Method for producing a plastic-ceramic (metal) composite and the plastic-ceramic (metal) composite component

Abstract

The invention relates to a method for producing a plastic-ceramic (metal) composite component (110) and the produced component (110, 120a, 120b, 120c). The method comprises: (1) applying a coating (40), comprising or consisting of ceramic microspheres (45), to at least a portion of a plastic surface (12) of a component (10.1); (2) pressing the ceramic microspheres (45) into the plastic surface (12) of the component (10.1) in a rolling process or in an alternative press-fit process, resulting in the plastic-ceramic (metal) composite component (110, 120a). Alternatively, prior to step (2) a second component (10.2) having at least one plastic or metal surface (14) is inserted and the pressing of the ceramic microspheres (45) in step (2) takes place simultaneously into both surfaces (12, 14) of the components (10.1, 10.2) in a rolling process to obtain the plastic-ceramic (metal) composite component (120c, 120d).The invention is characterized by the fact that tribologically highly resistant components with chemical and thermal resistance and simultaneously electrical and electromagnetic insulation and shielding properties are provided.

Description

[0001] The invention relates to a method for producing a plastic-ceramic (metal) composite component and to the plastic-ceramic (metal) composite component produced by the method.

[0002] It is known to apply coatings to a component that contain tribologically active hard material particles in order to better protect the component against wear and abrasion. These known coatings with hard material particles are usually applied to the component using a binder system. This often results in insufficient adhesion to the component, as the binder system is destroyed and then degraded over time under heavy stress. The tribologically active hard material particles also lose their adhesion due to the loss of the binder system, so that the surface of the component is no longer covered by a wear-resistant coating. The then released, usually irregularly shaped, sharp-edged hard material particles can also contribute to damage in the systems or equipment used due to their shape.

[0003] Some proposals for the provision of more wear-resistant composite materials have become known from the state of the art: EP 0 037 536 B1 describes a machine element with a hard bearing or guide surface containing hard bodies embedded in an investment material made of a plastic material, which hard bodies are machined down by an amount of their original height. The hard bodies are made of metal and, in their initial state, are spheres of the same size, on the order of magnitude of rolling bearing balls, arranged adjacent to one another. In the method for producing the machine element, the hard bodies are surrounded by investment material, the latter is solidified, and the resulting substrate is machined down in height, whereby surfaces are exposed on the hard bodies to form the hard bearing or guide surface, the investment material is applied to a surface, and spheres are inserted into it.

[0004] Furthermore, DE 10 2010 047 279 A1 discloses a piston for internal combustion engines, comprising a skirt coating consisting of a wear-resistant inner layer of a polymer matrix with ceramic particles, aramid fibers, and / or carbon fibers dispersed therein, and an outer layer of a polymer matrix with solid lubricants dispersed therein. The ceramic particles are selected, for example, from the group consisting of titanium oxide, silicon carbide, silicon nitride, aluminum oxide, silicon oxide, and iron oxide, and have a particle size of 0.1 to 20 µm.

[0005] DE 2 311 507 relates to a wear-resistant coating compound with high wear resistance against impact, abrasion, erosion, and corrosion. It consists of coarse-grained, abrasion-resistant particles and fine-grained, equally abrasion-resistant filler particles that are uniformly dispersed in a curable, initially thixotropic polymer matrix in such a way that the filler particles are statistically homogeneously distributed in the matrix surrounding and adjacent to the coarser particles. Before the matrix hardens, the compound has a viscous consistency suitable for spatula-like application. The polymer represents a plastic that is thermally curable or cured by crosslinking. The abrasion-resistant particles consist, for example, of aluminum oxide, preferably coated with a metal layer.

[0006] A disadvantage of the prior art proposals is that the abrasion-resistant particles are distributed in a polymer matrix, which is often subsequently cured. As a result, the abrasion-resistant particles are embedded in the polymer matrix in such a way that they are not located near the surface and thus cannot fully develop their effect. Furthermore, the particles are always distributed throughout the polymer matrix, making targeted positioning of the abrasion-resistant particles impossible. The polymer matrix serves as a binder system, the degradation of which would release the abrasion-resistant particles.

[0007] The invention is based on the object of overcoming the disadvantages of the prior art and providing a plastic-ceramic (metal) composite component that enables the adhesion of a tribologically effective coating to the component even if the binder is lost over time and even without a binder. It also aims to provide a simple and cost-effective process for producing a plastic-ceramic (metal) composite component with high tribological resilience.

[0008] According to the invention, the above-described object is achieved by a method for producing a plastic-ceramic (metal) composite component, comprising the following steps: (1) applying a coating comprising or consisting of ceramic microspheres to at least part of a plastic surface of a component; (2) Indenting, in particular partially indenting, the ceramic microspheres into the plastic surface in a rolling process and / or with an indentation process and / or a press-fitting process to obtain the plastic-ceramic (metal) composite component.

[0009] The method of the present invention will be explained in detail below: Before performing step (1), the component may be pretreated. This may include, for example, aligning the component and, if necessary, preheating it.

[0010] In step (1) of the method according to the invention, a coating comprising or consisting of ceramic microspheres is applied to at least part of a plastic surface of a component.

[0011] The component is not further restricted with regard to its shape, size, or type. According to one embodiment, the component can be a plastic component that contains plastic as its main component (e.g., more than 50% by weight) or consists of plastic. Naturally, the plastic component has at least one plastic surface that can be modified for high tribological loads using the method according to the invention.

[0012] For example, a plastic-coated metal component can also be present as a component. The metal component can be, for example, a metal plate, a metal layer such as a metal sheet, a metal strip, in particular a metal foil, and has at least one plastic surface, for example a polymer coating. A metal component comprises metal as its main component (e.g., more than 50% by weight) or consists of metal. The metal is, for example, selected from aluminum, aluminum alloys, copper, copper alloys, titanium, titanium alloys, iron, iron alloys, unalloyed steel, low-alloy steel, high-alloy steel, nickel or nickel alloys, and coated steel such as hot-laminated steel sheet or galvanized steel sheet. Metals other than those mentioned are also possible.

[0013] The plastic of the plastic surface or the plastic component is not further restricted within the scope of the present invention. It can contain one or more polymers, preferably chemically inert polymers such as polyethylene, polypropylene, polyvinyl chloride, or polymers with high chemical and thermal resistance, such as polyoxymethylene, polycarbonates, polyaryletherketones (PEAK), such as polyetheretherketone (PEEK), polyetherketone (PEK), polyetherketoneketone (PEKK), or polyetherketoneetherketoneketone (PEKEKK), polyimide, polyamideimide, polyphenylene sulfide, or mixtures of all of the specified polymers. Other polymers can also be used.

[0014] Ceramic microspheres are preferably applied evenly as a coating to the plastic surface of the component. The coating can be applied using local coating processes, for example, a printing process such as screen printing, printing as a ceramic ink, for example, inkjet printing, or locally distributing a pasty system using a dispenser onto at least part of the plastic surface of the component.

[0015] The coating comprises ceramic microspheres. The term "ceramic" means that the microspheres contain or consist of one or more ceramic materials as the main component (for example, more than 50 wt%). The ceramic material is not further restricted; in particular, oxidic (oxide-based), carbide (carbon-based), or nitridic (nitride-based) ceramics are used. The ceramic microspheres are preferably selected from the group consisting of zirconium oxide spheres, zirconium mixed oxide spheres, in particular yttrium-stabilized (yttrium oxide-stabilized) zirconium oxide spheres or cerium-stabilized (cerium oxide-stabilized) zirconium oxide spheres, zirconium silicate spheres, in particular sintered zirconium silicate spheres, aluminum oxide spheres, steatite spheres (based on magnesium silicate), and mixtures thereof. For example, sintered zirconium silicate spheres have the following chemical composition: 60 wt% (± 5 wt.-%) ZrO2 and 37.5 wt.% SiO2 (± 2.5 wt.%) and are known to be much harder, heavier, and more abrasion-resistant than glass spheres. Another example is yttrium-stabilized zirconia spheres, also known as yttria-stabilized zirconia spheres, with the following chemical composition: 95 wt.% (± 0.2 wt.%) ZrO2 and 5.0 wt.% Y2O3 (± 0.2 wt.%), with a notoriously high hardness and abrasion resistance.

[0016] The ceramic microspheres used have a preferred sphere size in the range of 0.01 mm (10 µm) to 10 mm, more preferably 0.05 to 9 mm or 0.1 to 8.5 mm or 0.2 to 8.0 mm or 0.3 to 7.5 mm, even more preferably 0.35 to 7.0 mm or 0.4 to 6.5 mm or 0.45 to 6.0 mm, most preferably in the range of 0.5 to 5.0 mm. The size of the spheres can be determined, for example, with the aid of sieve analysis, in particular with the aid of a sieve tower. Individual sieves are stacked on top of one another, with the sieve closest to the bottom having a smaller mesh size than the one above. The sphere size can thus be easily maintained by selecting only spheres of the corresponding size fraction for the further manufacturing process. Analytically, the sphere size can be determined using microscopic methods such as light microscope or SEM.

[0017] The ceramic microspheres preferably have a smooth surface and can be provided in a nearly perfectly spherical shape with a narrow size distribution. The ceramic microspheres have a high density, which makes the material highly abrasion-resistant, fracture-resistant, and fracture-resistant. The ceramic material is resistant to oxidation and corrosion and can therefore be used in conjunction with water. Generally, the ceramic microspheres used in the invention are solid spheres rather than hollow spheres.

[0018] For example, commercially available ceramic microspheres can be used. Examples of commercially available products include (note: brand names can be cited in the description of a patent application, but this is not permitted in the claims): ZYS-L - Zirconium oxide (yttrium-stab.) ZrO2 94.4% ZC-L - Zirconium oxide (Cerium-stab.) ZrO2 84% ZS-LZ - Zirconium silicate ZrO2 >57% ZYE-L - Zirconium oxide (yttrium-stab.) ZrO2 94.35% YTZ® - Zirconium oxide (yttrium-stab.) ZrO2 95% Zirmil®Y - Zirconium oxide (yttrium-stab.) ZrO2 93% Zirconox® - Zirconium oxide (Cerium-stab.) ZrO2 83% Zirmil®CE - Zirconium oxide (Cerium-stab.) ZrO2 82% SAZ - Zirconium mixed oxide ER 120 S ZrO2 68% Zircosil® - Zirconium mixed oxide ZrO2 60% RIMAX (ZS-R) - Zirconium silicate ZrO2 58% Aluminium oxide grinding granules and balls Al2O3 90% Aluminum oxide grinding balls Al2O3 99.5% Steatite grinding granules and balls Steatite grinding balls and cylinders Aluminum oxide grinding granules and balls Al2O3 92% Aluminum oxide grinding balls Al2O3 99.9%.

[0019] Preferably, at least one layer of ceramic microspheres, particularly preferably precisely one layer of ceramic microspheres, is applied with the coating. The coating can comprise the ceramic microspheres or consist of them. It is preferred if the ceramic microspheres used in the coating all have substantially the same sphere diameter, i.e., a sphere diameter with a narrow size distribution, so that the applied layer of microspheres has approximately the same layer thickness over the entire coated area. Particularly preferably, the ceramic microspheres of the coating all have the same composition and are selected from the same ceramic compound.

[0020] Optionally, an adhesion-promoting layer can be applied to the surface of the component to be coated before applying the coating in step (1). The microspheres are then dosed and applied.

[0021] After applying the coating in step (1), a suitable and uniform layer thickness can optionally be adjusted. This can be achieved, for example, using a stripping system. This also makes it possible to ensure that only one layer of ceramic microspheres is present in the coating.

[0022] After applying the coating in step (1) and, if necessary, adjusting a suitable and uniform layer thickness, the applied coating can optionally be fixed. The fixing method depends on the composition of the selected coating, which can be a solid, semi-solid, or liquid composition. For example, the coating can be a dispersion, such as an ink or a paste, which contains one or more carriers in addition to the microspheres.

[0023] The carrier(s) are selected, for example, from one or more binders and / or one or more organic adhesives and, optionally, one or more solvents.

[0024] The one or more adhesives are, for example, chemically curing adhesives or reactive adhesives. These are adhesives that cure through a crosslinking process. They are liquid to pasty or even film-like substances that cure through a catalyst or hardener, through elevated temperature, through humidity, or through the removal of oxygen. These include, for example, polymerization adhesives, polyaddition adhesives, or polycondensation adhesives. UV adhesives cure under UV light. One- and two-component adhesives are known.

[0025] The one or more binders are those that can be used under the rolling process conditions. These include, for example, curable epoxy resins, which are not adhesives.

[0026] The solvents are not further limited and may include organic solvents and water.

[0027] Fixing can then be carried out, for example, by thermal evaporation of solvent, thermal curing of an organic adhesive system, such as an epoxy and / or urethane-based adhesive, curing via atmospheric humidity, for example a cyanoacrylate-based adhesive, or particularly preferably optical curing of an adhesive system, e.g. a UV-sensitive epoxy or acrylate-based adhesive, via UV radiation.

[0028] The optional fixation of the coating can also be carried out during heating of the component before the rolling process in step (2).

[0029] In step (2) of the method according to the invention, the ceramic microspheres are pressed into the plastic surface of the component in a rolling process or by means of another pressing process to obtain the plastic-ceramic composite component.

[0030] For example, if the component is a metal component with a plastic surface, a plastic-ceramic-metal composite component is produced. In particular, only partial indentation into the plastic surface takes place, with the microspheres still remaining visible. Heating may be applied before and / or during the plating process in the form of a rolling process or another indentation process. Heating the component coated with ceramic microspheres obtained in step (1) can also be used to simultaneously fix the coating.

[0031] During the plating process, the ceramic microspheres are mechanically embossed into the plastic surface of the component, whereby preferably the polymeric material of the component can also at least partially flow around the ceramic microspheres, which causes additional fixing.

[0032] If a metal component is used that has at least one plastic surface, for example, a polymer coating, the thickness of the polymer coating can preferably be adjusted to ensure secure enclosing of the spheres. At the same time, due to the lower softening temperature of the plastic, the penetration depth of the microspheres can be precisely adjusted by adjusting the thickness of the plastic surface, since the underlying metal is preferably not softened upon heating and then acts as a penetration barrier.

[0033] In a particularly preferred embodiment, the ball diameter and / or the thickness of the plastic surface is selected such that, when used in a single-layer application during the rolling process, the balls are enclosed by the polymeric material to at least 30%, particularly preferably between 30 and 95% of the ball diameter. When applied to a polymer-coated metal component, this can be achieved particularly simply by using a metallic material beneath the polymer coating to determine the penetration depth. "Polymeric material" here refers to the one or more polymers contained in the plastic surface of the component, which may be present, for example, in the form of a coating.

[0034] According to one embodiment of the invention, before carrying out step (2), a second component having at least one plastic or metal surface is fed in such a way that the applied coating, comprising or consisting of ceramic microspheres, is located between them. The coating can be applied only to the first or second component, or simultaneously to both components. The second component is fed in such a way that the coating is present between the plastic surface of the first component and the plastic or metal surface of the second component. The ceramic microspheres are then pressed into both surfaces of the components in step (2) simultaneously in a rolling process, resulting in a plastic-ceramic composite component or a plastic-ceramic-metal composite component.

[0035] The second component is also not further limited as long as it has at least one plastic or metal surface. For example, the second component can be a metal component, such as a metal plate, a metal layer, such as a metal sheet, a metal strip, in particular a metal foil, a metal component with at least one plastic surface, or even a plastic component, such as a polymer plate or foil. The polymers of the plastic surface are not further limited and can, for example, be selected from the polymers exemplified for the first component. The metal of a metal component is also not particularly limited; the previously described metals can be used, for example.

[0036] The second component is therefore applied to the coating comprising or consisting of ceramic microspheres. For this purpose, a second component is first applied to the first component, on which the ceramic microspheres are present, forming a sandwich structure with the ceramic microspheres between the surfaces of the first and second components.

[0037] The coating with ceramic microspheres can be applied only to the first component or only to the second component (single-sided application), or the coating can also be applied to both components (double-sided application). Before and / or during the plating process in step (2), the two components can be heated if necessary. Heating the components can also be used to simultaneously fix the coating, comprising or consisting of the ceramic microspheres. During the plating process, the ceramic microspheres are then mechanically embossed simultaneously into the two surfaces of the first and second components, with additional fixing preferably being achieved by at least partially flowing around the ceramic microspheres with the material(s) of the two surfaces of the components.This can be one or more polymers from both surfaces of the components, or one or more polymers from the surface of the first component and a metal material from the surface of the second component. In the first case, a plastic-ceramic composite component is formed. In the second case, and if the first component is a metal component with at least one plastic surface, a plastic-ceramic-metal composite component is formed.

[0038] Through plating, the material is embedded as a wear-stopping intermediate layer in the roll-clad components.

[0039] If a sandwich structure is to be formed from two identical or different components and the ceramic microspheres in between, it is preferred if only one layer of ceramic microspheres is applied with the coating.

[0040] When used as an intermediate layer between two identical or different components in the plating process, the sphere diameter is preferably selected so that both components can form an intimate, enclosing bond with the spheres. The rolling process can then result in the ceramic microspheres being completely enclosed and surrounded by the two components within the interface of the cladding. By incorporating the microspheres, the separation plane between the two cladding components can be advantageously enlarged, thus optimizing the adhesion strength of the cladding.

[0041] The invention also relates to the plastic-ceramic composite component or plastic-ceramic-metal composite component which can be produced by the method according to the invention and which has a tribologically resilient, in particular highly resilient, surface area by mechanical introduction or plating of ceramic microspheres.

[0042] By using a plastic component or a metal component with at least one plastic surface as the first component and optionally a plastic component, a metal component or a metal component with at least one plastic surface as the second component, three variants result according to the invention: a plastic - To produce a ceramic (metal) composite component: a) a plastic-ceramic composite component, produced by directly embossing or pressing ceramic microspheres into at least part of the surface of a plastic component, preferably a highly thermally resistant plastic; b) a plastic-ceramic-metal composite component, produced by directly embossing or pressing ceramic microspheres into at least one plastic surface of a metal component; or c) a plastic-ceramic-(metal) composite component, produced by forming a sandwich structure by combining two components, the first component being either a plastic component or a metal component with at least one plastic surface, with a second component having at least one plastic or metal surface being added during the joining process in the form of the plating process in step (2). The plastic-ceramic-(metal) composite component is then produced by directly embossing or pressing ceramic microspheres simultaneously into both surfaces of the two components, the plastic surface of the first component and the plastic or metal surface of the second component, resulting in a particularly good enclosure of the ceramic microspheres.

[0043] According to one embodiment, a coating comprising or consisting of ceramic microspheres is applied to a component such that up to 95% of the coated area, more preferably up to 85% of the coated area, even more preferably up to 75% of the coated area, in particular up to 70% of the coated area of ​​the component represents ceramic microspheres.

[0044] Thus, according to the invention, it is possible to produce tribologically highly resilient plastic-ceramic composite components or plastic-ceramic-metal composite components by applying spheroidal ceramic components with preferably up to 95 area%, in particular up to 70 area% and mechanically anchoring the ceramic microspheres as a tribologically resistant layer in a rolling process.

[0045] According to a preferred embodiment, embedding as a wear-stopping intermediate layer in roll-clad components, also referred to here as a sandwich structure, is also possible.

[0046] With the present invention, therefore, tribologically highly resistant component regions can be provided in polymeric materials and polymer-metal composites by applying at least one defined layer of ceramic microspheres to produce a hard material-containing composite material.

[0047] The layer thickness can be ensured by using microspheres with preferably very uniform grain sizes, i.e., microsphere diameters with a narrow size distribution. Advantageously, ceramic microspheres, preferably yttrium- or cerium-stabilized zirconium oxide spheres or aluminum oxide spheres, are commercially available in suitable sizes. These are used, among other things, as grinding balls for bead mills, exhibiting high hardness, thermal resistance, and minimal abrasion. Particularly preferably, the ceramic microspheres are all of the same composition.

[0048] By using ceramic microspheres with a very uniform grain size, uniform positioning in the material surface and thus a clearly defined tribological plane can be ensured. The sphere diameter and the resulting layer thickness of the applied sphere layer can be selected such that during the rolling process or the pressing process, the sphere layer(s) are mechanically pressed into the surface of the polymeric and, if applicable, metallic material to a defined depth and are permanently fixed by flowing around the polymeric and, if applicable, metallic material, which is preferably already soft and / or doughy due to thermal pretreatment. If a metal component with a polymer layer is used, the penetration depth of the microspheres can be specifically adjusted by adjusting the layer thickness of the polymer layer, since the underlying metal can serve as a boundary.

[0049] When using a second component, it is preferably dimensioned so that the ceramic microspheres are completely enclosed but embedded close to the surface in order to be available as contact partners after a short time under tribological load.

[0050] This allows for improved coating durability compared to chemical binder systems for hard material particles. Should individual microspheres become detached during the manufacturing process or during subsequent operation, their spherical shape poses a significantly lower risk than the sharp-edged hard material particles previously used. Furthermore, the spherical shape of the ceramic spheres makes the interface less abrasive to the tribological partners. Furthermore, the use of ceramic microspheres, particularly yttrium- and cerium-stabilized zirconium oxide spheres, preferably in the range of 0.01 mm (10 µm) - 10 mm, particularly preferably 0.5 - 5 mm, virtually eliminates any subsequent chemical reaction with any operating materials that may be used.

[0051] The method of the invention will be explained in more detail with reference to the following embodiments in conjunction with the accompanying drawings, wherein the accompanying figures are schematic and not drawn to scale, so that no assumption can be made about exact geometric values ​​with respect to the actual size. The figures of the present disclosure are incorporated in and constitute a part of the description, illustrating embodiments of the invention without limitation to the specific embodiments described. The drawings, together with the description, serve to explain the principles of the present disclosure. Where possible, the same features are designated by the same reference numerals throughout the figures.

[0052] The figures show: Fig.1: a schematically simplified sectional view of the optional pretreatment of a component according to an embodiment of the invention; Fig. 2: a schematically simplified sectional view of the application of a coating comprising or consisting of ceramic microspheres by a local coating process in step (1) according to an embodiment of the invention; Fig. 3: a schematically simplified sectional view of the feeding of a second component and implementation of a rolling process after optional heating of the components according to an embodiment of the invention; Fig. 4A shows an enlarged schematically simplified section of a manufactured plastic-ceramic composite component according to an embodiment of the invention; Fig.4B: an enlarged schematically simplified section of a manufactured plastic-ceramic-metal composite component according to a further embodiment of the invention; Fig. 4C: an enlarged schematically simplified section of a manufactured plastic-ceramic-metal composite component in the form of a sandwich structure according to a further embodiment of the invention; and Fig. 4D: an enlarged schematically simplified section of a manufactured plastic-ceramic-metal composite component in the form of a sandwich structure according to yet another embodiment of the invention.

[0053] The figures are explained in detail below: Fig.1 illustrates, in a schematically simplified sectional view, the optional pretreatment of a component 10.1 according to an embodiment of the invention, which can be carried out before carrying out step (1). The component 10.1 is shown here as a polymer plate by way of example. Other components are possible. The pretreatment of the polymer plate 10.1 represents a calibration or alignment and, if appropriate, a preheating of the polymer plate 10.1, if this is to be done so. This relates, for example, to the exact position of the polymer plate 10.1, wherein, for example, the length deviation from the rolling direction, illustrated schematically here using two rollers 20a and 20b, can be used to orient the position of the polymer plate 10.1. The preheating can be carried out by schematically illustrated heating devices 25.1 and 25.2 (T stands for temperature). Fig.Figure 2 shows a schematically simplified sectional view of an application of a coating 40 comprising or consisting of ceramic microspheres 45 by a local coating process in step (1) according to an embodiment of the method according to the invention. The coating 40 is applied to at least a portion of the surface 12 of the polymer plate 10.1. The application can be carried out using any type of known locally applicable coating process, for example, by a printing process such as screen printing. According to Fig. 2, in the embodiment shown, a pasty coating 40 is applied to the polymer plate 10.1 by means of a dispenser 30 in the form of a manual, semi-automatic, or automatic dosing device. Optional stripping devices 35.1 and 35.2 ensure a uniform layer of the desired thickness.

[0054] Before applying the coating 40 in step (1), an adhesion-promoting layer can also first be applied to the areas of the surface 12 of the polymer plate 10.1 to be coated (not shown). Subsequently, the microspheres are then metered and applied. During this time, heating or keeping warm can take place in parallel.

[0055] Fig. Figure 3 illustrates, in a schematically simplified sectional view, the feeding of a second component and the implementation of a rolling process after optional heating of the components according to an embodiment of the invention. The first component 10.1 is shown in Fig.3 is a polymer plate, and the second component 10.2 is a polymer film. Other designs are possible. The polymers of the polymer plate and film can be the same or different and are preferably selected from chemically inert polymers, such as polyethylene, polypropylene, polyvinyl chloride, or polymers with high chemical and thermal resistance, such as polyoxymethylene, polycarbonates, polyaryletherketones (PEAK), such as polyetheretherketone (PEEK), polyetherketone (PEK), polyetherketoneketone (PEKK), or polyetherketoneetherketoneketone (PEKEKK), polyimide, polyamideimide, polyphenylene sulfide, polytetrafluoroethylene (PTFE), or mixtures of the aforementioned polymers.

[0056] The preferably uniformly applied microspheres 45 are pressed into the surfaces 12 and 14 of the polymer materials of the polymer plate 10.1 and polymer film 10.2 by one or more rollers 20a and 20b. If the polymer plate 10.1 and the polymer film 10.2 are additionally heated, the microspheres 45 are not only embossed into the polymer materials by the rollers 20a and 20b, but are further pressed into the soft and / or doughy polymer materials by the heating, at least partially enclosed by them and thereby additionally fixed.

[0057] If, as in Fig. 3, a second component 10.2 is supplied, this is preferably dimensioned such that the microspheres 45 are completely enclosed and embedded close to the surface of both components, here: the polymer plate 10.1 and the polymer film 10.2, after the rolling process in order to be able to act in a suitable manner under tribological load.

[0058] The coating 40, comprising or consisting of ceramic microspheres 45, is therefore embedded by the roller pair 20a and 20b as an intermediate layer 15 between the two components, the polymer plate 10.1 and the polymer film 10.2. This results in a sandwich structure 55. The ceramic microspheres 45 are thus enclosed and enclosed within the interface of the plating between the two components, the polymer plate 10.1 and the polymer film 10.2.

[0059] The ceramic microspheres 45 are not further limited; for example, yttrium-stabilized zirconium oxide spheres, cerium-stabilized zirconium oxide spheres, or aluminum oxide spheres are used. Other ceramic sphere materials are also possible. The preferred sphere size is in the range from 0.01 mm (10 µm) to 10 mm, most preferably in the range from 0.5 to 5.0 mm. Other sphere sizes are possible depending on the embodiment. Preferably, only sphere sizes with the same selected sphere diameter, i.e., a sphere diameter with a narrow size distribution, are used in the intermediate layer 15, so that all ceramic microspheres are approximately the same size, resulting in a uniform layer thickness.

[0060] The coating 40, in which the ceramic microspheres 45 are present, can comprise one or more binders and / or one or more adhesives, as well as optionally one or more solvents. The optional binder(s) and / or adhesive(s) serve to fix them to the component to be coated prior to the rolling or pressing process, but after the rolling process or pressing and embedding into the component(s), they contribute little to the adhesion of the microspheres to / in the metal component.

[0061] Before carrying out and / or during the plating process in the form of the rolling process, the two components, the polymer plate 10.1 and the polymer film 10.2, can be heated if necessary, as already explained. This is Fig.3 with the schematically shown heating devices 25.3 and 25.4 (T stands for temperature). The preferably uniformly applied microspheres 45 are then pressed into the polymeric material, which has already become soft and / or doughy due to heating, by one or more rollers 20a and 20b, and are fixed by the material by at least partially flowing around it.

[0062] Heating the polymer plate 10.1 and the polymer film 10.2 can also be used to simultaneously fix the coating 40. Fixing can be achieved, for example, by thermal evaporation of solvent, thermal curing of an organic adhesive, for example, based on epoxy and / or urethane, or curing through atmospheric humidity, for example, with cyanoacrylate-based adhesives. It is also possible to cure an adhesive via UV irradiation. Examples of this include epoxy- or acrylate-based adhesives. Fixing the coating 40 is optional and is preferably performed between steps (1) and (2).

[0063] Fig.4A shows an enlarged, schematically simplified section of the manufactured plastic-ceramic composite component according to an embodiment of the invention. In the embodiment shown, the plastic-ceramic composite component 110 is a polymer plate 10.1 comprising a layer of ceramic microspheres 45 partially embedded in the surface 12 by the rolling process or the indentation process. The microspheres 45 all have approximately the same sphere diameter (with a narrow size distribution) and are all selected from the same ceramic compound or a mixture of different ceramic types. Other configurations are possible.

[0064] According to one embodiment, a coating comprising ceramic microspheres is applied to the component such that up to 95% of the coated area, more preferably up to 85% of the coated area, even more preferably up to 75% of the coated area, in particular up to 70% of the coated area of ​​the component represents ceramic microspheres 45.

[0065] According to a particularly preferred embodiment, the sphere diameter of the ceramic microspheres 45 is selected such that, when used in a single-layer configuration during the rolling process, a sphere is enclosed by the polymer material of a component (here: polymer plate 10.1) to at least 30%, particularly preferably between 30 and 95% of the sphere diameter. This can be specifically adjusted and controlled both by the rolling process and by heating the polymer plate 10.1 before and / or during the rolling process.

[0066] Fig.4B illustrates an enlarged schematically simplified section of a plastic-ceramic-metal composite component 120a according to an embodiment of the invention, which as in Fig. 3. A metal component 10.1a is used as component 10.1, and a polymer coating 10.1b is used as the plastic surface, with the ceramic microspheres 45 pressed into the plastic surface by a rolling process or another indentation process. In the example shown, approximately 95% of the sphere diameter is enclosed by the polymer material of the polymer coating 10.1b, so that only approximately 5% of the sphere diameter protrudes from the polymer coating 10.1b. The plastic-ceramic-metal composite component 120a has electrically and EMC insulating properties.

[0067] Fig. 4C illustrates an enlarged schematically simplified section of a Fig.3 in the form of a sandwich structure 55 according to an embodiment of the invention. The first component 10.1 is a metal component 10.1a with a polymer coating 10.1b, and the second component 10.2 is a polymer film. The ceramic microspheres 45 represent a tribological protective layer within the plating interface of the two components 10.1 and 10.2. The plastic-ceramic-metal composite component 120b has electrical and EMC insulating properties.

[0068] Fig. 4D illustrates an enlarged schematically simplified sectional view of a Fig.3 in the form of a sandwich structure 55 according to an embodiment of the invention. The first component 10.1 is a metal component 10.1a with a polymer coating 10.1b, and the second component 10.2 is a metal foil. The ceramic microspheres 45 represent a tribological protective layer within the plating interface of the two components 10.1 and 10.2. The plastic-ceramic-metal composite component 120c has electrical and EMC insulating properties.

[0069] The advantages of the present invention are manifold: The method according to the invention enables the provision of tribologically highly resilient surface areas in polymeric and optionally additionally metallic materials by mechanical introduction or plating of ceramic microspheres.

[0070] According to the invention, a tribologically resistant surface coating is easily applied to polymeric and optionally metallic materials using a rolling process or another indentation process. The spherical shape of the applied ceramic particles results in lower tribological stress on the contact surfaces and the coating system compared to the use of conventional hard material particles. Furthermore, a reduction in the thermal conductivity of the surface is achieved.

[0071] In addition to providing complete components with a tribologically resistant coating, it is also possible to use it as a wear-resistant and chemically resistant insert / attachment element for conventionally manufactured components, which can be easily replaced if necessary, or as a wear protection or friction layer applied locally to existing components. By using a rolling process in which the majority of the hard particles are in one plane, comparatively small element layer thicknesses of up to 10 mm can be achieved. For example, the component can be designed as a tribologically effective platelet that can be easily attached to an existing component to be protected using conventional joining methods such as screwing, gluing, or clamping, thus creating a cost-effective, tribologically optimized complete component.

[0072] By selecting ceramic microspheres with essentially the same diameter, they are arranged at virtually the same height after the rolling process, providing a uniform surface profile under tribological stress. This is particularly easy to achieve when using polymer-coated metal materials, since the metal surface determines the penetration depth of the microspheres due to the lower softening temperature of the polymer material.

[0073] By using spherical ceramic particles, the surface is less abrasive to the tribological partner than typical hard material particles. By embedding these microspheres into the material surface, improved tribological properties can be achieved, potentially allowing for the replacement of tribologically resistant materials currently in use. This results in an overall improvement of the tribological system.

[0074] By using ceramic microspheres as an intermediate layer in a conventional plating process, a very intensive bonding of the particles can be achieved while simultaneously clearly defining a wear limit. The overlying material layer—either the same or different from the underlying polymer material coated with microspheres—can be selected so that the tribologically effective ceramic layer is exposed after a short period of time or only under extreme tribological stress.

[0075] Another possibility of using the teaching according to the invention is to use it as a mechanical clamping element when cladding dissimilar construction materials with, for example, very different thermal expansion coefficients or materials that are difficult to join due to their chemical structure.

[0076] The ceramic material is not further limited; in particular, oxidic (oxide-based), carbide (carbon-based) or nitridic (nitride-based) ceramics are used.

[0077] The ceramic microspheres, preferably selected from yttrium- or cerium-stabilized zirconium oxide spheres or aluminum oxide spheres, in the appropriate uniform size (with a narrow size distribution), particularly while producing technically relevant surface layers in the range of 0.01 mm (10 µm) - 10 mm, particularly preferably 0.5 - 5 mm, are already commercially available as grinding balls for bead mills and are thus optimized for high hardness and minimal abrasion. In contrast to typical hard material particles, such as SiC, these exhibit a lower abrasive effect on the tribological partner when exposed due to their spherical shape.

[0078] The variability of the components is very large: For example, a plastic component or a metal component with at least one plastic surface can be used as the first component and, if necessary, a plastic component, a metal component or a metal component with at least one plastic surface can be used as the second component.

[0079] According to the invention, application is possible to all typical polymer materials, especially thermoplastic polymer materials. Chemically inert polymers or polymers with high chemical and thermal resistance are preferred. For example, a lack of thermal strength in polymer materials can be easily compensated for by using a metallic carrier system. Examples of usable metals include aluminum, aluminum alloys, copper, copper alloys, titanium, titanium alloys, iron, iron alloys, unalloyed steel, low-alloy steel, high-alloy steel, nickel or nickel alloys, and coated steel, such as hot-laminated steel or galvanized steel.

[0080] The invention therefore also finds application, for example, for polymers or metal materials that are tribologically unstable without a coating.

[0081] When using coated, highly corrosion-resistant materials, such as Cr, CrNi, CrNiMo steel, Ni-based materials, titanium and the like, use in highly chemically stressed environments is also possible, since local penetration of the polymer can be compensated by the resistance of the underlying material.

[0082] According to the invention, it is therefore possible to provide a composite material that is mechanically more tribologically resistant than the purely polymeric construction material by roll cladding with ceramic balls or by incorporating them within the separating surface of a classic roll cladding as a tribological barrier layer.

[0083] In a particularly preferred variant, the diameter of the ceramic microspheres is selected such that, when used in a single layer in the rolling process or in the pressing or indenting process, a sphere is enclosed by the polymeric material of a component to at least 30%, particularly preferably between 30 and 95% of the sphere diameter. This results in particularly good adhesion of the ceramic microspheres, whereby the presence of a binder system to adhere the microspheres to the component surface is no longer necessary. The binder system preferably serves only to fix the ceramic microspheres prior to embedding by the rolling process and is subsequently superfluous.

[0084] The coating comprising ceramic microspheres can be applied to a component such that up to 95% of the coated surface, preferably up to 85% of the coated surface, even more preferably up to 75% of the coated surface, in particular up to 70% of the coated surface of the component is comprised of ceramic microspheres. Therefore, full-surface coatings with the ceramic microspheres are not required.

[0085] When using ceramic microspheres as an intermediate layer or ply between two identical or different components, the diameter of the ceramic microspheres can preferably be selected so that the component materials can form an intimate, enclosing bond with the spheres. The penetration, in particular the penetration depth into the surface(s) of the component(s) can be specifically controlled by selecting the sphere diameter, controlling the rolling or press-fitting process, if necessary, adjusting the thickness of the existing plastic surface, and optionally heating the component(s). By introducing the microspheres, the parting plane between the two cladding materials can be advantageously enlarged, thus optimizing the adhesion strength of the cladding.

[0086] If metallic materials are used in one or both components, the combination of metal and polymer reduces the thermal conductivity of the surface. In addition, electrical and EMC (electromagnetic compatibility) insulating properties are achieved. This means that tribologically highly resistant components are created that possess chemical and thermal resistance while simultaneously providing electrical and electromagnetic insulation and shielding properties, which are of particular interest in the field of electromobility. List of reference symbols: 10.1 first component 10.1a Metal component 10.1b Polymer coating 10.2 second component 12 Plastic surface of the first component 14 Surface of the second component 15 Intermediate layer 20a, 20b 25.1, 25.2, roller 25.3, 25.4 Heating device 30 dispensers 35.1, 35.2 Scraper device 40 Coating 45 ceramic microspheres 55 Sandwich structure 110 Plastic-ceramic composite component 120a, b, c Plastic-ceramic-metal composite component QUOTES CONTAINED IN THE DESCRIPTION

[0000] This list of documents submitted by the applicant was generated automatically and is included solely for the convenience of the reader. This list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions. Cited patent literature

[0000] EP 0 037 536 B1

[0003] DE 10 2010 047 279 A1

[0004] DE 2 311 507

[0005]

Claims

[1] Method for producing a plastic-ceramic composite component (110), comprising the following steps: (1) applying a coating (40) comprising or consisting of ceramic microspheres (45) to at least part of a plastic surface (12) of a component (10.1); (2) pressing the ceramic microspheres (45) into the plastic surface (12) of the component (10.1) in a rolling process or by means of another pressing or pressing process to obtain the plastic-ceramic composite component (110). [2] Method according to claim 1, characterized by that a metal component (10.1 a) with at least one plastic surface (12) is used as the component (10.1) in order to produce a plastic-ceramic-metal composite component (120a). [3] Method according to claim 1 or 2, characterized bythat before step (2), a second component (10.2) which has at least one plastic or metal surface (14) is fed in such a way that a coating (40) applied to the first and / or second component (10.1, 10.2) is present between the plastic surface (12) of the first component (10.1) and the plastic or metal surface (14) of the second component (10.2), and the pressing of the ceramic microspheres (45) in step (2) is carried out simultaneously into both surfaces (12, 14) of the components (10.1, 10.2) in a rolling process or by means of another pressing or press-in process, whereby a plastic-ceramic composite component (110, 120a) or a plastic-ceramic-metal composite component (120b, 120c) is obtained. [4] Method according to claims 1 to 3, characterized bythat the ceramic microspheres (45) are selected from the group consisting of zirconium oxide spheres, zirconium mixed oxide spheres, in particular yttrium-stabilized zirconium oxide spheres or cerium-stabilized zirconium oxide spheres, zirconium silicate spheres, in particular sintered zirconium silicate spheres, aluminum oxide spheres, steatite spheres or mixtures thereof. [5] Method according to one of claims 1 to 4, characterized by that the ceramic microspheres (45) are used with a sphere size in the range of 0.01 mm to 10 mm, more preferably 0.05 to 9 mm or 0.1 to 8.5 mm or 0.2 to 8.0 mm or 0.3 to 7.5 mm, even more preferably 0.35 to 7.0 mm or 0.4 to 6.5 mm or 0.45 to 6.0 mm, very particularly preferably in the range of 0.5 to 5.0 mm. [6] Method according to one of claims 1 to 5, characterized bythat a plastic component or a metal component (10.1a) with at least one plastic surface (12) is used as the first component (10.1) and optionally a plastic component, a metal component or a metal component with at least one plastic surface (14) is used as the second component (10.2). [7] Method according to one of claims 1 to 6 characterized by , that one or more polymers are selected for the plastic of the plastic surface (12, 14) or the plastic component; preferably chemically inert polymers, in particular selected from the group consisting of polyethylene, polypropylene, polyvinyl chloride; more preferably, chemically and thermally highly resilient polymers, in particular selected from the group consisting of polyoxymethylene, polycarbonates, polyaryletherketones (PEAK), such as polyetheretherketone (PEEK), polyetherketone (PEK), polyetherketoneketone (PEKK) or polyetherketoneetherketoneketone (PEKEKK), polyimide, polyamideimide, polyphenylene sulfide, polytetrafluoroethylene (PTFE); or mixtures of all of the above-mentioned polymers. [8] Method according to one of claims 2 to 7 characterized by that the metal of the metal surface (14) or of the metal component (10.1a) is selected from aluminum, aluminum alloys, copper, copper alloys, titanium, titanium alloys, iron, iron alloys, unalloyed steel, low-alloy steel, high-alloy steel, nickel or nickel alloys, coated steel, such as hot-laminated steel sheet or galvanized steel sheet. [9] Method according to one of claims 1 to 8, characterized bythat at least one, at least two or more of the following conditions are met: - before step (1), a pretreatment of the component(s) (10.1, 10.2) is carried out, in which an alignment of the component(s) (10.1, 10.2) and optionally a preheating of the component(s) (10.1, 10.2) is carried out; - a coating (10.1 b) comprising one or more polymers is selected as the plastic surface (12, 14); - before applying the coating (40) in step (1), an adhesion-promoting layer is applied to the component(s) (10.1, 10.2); - in step (1), the application of the coating (40) is carried out by a coating process, in particular a screen printing process or inkjet printing process, or by local distribution by means of a dispenser (30) onto the component(s) (10.1, 10.2); - after application of the coating (40) in step (1), the layer thickness is adjusted, in particular using a stripping system; - before and / or during the implementation of step (2), the component(s) (10.1, 10.2) are heated and, if necessary, kept warm; - the ceramic microspheres (45) in the coating (40) are selected so that all have the same sphere diameter with a narrow size distribution; - the coating (40), comprising or consisting of ceramic microspheres (45), is applied in such a way that a layer of ceramic microspheres (45) is present; - the coating (40) has a layer of ceramic microspheres (45) and the sphere diameter of the ceramic microspheres (45) is selected such that a sphere is enclosed by polymeric material of the component (10.1) to at least 30%, particularly preferably between 30 and 95% of the sphere diameter, in the rolling process or an alternative indentation or pressing process; - the coating (40), comprising ceramic microspheres (45), is applied to the component (10.1) such that up to 95% of the coated surface, more preferably up to 85% of the coated surface, even more preferably up to 75% of the coated surface, in particular up to 70% of the coated surface of the component (10.1) represents ceramic microspheres (45); and / or - if a metal component (10.1a) with at least one plastic surface (12, 14) in the form of a polymer coating (10.1b) is used as the first and / or second component (10.1, 10.2), the respective penetration depth of the ceramic microspheres (45) into the polymer coating (10.1b) during the rolling process, which penetrate only as far as the metal component (10.1a), can be determined by adjusting the layer thickness of the polymer coating (10.1b). [10] Plastic-ceramic composite component (110) or plastic-ceramic-metal composite component (120a, 120b, 120c) manufactured according to the method according to one of claims 1 to 9. [11] Plastic-ceramic composite component (110) or plastic-ceramic-metal composite component (120a, 120b, 120c) according to claim 10, comprising a component (10.1) having at least one plastic surface into which ceramic microspheres (45) are at least partially pressed by a rolling process or by another pressing or pressing process; or a first component (10.1) having at least one plastic surface (12), and a second component (10.2) having at least one plastic or metal surface (14), between which there is an intermediate layer (15) of ceramic microspheres (45) which are at least partially pressed into the plastic surface (12) of the first component (10.1) and into the plastic or metal surface (14) of the second component (10.2) by a rolling process or by another pressing or pressing process. [12] Plastic-ceramic composite component (110) or plastic-ceramic-metal composite component (120a) according to claim 10 or 11, characterized bythat the component (10.1) is a plastic component or a metal component with at least one plastic surface (12) which has a layer of ceramic microspheres (45), wherein the sphere diameter of the ceramic microspheres (45) is selected such that a sphere is enclosed by the polymeric material of the component (10.1) to at least 30%, particularly preferably between 30 and 95% of the sphere diameter, in the rolling process. [13] Plastic-ceramic composite component (110) or plastic-ceramic-metal composite component (120a) according to one of claims 10 to 12, characterized bythat the component (10.1) is a plastic component or a metal component (10.1a) with at least one plastic surface (12) which has a layer of ceramic microspheres (45), wherein the layer of ceramic microspheres (45) is applied to the component (10.1) in such a way that up to 95% of the coated surface, more preferably up to 85% of the coated surface, even more preferably up to 75% of the coated surface, in particular up to 70% of the coated surface of the component (10.1) represents ceramic microspheres (45).

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