According to a development of the invention, it is provided that the nanocontainers are fiber-shaped, particle-shaped and / or rod-shaped, and / or the nanocontainers are homogeneously distributed in the metal matrix.

According to a development of the invention, it is provided that the nanocontainers have a particle size of 20 nm to 200 nm, preferably from 50 nm to 100 nm. The particle size of the nanocontainers relates in particular to the longest dimension of the nanocontainers. The nanocontainers preferably have a particle size of 10 nm to 200 nm, preferably from 10 nm to 100 nm, preferably from 20 nm to 100 nm, preferably from 10 nm to 50 nm, preferably from 1 nm to 50 nm, preferably from 1 nm to 20 nm, or preferably from 1 nm to 10 nm.

The coating preferably has at most 10% of the nanocontainers, preferably at most 8% by weight, preferably at most 6% by weight, preferably at most 4% by weight, or preferably at most 2% by weight (based on the total weight of the coating ), or preferably at least 0.1% by weight to at most 20% by weight, preferably at least 0.1% by weight to at most 10% by weight, preferably at least 0.1% by weight to at most 5% by weight %, preferably at least 0.1% by weight to at most 2% by weight, preferably at least 0.5% by weight to at most 20% by weight, preferably at least 0.5% by weight to at most 10 % By weight, preferably at least 0.5% by weight to at most 5% by weight, preferably at least 1% by weight to at most 20% by weight, preferably at least 1% by weight to at most 10% by weight %, or preferably at least 1% by weight to at most 5% by weight (based on the total weight of the coating).

The coating preferably has at most 20% by weight of the nanocontainers and at least 80% by weight of the metal matrix. The coating preferably consists of the metal matrix and the nanocontainers.

The coating preferably has a layer thickness of at most 200 μm, preferably at most 100 μm, preferably at most 80 μm, preferably at most 60 μm, preferably at most 50 μm, preferably at most 40 μm, preferably at most 30 μm, preferably at most 25 μm, or preferably at most 20 µm, preferably the coating has a layer thickness of 1 µm to 100 µm, 1 µm to 80 µm, 1 µm to 50 µm, 1 µm to 40 µm, 1 µm to 30 µm, 1 µm to 20 µm, 10 µm to 100 µm, 5 µm to 100 µm, 5 to 80 µm, 10 µm to 80 µm, 5 µm to 50 µm, 10 µm to 50 µm, 10 µm to 30 µm, or preferably from 10 µm to 20 µm.

According to a development of the invention, it is provided that the nanocontainers have at least one protective layer, the at least one protective layer being arranged on the at least one layer composed of the at least one polymer.

The at least one protective layer preferably completely encloses the at least one layer composed of the at least one polymer.

The object is also achieved by providing a body part with a coating containing nanocontainers, in particular according to one of the exemplary embodiments described above. The advantages of the coated body part are those which have already been explained in connection with the coating containing the nanocontainer.

According to a development of the invention, it is provided that the body part is made of steel and / or the coating has a layer thickness of 5 μm to 100 μm.

The steel is preferably a high-strength steel without interstitial atoms (HSIF), a high-strength low-alloy steel (HSLA), a dual-phase steel (DP), a complex-phase steel (CP), a strain-induced hardening steel (RIP), a bake hardening steel or one similar steel grade. The body part for hot forming is preferably made of ultra-high-strength steel, preferably 6Mn3, 6Mn6, 22MnB5, 27MnCrB5, or 37MnB4, or martensitic steel.

The coating is preferably at least in regions on the body part formed, in particular on one side of the body part. The coating is preferably formed on the entire body part.

The invention is explained in more detail below with reference to the drawing. The single figure shows a schematic representation of a body part with a nanocontainer-containing coating in one embodiment.

The single figure shows a schematic representation of a body part 3rd with a coating containing nanocontainers 7 1 in one embodiment. The body part 3rd According to the exemplary embodiment shown here, the coating containing nanocontainers 7 has 1 on. The coating 1 exhibits a metal matrix 5 on, the metal matrix 5 has at least one element selected from the group consisting of Al, Co, Fe, Mg, Mn, Ni and Zn. The coating 1 also shows nanocontainers 7 on. The nanocontainers 7 are coated with at least one layer of at least one polymer, the at least one polymer being impregnated with at least one corrosion inhibitor. The share of nanocontainers 7 in the coating 1 is at most 20% by weight (based on the total weight of the coating), and the proportion of the metal matrix 5 in the coating 1 is at least 70% by weight (based on the total weight of the coating). The nanocontainers 7 are in the metal matrix 5 embedded.

The coating 1 can in particular by depositing an alloy on the body part 3rd are obtained, for example by a hot-dip process, an electrolytic process, a PVD process (Physical Vapor Deposition), a CVD process (Chemical Vapor Deposition), an IVD process (Ion Vapor Deposition), and / or a slurry process. The coating 1 can in particular be deposited from an aqueous electrolyte solution, for example a sulfate and / or chloride solution. The nanocontainers 7 can be produced by a layer-by-layer process.

Overall, it shows that the coating 1 for the body part 3rd has improved corrosion protection compared to known coatings, in particular coatings made of pure zinc. Through the coating 1 local corrosion is reduced in particular. The corrosion of the body part is advantageous 3rd reduced by the formation of stable corrosion products, which reduces the passivation behavior of the coating 1 can be improved. The coating advantageously enables 1 an improved cold forming and / or hot forming of a body part coated with it 3rd , especially by reducing macro and micro cracks. The coating advantageously shows 1 an improved temperature resistance. The coating advantageously shows 1 reduced wear properties.

In one embodiment of the invention, the at least one polymer is selected from the group consisting of polyacrylic acid (PAA), polydiallyldimethylammonium chloride (PDAD), polyethylene oxide (PEO), polypropylene oxide (PPO), and polystyrene (PS).

In a further embodiment of the invention, the corrosion inhibitor is benzotriazole and / or at least one nitrite, preferably sodium nitrite or calcium nitrite.

In a further embodiment of the invention, the metal matrix is made 5 from Zn, or from Mn and Zn, where the proportion of Mn in the metal matrix 5 is at most 40% by weight, preferably 10 to 25% by weight (based on the total weight of the coating).

In a further embodiment of the invention, the nanocontainers 7 a core of a hematite-based composition, preferably with at least one oxide selected from the group consisting of aluminum oxide, cerium oxide, chromium oxide, iron oxide, cobalt oxide, magnesium oxide, manganese oxide, molybdenum oxide, nickel oxide, silicon oxide, titanium oxide, yttrium oxide, zinc oxide, tin oxide, and Zirconium oxide.

In a further embodiment of the invention, the nanocontainers are 7 Fiber-shaped, particle-shaped and / or rod-shaped, and / or are the nanocontainers 7 homogeneous in the metal matrix 5 distributed.

In a further embodiment of the invention, the nanocontainers 7 a particle size of 20 nm to 200 nm, preferably from 50 nm to 100 nm. The particle size of the nanocontainers relates in particular to the longest dimension of the nanocontainers.

In a further embodiment of the invention, the nanocontainers 7 at least one protective layer, the at least one protective layer being arranged on the at least one layer composed of the at least one polymer.

The coating 1 is particularly on the body part 3rd applied. In one embodiment of the invention, the body part 3rd made of steel. In a further embodiment of the invention, the coating has 1 a layer thickness of 5 µm to 100 µm.

QUOTES INCLUDE IN THE DESCRIPTION

This list of documents listed by the applicant has been generated automatically and is only included for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.

Patent literature cited

• DE 102015113677 A1 [0006]

Claims (10)

Nanocontainer (7) -containing coating (1) for a body part (3), the coating having a metal matrix (5), the metal matrix (5) having at least one element selected from the group consisting of Al, Co, Fe, Mg , Mn, Ni and Zn, characterized in that the coating has nanocontainers (7), the nanocontainers (7) being coated with at least one layer of at least one polymer, the at least one polymer being impregnated with at least one corrosion inhibitor, the The proportion of the nanocontainers (7) in the coating (1) is at most 20% by weight, the proportion of the metal matrix (5) in the coating (1) being at least 70% by weight, and the nanocontainers (7) in the metal matrix (5) are embedded. Coating (1) after Claim 1 , characterized in that the at least one polymer is selected from the group consisting of polyacrylic acid (PAA), polydiallyldimethylammonium chloride (PDAD), polyethylene oxide (PEO), polypropylene oxide (PPO), and polystyrene (PS). Coating (1) after Claim 1 or 2nd , characterized in that the corrosion inhibitor is benzotriazole and / or at least one nitrite, preferably sodium nitrite or calcium nitrite. Coating (1) according to one of the preceding claims, characterized in that the metal matrix (5) consists of Zn, or consists of Mn and Zn, the proportion of Mn in the metal matrix (5) being at most 40% by weight, preferably 10 to 25% by weight. Coating (1) according to one of the preceding claims, characterized in that the nanocontainers (7) have a core made of a hematite-based composition, preferably with at least one oxide selected from the group consisting of aluminum oxide, cerium oxide, chromium oxide, iron oxide, cobalt oxide, Magnesium oxide, manganese oxide, molybdenum oxide, nickel oxide, silicon oxide, titanium oxide, yttrium oxide, zinc oxide, tin oxide, and zirconium oxide. Coating (1) according to one of the preceding claims, characterized in that the nanocontainers (7) are fiber-shaped, particle-shaped and / or rod-shaped, and / or the nanocontainers (7) are homogeneous in the metal matrix (5) are distributed. Coating (1) according to one of the preceding claims, characterized in that the nanocontainers (7) have a particle size of 20 nm to 200 nm, preferably from 50 nm to 100 nm. Coating (1) according to one of the preceding claims, characterized in that the nanocontainers (7) have at least one protective layer, the at least one protective layer being arranged on the at least one layer composed of the at least one polymer. Body part (3) with a coating (1) according to one of the Claims 1 to 8th . Body part (3) after Claim 9 , characterized in that the body part (3) is made of steel and / or the coating (1) has a layer thickness of 5 µm to 100 µm.

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