DE10317795A1 - Object with layers of composite material comprising a first nonmetallic layer and a second metallic layer applied to the first layer and containing polymer useful for various rollers and for turbomolecular pump components - Google Patents

Abstract

An object with layers of composite material comprising a first nonmetallic layer and a second metallic layer applied to the first nonmetallic layer which contains at least one polymer. The boundary layer between the two layers has a roughness of maximum Ra value 5 micron, an adherence strength of at least 12 N/mm, and a standard adherence deviation of 25% at maximum of the mean arithmetic mean value, distributed over the surface of the composite material as measured by 6 different measurements.

Description

The The present invention relates to an object with a layer composite, consisting of a polymer and a metallic on it Layer.

Such objects are known and are used in particular in the decorative field, such as. chrome-plated items made of ABS (acrylic / butadiene / styrene plastics) or polymer blends, in particular moldings, shower heads, radiator grill of automobiles, coffee pots.

Such Composites have no significant adhesive strengths, so - regardless of decorative properties - such objects no technical functions in terms of wear protection, Corrosion protection, stiffening, mechanical, thermal and / or chemical stress can.

In recently, The past has considerations given, composite materials or surfaces made of such composite materials to develop with such functions.

On The method for producing such layers is thermal spraying. Here metallic particles are heated and onto the one to be coated Substrate accelerates. This can create metallic layers be made on plastics. With this procedure you can however exclusively Coating geometrically simple components. The main disadvantages are above about this procedure in addition, that the layers have high porosity, high internal stress, high thicknesses and insufficient liability for have mechanically highly stressed components.

A another possibility for the production of such composite materials is the vapor deposition of Metal on plastic in a vacuum (CVD / PVD process). Herewith closed metallic coatings on non-metallic Substrates, such as plastics, applied. This method is for Components with larger dimensions economically unsuitable. Furthermore, components with recesses or cavities not completely metallized. Have the items made in this way a metal layer with a thickness of at most 3 µm, which for many technical application is not sufficient. Furthermore they have Composite layers only have a very low adhesive strength.

There is also a process for special plastics in which the objects to be coated are first swollen with suitable substances and then chemically etched. The achieved adhesive strength of the applied metal layer on the plastic is a maximum of 2 N / mm ² .

On The main disadvantage of this method is the considerable environmental impact through the two chemical treatment agents, so this process no longer used for environmental policy reasons can be.

Further is known from the dissertation by H. Sauer, Siegen 1999, composite materials made of a plastic and a metal layer on it to produce, before applying the metallic layer the plastic surface roughened using an abrasive and then with a special one Ethanol / calcium carbonate suspension is treated.

Such Composites have an extraordinarily high adhesive strength the metal layer on the plastic substrate.

Indeed are no larger areas in the process described there industrial scale produced. About that also have the so available Layers the disadvantage that small amounts of calcium carbonate in the boundary layer between the plastic substrate and the metal layer remains, so that a "predetermined breaking point" arises. This "predetermined breaking point" leads to that the adhesive strength in different places of an object is quite different. These deviations cause the posts with the lowest adhesive strengths for mechanically very high loads objects early lead to defects.

task the present invention is to provide an object that is mechanically extremely resilient and its surface is completely or partially a composite consisting of at least a polymer and a metal layer, which the previously described Overcomes disadvantages of the prior art.

The object is achieved according to the invention by an object with a layer composite, comprising a first non-metallic layer and a second metallic layer applied thereon, the first non-metallic layer containing at least one polymer, the boundary between the non-metallic and metallic layer having a roughness with a R _a - Has a value of at most 5 μm and the metallic layer has an adhesive strength of at least 12 N / mm ² and a standard deviation of the adhesive strength at six different measured values distributed over the surface of the layer composite of at most 25% of the arithmetic mean.

To determine the roughness values R _a and the adhesive strength, a sample is taken from an object according to the invention and a cross-section is made in accordance with the method given below.

at cross-section production is particularly difficult that the interface between substrate and surface can be destroyed or replaced very quickly by processing can. To avoid this, every cross-section is made used a new cutting disc from Struer type 33TRE DSA No. 2493. About that In addition, care must be taken to ensure that the contact pressure generated by the cutting disc is transferred to the substrate coating, so directed is that the force from the coating towards the substrate runs. When separating, make sure that the contact pressure is so as low as possible is held.

The sample to be examined is placed in a transparent investment material (Epofix putty, available from Struer). The embedded sample is ground on a table grinding machine from Struer, type KNUTH-ROTOR-2. Different sanding papers with silicon carbide and different grain sizes are used. The exact order is as follows:

During the Water is used to remove the abrasive particles. The tangential force that occurs at the cross section and due to friction arises, is directed so that the metallic layer against the non-metallic substrate is pressed. This effectively prevents that the metallic layer differs from the grinding process peels off non-metallic substrate.

Then will the sample treated in this way with a motor-operated preparation device of the DAP-A type from the Struer company. The usual sample winder is not used, rather, the sample is only polished by hand. ever depending on the substrate to be polished, a speed of between 40 to 60 U / min and a contact force between 5 and 10 N applied.

The Cross section is then undergo an SEM image. For the determination of the boundary line enlargement becomes the boundary line the layer between the non-metallic substrate and the metallic surface 10,000x magnification determined. The program OPTIMAS from Wilhelm Mikroelektronik is used for evaluation used. As a result, X-Y value pairs are determined, which are the Describe the boundary line between the substrate and the layer. For determination the enlargement of the borderline in For the purposes of the present invention, a distance of at least 100 μm required. The course of the border line is at least 10 measuring points per μm too determine. The boundary line enlargement determines resulting from the quotient of true length by geometric length. The geometric length corresponds to the distance of the measuring section, i.e. between the first and last measuring point. The real length is the length the line that runs through all recorded measurement points.

The surface roughness value R _{a is} determined according to the DIN 4768 / ISO 4287/1 standard, also using the XY value pairs previously recorded.

The R _a value is a measurement-reproducible measure of the roughness of surfaces, whereby profile outliers (ie extreme valleys or hills) are largely ignored due to the area integration.

The adhesive strengths (specified in N / mm ² ) of the composite materials according to the invention are determined exclusively on the basis of the front tensile test according to DIN 50160:
The forehead tensile test (vertical tensile test) according to DIN 50160 has been used for years to test semiconductors, determine the adhesive tensile strength of thermally sprayed layers and in various coating technologies.

(mit σ_{H exp}: experimentell erfassbare Haftfestigkeit, F_max: Maximalkraft beim Bruch des Verbundes und A_G: geometrische Bruchfläche) die Haftfestigkeit berechnet werden.

To determine the adhesive strength in the forehead tensile test, the layer / substrate composite to be tested is glued between two test stamps and subjected to uniaxial brisk force until it breaks (see Figure 0.1). If the adhesive strength is greater than that of the coating and the layer and substrate break,

(with σ _{H exp} : experimentally detectable adhesive strength, F _max : maximum force when the bond breaks and A _G : geometric fracture area) the adhesive strength can be calculated.

at the base materials of the prior art, which is a metallic Hold the layer on a microstructured plastic surface, are traces of calcium carbonate due to the manufacturing process detectable. These contaminants are required by the Pretreatment using a suspension of ethanol and calcium carbonate brought in. A possible Explanation for the improved uniformity the adhesive strength of the articles according to the present invention can be seen in the fact that the remaining proportion of foreign components is so reduced that it is no longer used as a release agent or also Separating layer between plastic surface and metallic layer acts.

The The proportion of calcium in the interface is determined using EDX spectroscopy.

example for one such subject matter of the invention are pump housings and corresponding runners (Impeller) of fuel pumps for the automotive industry. at these items are those made of thermoplastics, in particular of polyoxymethylene (POM) and polyphenylene sulfide (PPS). This is particularly preferred Phenolic resin PF used. After the pretreatment described above these fuel pump parts are de-energized with a chemical nickel layer coated in a thickness of 5 μm. The corresponding objects according to the invention are characterized by a particularly high protection against corrosion and wear. The downtimes of the objects so produced are - compared with those of the prior art - increased by a factor of 100.

In a preferred embodiment of the present invention, the boundary layer between the non-metallic layer and the metallic layer in addition to a R _a value of maximum 5 microns and an adhesive strength of at least 12 N / mm ² with a standard deviation of the adhesive strength of six different measured values distributed over the surface of the layer composite of at most 25% of the arithmetic mean value, and also a roughness with an R _z value of at most 35 μm.

The R _z value is a measure of the average vertical surface fissure.

The above-described values for the roughness (R _a and R _z value) and for the adhesive strength are achieved if the polymer of the non-metallic layer is not selected from polypiopylene and / or polytetrafluoroethylene.

Consequently, these polymers are not used when an adhesive strength of more than 6 N / mm ^{2 is} crucial.

According to one another embodiment of the present invention the non-metallic substrate is at least one fiber-reinforced polymer, especially a carbon fiber reinforced polymer, and the diameter the fiber is less than 10 μm.

Provided the composite materials are not only subject to thermal stresses but also mechanical reinforced plastics are particularly preferred used, in particular plastic fiber reinforced plastics (CFRP), glass fiber increased Plastics (GRP), including plastics reinforced with Aramite fibers or mineral fibers increased Plastics.

On this way become objects obtained from high rigidity with very low weight, the one show excellent adhesion of the metallic layer. This property profile is for interesting in a wide range of technical applications, such as for example for the aerospace industry and for the automotive industry.

The object of the present invention is equally achieved by an object with a layer composite, comprising a first non-metallic layer and a second metallic layer applied thereon, the first non-metallic layer containing polypropylene and / or polytetrafluoroethylene, the roughness between the non-metallic and metallic layers with an R _z value of at most 35 μm and an R _a value of at most 5 μm and the metallic layer has an adhesive strength of at least 5 N / mm ² and a standard deviation of the adhesive strength at six different, distributed over the surface of the layer composite Has a maximum of 25% of the arithmetic mean.

In cases where the non-metallic layer contains either polypropylene and / or polytetrafluoroethylene, adhesive strengths of at least 5 N / mm ^{2 are} achieved. This is an excellent value, especially in connection with the high uniformity of the adhesive strength, which could not be achieved so far.

Consequently is it possible for the first time objects with a layered composite to provide the special properties in terms of their wettability, their permeability to certain substances (permeability) or also in terms of their tolerance show with blood and blood plasma. A possible application could be such objects made of polytetrafluoroethylene, for example in medical technology, as Membrane for Find pumps or in fuel cell technology.

The object of the present invention is also achieved by an object with a layer composite, comprising a first non-metallic layer and a second metallic layer applied thereon, the first non-metallic layer containing at least one fiber-reinforced polymer, in particular a glass fiber-reinforced polymer, the diameter of the fiber is more than 10 μm, the boundary between the non-metallic and metallic layers has a roughness with an R _a value of at most 10 μm and the metallic layer has an adhesive strength of at least 12 N / mm ² and a standard deviation of the adhesive strength on six different ones the surface of the layer composite has measured values of at most 25% of the arithmetic mean.

With the provision of these objects, a high stiffness of the resulting components is achieved with low weight, which are of interest for their industrial use due to their low cost. In particular, glass fiber-reinforced polymers as part of the non-metallic layer, which have fibers with a diameter greater than 10 μm, are very inexpensive and easy to process. The fiber diameter has a great influence on the roughness, so that, when such materials according to the present invention is achieved a roughness value R _a of at most 10 microns. At the same time, it is possible according to the invention to achieve excellent values for the adhesive strength. In addition, the objects according to the invention have a high uniformity of adhesion. For the first time, this makes it possible to significantly increase the service life for the stressed component. Because even local delamination of the layer composite leads to failure of the entire component. The advantage is particularly serious in the case of components with a surface covered by the layer composite of more than 10 dm ² , that is to say in the case of large components or components with a large surface.

In a further embodiment, the object described above has a boundary between the non-metallic layer and the metallic layer, which has a roughness with an R _z value of at most 100 μm.

Especially for the use of fiber-reinforced polymers with a fiber thickness of more than 10 μm, it is important to achieve the lowest possible R _z values. With this combination it is surprisingly possible to achieve high adhesive strengths with low R _z values in relation to the large fiber diameters used.

According to one preferred embodiment the first non-metallic layer is also the surface of the Object. These surfaces are preferably based on a polymeric material. Fiber-reinforced plastics and thermoplastics are particularly preferred and to name other polymers used industrially.

Is alike but it is also possible objects to use whose first non-metallic layer does not cover the surface of the Object is. So the object can be made of a metallic or ceramic material consist of a first, non-metallic Layer coated is that contains at least one polymer. Examples of such Substrates are painted components (e.g. EX protection for painted items) and anodized or hard anodized aluminum components with a polymer layer located on the conversion layer.

Especially embodiments according to the invention are preferred, which is a standard deviation of the adhesive strength of six different ones surface of the layered composite measured values of at most 15%, especially at most 10% of the arithmetic mean.

On this way is an even higher one guaranteed mechanical strength of the resulting components.

The Polymer of the non-metallic layer is preferably selected from the group of polyamide, polyethylene, polyvinyl chloride, polystyrene, Epoxy resins, polyether ether ketone, polyoxymethylene, polyformaldehyde, Polyacetal, polyurethane, polyetherimide, polyphenyl sulfone, polycarbonate and polyimide.

According to one another, also preferred embodiment of the present Invention is the metallic layer a metal layer deposited without external current, Metal alloy or metal dispersion layer.

On these sages can objects for the first time be provided with a laminate that is excellent Adhesion of the metallic layer to the non-metallic layer exhibit. Even the uniformity the adhesion of the metallic layer plays an essential role for the Suitability of these items as highly stressed components for industrial machines. A Targeted selection of the non-metallic substrate and the one on it metallic layer allows an exact adjustment the property profile to the conditions of the area of application. For example, it is important for CFRP rollers that have a length between 1,000 and 12,000 mm can be used with a constant length Line load to set a precisely defined adhesive strength so the roller meets the requirements for withstands the entire lifespan.

Especially preference is given to the non-metallic layer of the object according to the invention as without external current deposited metal layer applied a copper, nickel or gold layer.

However, it is also possible to apply a metal dispersion layer deposited without external current, preferably a copper, nickel or gold layer with embedded non-metallic particles. You can the non-metallic particles have a hardness of more than 1,500 HV and are selected from the group of silicon carbide, corundum, diamond and tetraborarbide.

This Dispersion layers thus have in addition to those previously described Properties on other functions, for example wear resistance, Surface wetting or emergency running property of the objects according to the invention can be improved.

Likewise can prefer the non-metallic particles have friction-reducing properties have and selected be from the group of polytetrafluoroethylene, molybdenum sulfide, cubic boron nitride and tin sulfide.

The objects according to the present invention initially have a first non-metallic layer as a layer composite, which contains at least one polymer. To produce the layer composite according to the invention, the surface of the non-metallic layer is microstructured in a first step by means of a blasting treatment. The method used is for example in the DE 197 29 891 A1 described. Particularly wear-resistant, inorganic particles are used as blasting media. It is preferably copper-aluminum oxide or silicon carbide. It has proven to be advantageous that the blasting agent has a particle size between 30 and 300 μm. It is further described there that a metal layer can be applied to the roughened surfaces by means of a metal deposition without external current.

How the name of the process already says, in the case of external currentless Metal deposition during of the coating process is not supplied with electrical energy from the outside but the metal layer is made exclusively by a chemical Relation deposited. The metallization of non-conductive plastics in a chemically reductive metal salt solution requires one Catalyst on the surface, to this the metastable balance of the metal reduction bath disturb and on the surface of the catalyst to separate metal. This catalyst exists from precious metal seeds such as palladium, silver, gold and isolated Copper on the plastic surface from an activator bath be attached. It is preferred, however, for reasons of process technology activation with palladium seeds.

in the the substrate surface is essentially activated in two Steps. In a first step, the component is colloidal solution (Activator bath) immersed. The necessary for metallization, already in the activator solution existing palladium nuclei adsorbed on the plastic surface. After germination is done by rinsing in an alkaline, aqueous solution (conditioning) the tin-II or Tin IV oxide hydrate dissolved thereby exposing the palladium seed. After rinsing can with chemical reduction baths be nickel-plated or copper-plated.

This takes place in a metastable equilibrium through a stabilizer held bath, which contains both the metal salt and the reducing agent contains. The baths for the Nickel or copper deposition have the property that is in them dissolved To reduce metal ions on the germs and elemental nickel or To deposit copper. The two reactants must be in the coating bath approach the precious metal nuclei on the plastic surface. Because of this Redox reaction creates the conductive layer, whereby the precious metal nuclei thereby taking up the electrons of the reducing agent and adding them approach of a metal ion again. This reaction turns hydrogen released. After the palladium seeds are coated with nickel or copper were taken over the applied layer has the catalytic effect. This means, that the layer grows together from the palladium seeds until them totally closed is. The deposition is exemplified at this point received from nickel. When coating with nickel, the germinated and conditioned plastic surface in a nickel metal salt bath immersed, which is a chemical in a temperature range between 82 ° C and 94 ° C Allows reaction. The electrolyte is generally a weak acid with a pH value between 4.4 and 4.9.

The thin nickel coatings applied can be reinforced with an electrolytically deposited metal layer. Coating components with layer thicknesses> 25 μm is not economical due to the low deposition rate of chemical coating processes. Furthermore, only a few coating materials can be deposited with the chemical coating processes, so that it is advantageous to use electrolytic processes for other technically important coating materials. Another important point is the different properties of chemically and electrolytically deposited layers with layer thicknesses> 25 μm, for example leveling, hardness and gloss. The basics of electrolytic metal deposition are in B. Gaida, "Introduction to electroplating", EG Leuze-Verlag, Saulgau, 1988 or in H. Simon, M. Thoma, "Applied Surface Technology for Metallic Materials", C. Hanser-Verlag, Munich (1985).

Plastic parts, by an external currentless Coating process have an electrically conductive layer, differ in terms of electrolytic metallization only marginally from those of metals. Still, some should Points in the electrolytic metallization of metallized plastics not except be careful. Due to the usually low conductive layer thickness the current density at the beginning of the electrolytic deposition is reduced become. If this point is ignored, it can become detached and come to burn the conductive layer. Care should also be taken be that distracting Tarnish layers with specially for this suitable decapitation baths be removed. Can continue Residual stresses to destroy lead the shift. When depositing nickel layers from an ammoniacal Can bath for example tensile stresses on the order of 400 to 500 MPa occur. Through additives, like saccharin and butynediol, can change the structure of the nickel plating in shape one changed Grain size and formation micro-deformations promote the reduction of internal tensions, what is on a possible premature coating failure can have a positive effect.

Examples for external currentless applied metal layers are in the manual of AHC Oberflächentechnik in detail described ("The AHC surface "manual for construction and manufacturing, 4th edition, 1999).

On the metallic layer additionally another one or more layers, in particular metallic, ceramic as well as networked or hardened Polymer layers can be arranged.

So for example, is it possible on an external currentless deposited nickel layer as the metallic layer of the present Invention a further, electrolytically deposited nickel layer to apply and deposit a chrome layer on it. The so obtained surfaces can be applied to rollers that have a high surface quality and a must have high mechanical strength. Electrolytic separation The second nickel layer is made to have larger layer thicknesses manufacture inexpensively to be able to.

Of more can things of the present invention as a metallic layer, a copper layer to which subsequently a tin or another copper layer can be applied. Subsequently For example, there will be a gold layer on top of the existing metal layers applied. Such coatings can be used for example for EMC shielding of electronic components or for improvement thermal conductivity of the coated objects Find.

Also can things according to the present Invention have a nickel layer as a metallic layer, to which another nickel layer is applied. In this way Is it possible, to achieve a high rigidity of the resulting plastic parts and such an application for mechanically stressed components such as for gears, suspensions or housing parts to ensure.

Further can be as a metallic layer on an object according to the present Invention present a copper layer with a nickel layer and subsequently covered with a chrome layer can be. A possible Application of such an object is as quick positionable mirror used in copiers and in laser technology to become.

In another application example of the present invention on an external currentless deposited nickel layer an epoxy resin can be applied. The surface this epoxy resin is then coated again with a nickel layer. That way you can across from Hydrocarbons, even under high pressure, diffusion-resistant components for the petrochemical industry, such as pipes and housing to complete Admission of pumps.

A filter housings for high-frequency components are a particularly industrial preferred embodiment in the telecommunications industry, especially for the transmitter mast unit in the mobile communications sector. These are items made from PPS / PEI, their entire surface first with a chemical, external currentless applied nickel / phosphorus alloy in a layer thickness of 6 μm and subsequently with an electrolytically applied silver layer in a thickness covered by 6 μm becomes.

So far became such objects made of aluminum, then nickel-plated and finally silver-plated. This objects of the prior art have significant corrosion problems, especially in congested areas with high emissions. So far had to this filter housing be replaced every 6 months. With the subject of the invention In contrast, the duration of use can be increased to more than 2 years.

Of more can metallic layers not only electrolytically but also with Using other methods such as CVD / PVD or thermal spraying an object with a metallic layer of the present Invention are applied.

On this way it is possible To apply aluminum or stainless steel to an object that is used to Example consists of plastic and with a nickel layer according to the present Invention is provided.

On another interesting example of an object according to the invention is a plastic that initially with an external currentless applied nickel layer is provided. On this nickel layer are then successively layers of silver and gold applied electrolytically. Such a, rather special, sequence of layers takes place in medical technology Application for components for diagnostic devices.

All in all show the above Examples that the objects of the invention in a very wide range technical applications can be used.

On Subject according to the present The invention can, for example, process a roller for the web goods Industry (foils, paper, textiles, printers), components from Turbomolecular pumps (rings for the compressor stage), handles for domestic appliances (Pots, Cover), components (handles, handrails, sun sails) for the air and space industry, components for the electronics industry (capacitors, Sound field capacitors, sound riders, microwave waveguides, switch surfaces), components for the moving components of cyclones, air classifiers, mechanical, thermal and / or chemically stressed components for the automotive industry (brake pistons for automobiles) or molds or components for Represent injection molding industry.

Example (according to the invention)

A plate made of polyamide-6 with the dimensions 200 x 100 x 12 mm with an initial roughness of R _a = 0.64 μm and R _z = 7.5 μm was surface-treated:
The surface pretreatment is carried out with a modified pressure jet system from Straaltechnik International. The blasting system is operated at a pressure of 4 bar. A boron carbide nozzle with a diameter of 8 mm is used as the jet nozzle. The beam duration is 4.6 s. SiC with P80 grit with an average grain diameter of 200 to 300 μm is used as the abrasive.

Around the blasting system specifically for the requirements of plastic modification adapt with regard to reproducible surface topographies, were 2 pressure cycles installed, one for each the transport of the abrasive and the actual acceleration process. This modification resulted in a very constant volume flow and a big Print area.

On Compressed air flow transports the abrasive with one if possible low pressure to the nozzle. The flow conditions guarantee, caused by a high volume flow of the abrasive and a low proportion of compressed air, low wear and tear on the system and the abrasive. Only at the end of the transport hose the mixing nozzle the cross-section is reduced to set the desired volume flow. A constant volume flow was used for all plastic pretreatments of 1 l / min. In the second part of the system flows up to Compressed air nozzle (Volume flow 1), which is infinitely variable in a pressure range of 0.2–7 bar can be adjusted. The abrasive, which has a very low flow rate into the mixing nozzle promoted is then due to the high flow velocity of the compressed air flow accelerated.

The we roughened the plate into an ultrasonic bath with a mixture from deionized water and 3% by volume butyl glycol for five minutes treated long.

• (1) Aktivatorvortauchlösung: Dient zur Vermeidung der Einschleppung von Verunreinigungen und zur vollständigen Benetzung der Probe vor dem eigentlichen Aktivieren der Oberfläche. Tauchzeit: 2 min, Raumtemperatur
• (2) Aktivator GS 510: Aktivierung der Oberfläche mit Zinn/Palladium-Kolloid. Tauchzeit: 4 min, Raumtemperatur
• (3) Spülbäder: entionisiertes Wasser Vermeidung der Einschleppung von Aktivator GS 510-Bestandteilen durch Spülen in entionisiertem Wasser. Tauchzeit: 1 min, Raumtemperatur
• (4) Conditioner 101: Konditionierung der Werkstoffoberfläche durch Ablösen störender Zinnverbindungen von der Oberfläche. Tauchzeit: 6 min, Raumtemperatur
• (5) Spülbäder: entionisiertes Wasser. Tauchzeit: 1 min, Raumtemperatur
• (6a) Chemisches Nickelbad SH 490 LS: Metallisieren der Kunststoffe mit einer hellen, halbglänzenden amorphen Schicht bei einer Abscheidetemperatur von 88–92°C. Tauchzeit: 10 Minuten

The bath series used for the metal deposition of the conductive layer are based on the well-known col loidal palladium activation in conjunction with a final catalyzed metal reduction. All of the bath rows required for this were purchased from Max Schlötter. The diving sequences, treatment times and temperatures specified by the manufacturer were observed in all process steps of nickel deposition:

• (1) Activator pre-immersion solution: Used to avoid the introduction of contaminants and to completely wet the sample before the surface is actually activated. Diving time: 2 min, room temperature
• (2) Activator GS 510: activation of the surface with tin / palladium colloid. Diving time: 4 min, room temperature
• (3) Rinsing baths: deionized water Prevention of activator GS 510 components by rinsing in deionized water. Diving time: 1 min, room temperature
• (4) Conditioner 101: Conditioning the material surface by detaching annoying tin compounds from the surface. Diving time: 6 min, room temperature
• (5) Rinse baths: deionized water. Diving time: 1 min, room temperature
• (6a) Chemical nickel bath SH 490 LS: Metallizing the plastics with a bright, semi-glossy amorphous layer at a deposition temperature of 88–92 ° C. Diving time: 10 minutes

at the chosen one Dipping time in the nickel bath resulted in a layer thickness of 1.4 μm. This Strength the nickel layer is sufficient for an electrolytic coating. All process steps, that were necessary for the deposition of the conductive layer took place in 50 l plastic tub, whereby in the nickel deposition by an additional Heating plate with temperature control a bath temperature of 90 ° ± 0.5 ° C throughout Coating cycle was observed. To be even and reproducible layer quality to obtain the bath rows after a throughput of 20 samples according to Max Schlötter analyzed and supplemented.

After this the nickel conductive layer was chemically applied, the sample of approx. 90 ° C to approx. 60 ° C in cooled distilled water, then at 55 ° C to be electrolytically coated with nickel. This intermediate step served to avoid the formation of reaction layers and by rapid cooling to exclude internal stresses. The samples made exclusively with a nickel conductive layer were cooled in a distilled Water bath slowly up to 25 ° C from.

The cross-section examination by SEM (1,500 times and 3,000 times) are shown in the following figures ( 1 ) reproduced.

The Evaluation of the EDX analysis showed a residual amount of calcium of 0.03 Wt.%.

The Results of the adhesive strength tests are shown in Table 1.

Fig. 1

Table 1

Comparative example (not according to the invention) The example according to the invention is repeated, but after the blasting treatment the plate is treated in an ultrasonic bath in a suspension of 5% by weight CaCO ₃ in 96% ethanol for 5 minutes.

Then will the plate in another ultrasonic bath with pure, 96% Ethanol for another five Treated for minutes.

The cross-section examination by SEM (1,500 times and 3,000 times) are shown in the following figures ( 2 ) reproduced.

The evaluation of the EDX analysis showed a residual amount of calcium of 0.91% by weight, which comes from the treatment of the CaCO ₃ / ethanol suspension.

The Results of the adhesive strength tests are shown in Table 2.

Fig. 2

Table 2

The Results clearly show a significant difference in the Standard deviation of the adhesive strength of the various over which surface of the composite material.

This difference, for example in the manufacture of rollers for the printing industry, means that rollers with a coefficient of variance of more than 25% show local detachments of the metal layer from the roughened plastic substrate during the necessary post-treatment by grinding, which are low lower adhesive strengths.

comparable Rollers according to the present invention show no peeling during the Grinding process.

Claims (17)

Object with a layer composite , comprising a first non-metallic layer and a second metallic layer applied thereon , characterized in that the first non-metallic layer contains at least one polymer, that the boundary between the non-metallic and metallic layer has a roughness with an R _a value of has at most 5 μm and that the metallic layer has an adhesive strength of at least 12 N / mm ² and a standard deviation of the adhesive strength at six different measured values distributed over the surface of the layer composite of at most 25% of the arithmetic mean. Object according to claim 1, characterized in that the boundary between the non-metallic and metallic layer has a roughness with an R _z value of at most 35 μm. Article according to claim 1 or 2, characterized in that the polymer is not made of polypropylene and / or polytetrafluoroethylene selected is. Article according to one of the preceding claims, characterized characterized in that the non-metallic layer is at least one fiber reinforced Polymer, in particular a carbon fiber reinforced polymer, contains and Diameter of the fiber is less than 10 microns. Object with a layer composite, comprising a first non-metallic layer and a second metallic layer applied thereon, characterized in that the first non-metallic layer contains polypropylene and / or polytetrafluoroethylene, that the boundary between the non-metallic and metallic layer has a roughness with an R _z value of at most 35 μm and an R _a value of at most 5 μm and that the metallic layer has an adhesive strength of at least 5 N / mm ² and a standard deviation of the adhesive strength at six different measured values distributed over the surface of the layer composite of at most 25% of the arithmetic mean. Object with a layer composite, comprising a first non-metallic layer and a second metallic layer applied thereon, characterized in that the first non-metallic layer contains at least one fiber-reinforced polymer, in particular a glass fiber-reinforced polymer, that the diameter of the fiber is more than 10 μm, that the boundary between the non-metallic and metallic layers has a roughness with an R _a value of at most 10 μm and that the metallic layer has an adhesive strength of at least 12 N / mm ² and a standard deviation of the adhesive strength at six different, over the surface of the layer composite distributed measured values of at most 25% of the arithmetic mean. Article according to claim 6, characterized in that the boundary between the non-metallic layer and the metallic layer has a roughness with an R _z value of at most 100 μm. Article according to one of the preceding claims, characterized characterized in that the first non-metallic layer covers the surface of the Object is. Article according to one of claims 1 to 7, characterized in that that the first non-metallic layer does not cover the surface of the Object is. Article according to one of the preceding claims, characterized characterized that the standard deviation of the adhesive strength at most 15%, especially at most 10% of the arithmetic mean. Article according to one of the preceding claims, characterized characterized in that the polymer is selected from the group of Polyamide, polyethylene, polyvinyl chloride, polystyrene, epoxy resins, Polyether ether ketone, polyoxymethylene, polyformaldehyde, polyacetal, Polyurethane, polyetherimide, polyphenyl sulfone, polycarbonate and polyimide. Article according to one of the preceding claims, characterized characterized in that the metallic layer has no external current deposited metal layer, metal alloy or metal dispersion layer. Article according to one of the preceding claims, characterized characterized that the external currentless deposited metal layer a copper, nickel or gold layer is. Article according to one of the preceding claims, characterized characterized that the external currentless deposited metal dispersion layer a copper, nickel or gold layer with embedded non-metallic particles. Article according to claim 14, characterized in that the non-metallic particles have a hardness of more than 1,500 HV and selected are from the group of silicon carbide, corundum, diamond and tetrabor carbide. Article according to claim 14 or 15, characterized in that the non-metallic particles have anti-friction properties have and selected from the group of polytetrafluoroethylene, molybdenum sulfide, cubic boron nitride and tin sulfide. Article according to one of the preceding claims, characterized characterized in that the item is processing a roller for the web goods Industry (foils, paper, textiles, printers), components from Turbomolecular pumps (rings for the compressor stage), handles for domestic appliances (Pots, Cover), components (handles, handrails, sun sails) for the air and space industry, components for the electronics industry (capacitors, Sound field capacitors, sound riders, microwave waveguides, switch surfaces), components for the moving components of cyclones, air classifiers, mechanical, thermal and / or chemically stressed components for the automotive industry (brake pistons for automobiles), Molds or components for the injection molding industry is.