EP2424683A1 - Substrats métalliques avec couche anticorrosion résistante aux rayures et extensible et procédé pour sa fabrication - Google Patents

Substrats métalliques avec couche anticorrosion résistante aux rayures et extensible et procédé pour sa fabrication

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Publication number
EP2424683A1
EP2424683A1 EP10718958A EP10718958A EP2424683A1 EP 2424683 A1 EP2424683 A1 EP 2424683A1 EP 10718958 A EP10718958 A EP 10718958A EP 10718958 A EP10718958 A EP 10718958A EP 2424683 A1 EP2424683 A1 EP 2424683A1
Authority
EP
European Patent Office
Prior art keywords
coating
plasma
metal substrate
range
substrate
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP10718958A
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German (de)
English (en)
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EP2424683B1 (fr
EP2424683B2 (fr
Inventor
Dirk Salz
Klaus-Dieter Vissing
Matthias Ott
Uwe Bultmann
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV
Aalberts Surface Technologies GmbH Landsberg am Lech
Original Assignee
Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV
Impreglon Beschichtungen GmbH Landsberg am Lech
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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/62—Plasma-deposition of organic layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2202/00—Metallic substrate
    • B05D2202/10—Metallic substrate based on Fe
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2202/00—Metallic substrate
    • B05D2202/40—Metallic substrate based on other transition elements
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2202/00—Metallic substrate
    • B05D2202/40—Metallic substrate based on other transition elements
    • B05D2202/45—Metallic substrate based on other transition elements based on Cu
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies

Definitions

  • the invention relates to a method of coating the surface of a metal substrate which is not a light metal substrate.
  • the metal substrate may in particular comprise non-ferrous metal, such as e.g. Brass, nickel silver, bronzes or precious metal, such as silver or gold alloys, but also steel material, e.g. Be stainless steel or tool steel.
  • the layer to be applied is characterized by an advantageous combination of scratch and abrasion resistance, extensibility, possibly transparency and corrosion protection effect. Further layer properties are very good specific electrical insulation effect, chemical and thermal stability, as well as barrier properties.
  • the invention further relates to coated metal substrates.
  • Untreated surfaces of articles for example semi-finished products, sanitary articles, metal strips, in particular steel and brass and copper, instruments, in particular percussion instruments or basins, food processing articles such as pans or baking molds, (stainless steel) containers, for example for the chemical industry, Jewelery, fittings) made of non-light metals, especially brass, copper, steel have a strong susceptibility to corrosion, especially in certain media, such as alkalis or acids, in an aqueous environment, or in contact with finger sweat. In addition, her Scratch resistance comparatively low. Therefore, for. B. brass surfaces often refined by powder coatings or PVD coatings.
  • PVD coatings Often, corresponding surface property improvements are produced by PVD coatings.
  • a disadvantage of PVD coatings is their low extensibility. Typical is a crack elongation (crack-onset strain, elongation to microcracking) of max. 1 to 1.5%, which is thus worse than the metal substrate.
  • the surface is improved, for example by ceramic spray coatings in mechanical wear behavior.
  • this achieves a thermal insulation that can be used for forms of plastics processing.
  • a disadvantage is their granular surface, so that no high-quality components can be produced.
  • a layer of protective lacquer lacquer infiltration often occurs when a surface finish is damaged. The defect increases rapidly. The corrosion protection effect is lost. In addition, strong visual impairments occur. It was an object of the present invention to provide a method with which a protective layer can be produced on a metal substrate which is not light metal, which does not or at least only to a reduced extent have some or all of the disadvantages of the prior art described above.
  • a layer should have improved crack elongation and low residual stresses, so that cold or hot deformation is better possible.
  • an improved chemical stability to alkaline media and generally a good corrosion protection effect is desirable.
  • Such a layer should preferably have a high abrasion and scratch resistance, so that it can also be applied with layer thicknesses of more than 20 ⁇ m.
  • the coating process should be economical, preferably also be carried out in a continuous process.
  • step B coating the optionally cleaned in step A substrate surface in a plasma polymerization reactor by plasma polymerization, wherein
  • step B one or more organosilicon and (a) no further or (b) further compounds are used in step B as precursor (s) for the plasma and in step B the metal substrate is arranged in the plasma polymerization reactor so that it is connected as a cathode,
  • the metal substrate is not a light metal substrate and provided that in case of elongation to micro crack of the coating of ⁇ 2.2%, the hardness to be measured by nano identification is> 6 GPa.
  • Metal in the context of the present invention is a metallic material having a density of> 4.5 g / cm 3 at 2O 0 C. These include in particular iron, nickel, copper, zinc, nickel, lead, chromium and precious metals and their alloys such as Steel, brass and bronze. Preferred metal substrates are brass and copper substrates, and especially steel substrates.
  • a light metal is a metallic material according to the present invention with a maximum density of 4.5 g / cm 3 at 2O 0 C. For metal substrates, the density of the region is crucial for the classification as light metal, on which the coating rests.
  • the metal substrate is preferably a semifinished product which is subsequently deformed in further preferred processes according to the invention.
  • a coating produced by the process according to the invention is characterized by a hitherto unknown advantageous combination of properties which were hitherto considered incompatible, namely good scratch and corrosion resistance with high ductility (crack elongation preferably greater than or equal to 2%, in particular greater or equal 2.5%).
  • a good substrate adhesion, good optical transparency in the visible range and / or high layer thickness homogeneity can be achieved by the method according to the invention.
  • the coating preferably has a thermal conductivity of ⁇ 5 W / m 0 K and preferably an electrical breakdown strength according to DIN 53841 of 10 - 100 kV / mm.
  • Coatings with a yellow index of 2.5 or below generally have no yellowing discernible to the human eye.
  • a minimum yellowing is tolerable, as with a yellow index in the range of over 2.5 to 3.
  • the yellow index is further determined substantially by the proportion of Si-H bonds in the coating produced by the process according to the invention, which, as explained below, is crucial for achieving favorable ranges of hardness and elasticity and thus for achieving the advantageous property combination. If you want to increase the hardness of the coating and / or a slightly yellowish color, which ultimately can lead to an intense gold tone, allowed, so restrictions in the elongation to micro crack must be accepted.
  • the yellow index can be adjusted to 4 without losing the corrosion protection effect. To do this, you can increase the self-bias by increasing performance.
  • Another important parameter is the carbon content in the coating produced by the process according to the invention, which is influenced by the proportion of organic groups. This in turn is just as important for the hardness and elasticity of the coating, which is also desirable for achieving the advantageous property combination. Due to a high elasticity of the coating, this can e.g. be stretched together with the coated article without causing cracking. With very high elasticity of the coating, the substrate can even be plastically deformed without the coating being damaged. As a result, forming processes of the coated material are possible to some extent.
  • the scratch resistance of the layers is in many cases comparatively easy to that of glass surfaces. It turned out, surprisingly, that it is possible by use of the inventive (dry chemical) method, for. B. completely to renounce the (wet chemical) chrome plating (decorative chrome plating). This is advantageous because the chromium plating is an expensive and environmentally problematic process because of the high energy input.
  • the surface properties can be adjusted at the same time as the surface properties of the surface (s).
  • the achievable layer property function is not only of interest as a chromating substitute, but also for the general coating of non-light metals.
  • DE 197 48 240 A1 discloses a method for the corrosion-resistant coating of metal substrates, in particular of aluminum or aluminum alloys, by means of plasma polymerization.
  • precursor (s) at least one hydrocarbon or organosilicon compound is used.
  • DE 197 48 240 A1 does not contain information on the proportion of carbon atoms in the plasma polymer coatings produced or on their yellowness index.
  • the layers disclosed there protect the surface well against corrosion without changing it visually.
  • One limitation, however, is their low scratch resistance.
  • the method disclosed there is not suitable for the low deposition rates, but is economically higher Produce layer thicknesses, as they are necessary for scratch-resistant coatings. For putting in, it places very high demands on the surface roughness of the substrate.
  • WO 03/002269 A2 discloses articles comprising a substrate and a plasma-polymer coating comprising O, C and Si, which are surface-bonded to the substrate, in which the molar ratios of O to Si and C to Si are determined in each case
  • the coatings disclosed therein have at least 25 atomic% of a higher carbon content than the coatings produced by the process according to the invention and do not have the above-mentioned combination of favorable properties. Also, nothing is said about the yellow index to be set.
  • Domingues et al. (2002) Electrochimica Acta 47, 2253-2258 discloses an aluminum alloy with a plasma polymer coating that provides some corrosion protection (as detected by electrochemical impedance spectroscopy).
  • the disclosed coating lacks, in particular, the good scratch resistance and the high ductility which are inherent in the coating according to the invention. Furthermore, they indicate a high water absorption, comparable with that of organic coatings.
  • Domingues et al. contains no information regarding yellowing or carbon content. Due to the procedure (ratio of the gas flows of oxygen to the organosilicon precursor about 23: 1, for details on the influence of these parameters see below) has the in Domingues et al. disclosed coating a lower carbon content than the coating produced by the inventive method.
  • EP 0 748 259 B1 discloses coatings for soft substrates. It is not disclosed that the coatings could be suitable for protecting metal substrates from corrosion. However, the coatings disclosed in EP 0 748 259 B1, which have a yellow index of ⁇ 3, have a nanoindentation hardness of less than 2.5 GPa.
  • the method according to the invention is able to meet the demand for a cost-effective method for producing a thin layer which does not change the surface color of the metal (no intrinsic color and thus has a sufficiently high transmission in the visible range), which polishes the surface structure (eg. grinded, matted) simulates, so that no "gloss lacquer" is formed, which in addition to a high corrosion resistance has a high mechanical resistance (scratch resistance, ductility) and which, even with complex geometries has a high layer thickness uniformity.
  • the layer properties can be set within wide limits as described below.
  • the hardness and the thickness of the coatings which can be produced by the process according to the invention, it is possible for a person skilled in the art to achieve an optimum with regard to the scratch resistance of the coating. If the hardness is too low, the deposited plasma polymer layer is not sufficiently scratch-resistant. However, if the hardness is too high, the scratch resistance will also decrease because the layer will then become too brittle. This can be recognized, for example, in the microscopic assessment of the defect image. Generally, the scratch resistance of the layer is determined by the appropriate choice of layer thickness and composition.
  • the measurement of the hardness by means of nanoindentation is explained in Example 2.
  • the composition of the gas mixture from which the plasma is generated must also be taken into account.
  • a lower self-bias is generally to be chosen than at a low. The more readily a precursor can be ionized, the lower the plasma power must be to achieve a given self-bias. With a high electrical conductivity of the plasma, a low plasma power is needed to achieve a given self-bias.
  • step B Preference is given to a method according to the invention, wherein a control takes place during step B, so that the self-bias is in the range from 50 to 1000 V, preferably in the range from 100 to 400 V, preferably in the range from 100 to 300 V.
  • the self-bias can e.g. be reduced with constant plasma power by the plasma excitation frequency is increased.
  • it can be set or adjusted by applying an additional DC voltage to the electrode, so that it can be adjusted in accordance with the process parameters.
  • An increase in the self-bias also causes an improvement in the layer thickness homogeneity. For example, it could be determined in own experiments that on a round substrate with a diameter of 10 cm, the maximum layer thickness can differ from the minimum layer thickness at 100 V self-bias by a factor of 1. 1, while this factor at 200 V self -Bias can be 1, 005.
  • step B the metal substrate in the plasma polymerization reactor is arranged so that it is connected as a cathode.
  • the metal substrate acts when in direct electrically conductive contact with the portion of the cathode which is distinguishable from the metal substrate. This facilitates the achievement of a high rate of deposition of the positively charged ions of the plasma attracted to the cathode.
  • the substrate itself acts as a cathode, the kinetic energy at which the positively charged ions impinge on the surface is increased.
  • the structure of the layer changes in the direction of a smaller proportion of organic (usually consisting mainly of C and H) groups and a correspondingly higher proportion of Si and O. The same effect also occurs (possibly reduced) when the substrate Although not acting as a cathode, but is arranged in the acceleration path of the cations.
  • no separate ion source is used in the process according to the invention.
  • increased kinetic energy of the ions facilitates the knocking off of organic groups in both the layering ions and the resulting coating, with the cleaved groups having a low probability of being trapped Layer to be installed.
  • the high kinetic energy of the impacting ions reduces the internal stress (residual stresses) of the layer, which increases the strain to microcracking of the layer.
  • layer thickness ranges of considerably more than 30 ⁇ m with this method For measuring the elongation to microcrack (crack elongation), compare Example 1.
  • the layers which can be produced by the process according to the invention are organically modified SiO 2 frameworks.
  • the organic components can be detected in the IR spectrum by bands at about 2950 cm -1 and at about 1275 cm -1 .
  • they can be detected by measuring the surface energy with test inks. The higher the proportion of organic groups, the lower the surface energy. Therefore, the higher the self-bias is set, the greater the surface energy.
  • step B the self-bias is set on the substrate.
  • the dependence of the deposition rate and the layer properties of self-bias has already been explained. If the self-bias is set directly on the substrate and thus on the object to be coated, this facilitates the achievement of a layer with the desired precisely defined properties.
  • a regulation is preferably carried out during step B, so that the self-bias is constant.
  • the structure of the layer can be precisely controlled.
  • Advantages of a self-bias which is as constant as possible are a homogeneous layer structure and a simple process transfer to a variety of substrates or a plurality of substrates.
  • the self-bias is controlled directly. If the plasma power is regulated, the self-bias will generally not be completely constant, but will fluctuate by a certain amount. In such a case, it is preferable that the total fluctuation width of the self-bias is at most 5% of the time average, preferably at most 3%.
  • a regulation takes place during step B so that the self-bias on the substrate is in the range from 50 to 1000 V. , preferably in the range of 100 to 400 V, more preferably in the range of 100 to 300 V, in particular such that the self-bias is constant.
  • an AC voltage be applied to the metallic substrate so that a self-bias is formed on the metallic ribbon.
  • a microwave discharge in spatial proximity to the unwound strip can burn and thus provide the necessary high number of ions.
  • a method according to the invention is particularly preferred (in particular in combination with one or more features of another method described as preferred or particularly preferred), wherein the bias applied to the electrode is not determined solely by the plasma process parameters, but increased by an additional external DC voltage or is lowered. This is particularly important if the electrode surface is chosen to be large and a DC voltage increase becomes necessary for this reason.
  • An increase in the inflow of the organosilicon precursor (s) (in relation to optionally also inflowing O 2, in particular keeping the total inflow constant) generally causes a reduction in the hardness, an increase in the visible absorption (increase in the yellow index) Deterioration of the corrosion protection effect and an improvement in crack elongation.
  • Si-H bonds With a high number of Si-H bonds in a layer according to the invention, an increased absorption of light of the ultraviolet and blue spectral range can be detected in the UV / Vis spectrum. This leads to an undesirable yellowing (increase in the yellow index). It is therefore desirable not to make the proportion of Si-H bonds too large. A reduction in self-bias prevents the formation of Si-H bonds in the coating. Likewise, the formation of Si-H bonds can be inhibited by a suitable selection of the amount and / or type of precursor (s). This is usually achieved by a reduction in the inflow of organosilicon precursors, which also reduces the proportion of organic groups in the coating. The occurrence of Si-H bonds can also be detected in the IR spectrum (2150 to 2250 cm -1 ).
  • the formation of Si-H bonds in the coating is also reduced when a sufficient amount of oxygen is added to the plasma, which also reduces the level of organic groups in the coating.
  • oxygen in the form of O 2
  • all the substances supplied to the plasma in step B are gaseous before they enter the plasma polymerization reactor.
  • An increase in the oxygen supply leads to an increase in hardness, a reduction in visible absorption (reduction in yellowness index), an improvement in the corrosion protection effect, a reduction in the content of organic groups in the coating and a reduction in crack elongation.
  • oxygen (O 2 ) is supplied to the plasma, all the substances supplied to the plasma in step B are gaseous before entering the plasma polymerization reactor and the ratio of the oxygen and other precursor gas flows supplied to the plasma in step B is greater (s) (in particular organosilicon precursors) in the range of 1: 1 to 6: 1, preferably 3: 1 to 5: 1.
  • s in particular organosilicon precursors
  • the O 2 flux can be increased.
  • the inflow of the organosilicon precursor (s) or the self-bias can be reduced. If the coating is too hard and therefore too brittle, the self-bias can be reduced or the inflow of the organosilicon precursor (s) can be increased.
  • the thermal conductivity, as well as the electrical conductivity is only slightly changed by the change in the actual plasma parameters within the claimed coating. Only the layer thickness is an essential parameter, so that it is possible to adapt the mechanical requirements of the coating as well as possible to the problem.
  • step B as precursor (s) for the plasma one or more siloxanes, optionally oxygen (O 2 ) and preferably no further compounds are used.
  • Siloxanes in particular hexamethyldisiloxane (HMDSO)
  • HMDSO hexamethyldisiloxane
  • the precursor (s) used for the plasma are HMDSO, optionally oxygen, and preferably no further compound.
  • An increase of the inflow of HMDSO in relation to oxygen causes inter alia Lowering of the hardness, an increase of the absorption in the visible range and a deterioration of the corrosion protection effect.
  • a method according to the invention in which oxygen is supplied to the plasma in step B, all substances supplied to the plasma in step B are gaseous before entering the plasma polymerization reactor, the ratio of the gas flows of oxygen and further precursor supplied to the plasma in step B. en) is in the range from 1: 1 to 6: 1 and is used as precursor (s) for the plasma HMDSO, oxygen and in particular no further compound.
  • Pressure of less than 1 mbar preferably carried out in the range of 10 3 to 10 ⁇ 1 mbar.
  • step B is preferably up to a thickness of the deposited coating of greater than or equal to 2 .mu.m, preferably greater than or equal to 4 .mu.m.
  • a thickness of the deposited coating of greater than or equal to 2 .mu.m, preferably greater than or equal to 4 .mu.m.
  • step B the deposition rate is set to a value of greater than or equal to 0.2 ⁇ m / min, preferably greater than or equal to 0.3 ⁇ m / min.
  • a value of 0.5 ⁇ m / min can be selected.
  • high deposition rates increase the economic efficiency of the process according to the invention and also facilitate the adjustment of the desired layer properties.
  • the metal substrate is a non-ferrous metal substrate selected from the group of substrates consisting of: brass, copper or bronze with a cleaned, uncoated surface.
  • the substrate surfaces are optionally mechanically and / or electrically glazed and / or luster-etched or refined by a chemical, electrochemical or mechanical pretreatment, for example, luster-bleached, electropolished or polished.
  • a chemical, electrochemical or mechanical pretreatment for example, luster-bleached, electropolished or polished.
  • the plasma is added to the plasma cleaning a gas or gas mixture, wherein the gas or gas mixture is selected from the group consisting of: argon, argon-hydrogen mixture, oxygen.
  • step B non-fragmented organosilicon compounds are present within the plasma polymerization reactor which react with reactive sites on the surface of the coating to form a hydrophobic surface.
  • This can be achieved by first leaving the un-fragmented organosilicon precursor (s) in the reactor after switching off the plasma source in order to react with the surface radical of the plasma polymer layer.
  • layers can be produced that are particularly easy to clean.
  • the formation of a near-surface hydrophobic layer can be detected by XPS.
  • the signals C1s, Si2p and O1s are used to quantify the carbon, silicon and oxygen content.
  • a trimethylsiloxy-terminated polydimethylsiloxane (PDMS) with a kinematic viscosity of 350 mm 2 / s at 25 0 C and a density of 0.970 g / mL at 25 0 C is examined.
  • An example of this is the product DMS-T23E Gelest.
  • the relative atomic sensitivity factors are adjusted so that the determined atomic stoichiometric ratio between silicon and oxygen is 1.00 ⁇ 0.05 and the atomic stoichiometric ratio between silicon and carbon is 0.50 ⁇ 0.03.
  • Example 1 For a preferred method according to the invention for carrying out the XPS examination, compare Example 1 below.
  • a layer produced by the method according to the invention preferably contains in the upper (5 nm away from the substrate) a carbon content of 40-55 atomic%, a silicon content of 15-25 atomic% and an oxygen content of 20-35 atom %, based on the total number of Si, C and O atoms contained in the coating. It is clear to the person skilled in the art that this superficial area is applied only after carrying out the steps essential to the invention.
  • the plasma is preferably not generated by means of DC voltage, but preferably by means of high frequency (HF) and in special preferred cases (s.v.) with microwaves.
  • HF high frequency
  • s.v. special preferred cases
  • Radio frequency should be understood to mean frequencies greater than or equal to 100 kHz.
  • step B oxygen is supplied to the plasma; all the substances supplied to the plasma in step B are in front of them
  • the present invention also relates to a coated metal substrate preparable by the process according to the invention, preferably in one of the embodiments described above as preferred.
  • a metal substrate coated according to the invention comprises a metal substrate and, arranged thereon, a plasma-polymer coating having the following features:
  • the hardness to be measured by nano identification is> 6 GPa.
  • Preferred coated metal substrates according to the invention comprising the substrates and / or coatings described above as being preferably characterized.
  • the coating preferably has determinable proportions of 5 to 30 atomic%, preferably 10 to 25 atomic% silicon and 30 to 70 atomic%, preferably 40 to 60 atomic% oxygen, by measurement by XPS, based on the total number of carbon, silicon and oxygen atoms contained in the coating.
  • the coating preferably has a fraction of carbon which can be determined by measurement by means of XPS of from 3 to 28 atomic%, preferably from 5 to 28 atomic % more preferably 7 to 28 atom% based on the total number of carbon, silicon and oxygen atoms contained in the coating.
  • an IR spectrum recorded by the coating has one or more, preferably all of the following bands (peaks) with a respective maximum in the following ranges: CH stretching vibration in the range from 2950 to 2970 cm -1 , Si-H vibration in the range of 2150 to 2250 cm -1 , Si-CH 2 -Si vibration in the range of 1350 to 1370 cm -1 , Si-CH 3 deformation vibration in the range of 1250 to 1280 cm -1 and Si -O vibration greater than or equal to 1 150 cm "1 .
  • the location of the maximum of the Si-O-Si oscillation gives information about the degree of crosslinking of the layer.
  • the higher its wave number the higher the degree of crosslinking.
  • Layers in which this maximum is greater than or equal to 1200 cm “1 , preferably greater than or equal to 1250 cm “ 1 have a high degree of crosslinking, while about non-stick layers with this maximum at typically about 1100 cm “1 have a low degree of crosslinking.
  • a detectable Si-CH 2 -Si vibrational band indicates that in addition to Si-O-Si linkages, Si-CH 2 -Si linkages are present in the coating.
  • Such a material regularly has increased flexibility and elasticity.
  • the ratio of the intensity of the Si-H band to the intensity of the Si-CH 3 band can serve. Coatings where this ratio is less than or equal to about 0.2 are colorless. At a ratio greater than about 0.3, the coatings are yellowish. Preference is given to a coated metal substrate according to the invention, wherein in an IR spectrum recorded by the coating, the ratio of the intensity of the Si-H band to the intensity of the Si-CH 3 band is less than or equal to 0.3, preferably less than or equal to 0.2 is.
  • an inventive coated metal substrate wherein the coating has an absorption constant k 3O o nm of less than or equal to 0.05 and / or an absorption constant k ⁇ o nm of klei ner or facilitated g 0, 01.
  • the coating of a coated metal substrate according to the invention has a surface energy in the range of 20 to 40 inN / m, preferably 25 to 35 inN / m. The surface energy is determined by the proportions of organic groups and thus by the amount of self-bias, as stated above.
  • the anti-corrosion properties of the coating by z For example, self-biasing, infiltration of the organosilicon precursor (s) and oxygen may be adjusted.
  • the coating has an elongation to microcracking (crack elongation) of greater than or equal to 1.5%, preferably greater than or equal to 2.5%.
  • the self-bias influences the layer thickness homogeneity in the above manner.
  • the gas flows are also of great importance.
  • H ieru nter for example, those reactors are to be understood, in which the reactor chamber (recipient) 2 m 3 or greater.
  • the layer thickness homogeneity is defined by the electric fields generated on the substrate, ie a high field strength means a high deposition rate. Homogeneity can only be achieved if the electric field strength on the substrate is largely the same everywhere.
  • the layer thickness homogeneity on the arbitrary three-dimensional substrate obeys the Laplace equation, which indicates the solution for the electric field strength on the substrate.
  • the maximum layer thickness differs from the minimum layer thickness by a factor of 1, 1 or less.
  • the present invention also relates to the use of a coating which can be produced or produced by a method according to the invention (in particular in a configuration marked as preferred) as a protective or functional layer on metals.
  • XPS measurements were carried out using the KRATOS AXIS Ultra spectrometer from Kratos Analytical. The calibration of the meter was made so that the aliphatic portion of the C 1s peak is 285.00 eV. Due to charging effects, it will usually be necessary to shift the energy axis to this fixed value without further modification.
  • the analysis chamber was equipped with an X-ray source for monochromatized AI K ⁇ radiation, an electron source as neutralizer and a quadrupole mass spectrometer. Furthermore, the system had a magnetic lens, which focused the photoelectrons via an entrance slit in a hemispherical analyzer. During the measurement, the surface normal pointed to the entrance slot of the hemisphere analyzer. The pass energy was 160 eV when determining the molar ratios. In determining the peak parameters, the pass energy was 20 eV each.
  • the measurement conditions mentioned are preferred in order to enable a high degree of independence from the spectrometer type and to identify plasma-polymer products according to the invention.
  • the reference material used was the polydimethylsiloxane silicone oil DMS-T23E from Gelest Inc. (Morrisville, USA). This trimethylsiloxy-terminated silicone oil has a kinematic viscosity of 350 mm 2 / s ( ⁇ 10%) and a density of 0.970 g / mL at 25 0 C and an average molecular weight of about 13 650 g / mol.
  • the selected material is characterized by an extremely low level of volatiles: after 24 hours at 125 ° C. and 10 ⁇ 5 Torr vacuum, less than 0.01% volatiles were detected (according to ASTM-E595-85 and NASA SP-R0022A ). It was applied as a 40 or 50 nm thick layer to a silicon wafer by means of a spin coating process; In this case, hexamethyldisiloxane was used as the solvent or diluent.
  • the nanoindentation hardness of a sample was determined using a Berkovich indenter (manufacturer: Hysitron Inc. Minneapolis, USA). The calibration and evaluation was done according to the established method of Oliver & Pharr (J.Mos.Res., 7, 1564 (1992)). The machine rigidity and area function of the indenter were calibrated prior to measurement. In the indentation, the "multiple partial unloading" method (Schiffmann & Strandr, Z. Metallischen 95, 31 1 (2004)) was used to obtain depth-dependent hardness values and thus to exclude a substrate influence.
  • a 0.5 mm thin and 10 cm long steel sheet (ST 37) is coated analogously and stretched until optical cracks are visible.
  • the crack extension limit is equal to the quotient of elongation to the original total length of the steel.
  • Example 4 IR spectroscopy and determination of the intensity ratio of two bands in the IR spectrum
  • the measurements were carried out using an IFS 66 / S IR spectrometer from Bruker. As a method, the IRRAS technique was used, with the help of which even the thinnest coatings can be measured.
  • the spectra were recorded in the wavenumber range of 700 to 4000 cm -1 using small platelets of very clean and particularly even aluminum as the substrate material, the angle of incidence of the IR light was 50 ° during the measurement while the sample was in the IR spectrometer
  • the sample chamber was continuously purged with dry air and the spectrum was recorded under such conditions that the water vapor content in the sample chamber was so small that no rotation bands of water were found in the IR spectrum One used aluminum plate.
  • the intensity ratio of two bands is determined as follows: The baseline in the region of a peak is defined by the two minima which include the maximum of the band and corresponds to the distance between them. It is assumed that the absorption bands are Gaussian. The intensity of a band corresponds to the area between the baseline and the measurement curve, bounded by the two minima which include the maximum, and can easily be determined by the person skilled in the art according to known methods. The determination of the intensity ratio of two bands is done by taking the quotient of their intensities. The basic prerequisite for the comparison of two samples is that the coatings have the same thickness and that the angle of incidence is not changed.
  • a zinc sheet is additionally provided with a transparent, elastic scratch and corrosion resistant coating.
  • the substrate is mounted on or in the immediate vicinity of the HF (13.56 MHz) operated cathode (area approximately 15 x 15 cm), so that the substrate itself acts as a cathode.
  • HF 13.56 MHz
  • cathode area approximately 15 x 15 cm
  • This step as step A of the method according to the invention has a duration of 5 min.
  • the plasma coating is then deposited on the prepurified substrate surface in step B of the method according to the invention.
  • hexamethyldisiloxane HMDSO
  • the self-bias voltage is controlled to set a value of 100V, 250V, 300V and 400V respectively.
  • Table 2 Optical constants of the coating at the variation of the BIAS voltage.
  • the coating proved to be more scratch-resistant than a compacted anodized coating with a layer thickness of about 8 ⁇ m, but a significantly higher crack elongation of 2.8% was observed. By contrast, the crack elongation for the anodized coating was only 0.5%.
  • an eccentric device (Starnberger) was used.
  • an approximately 8 ⁇ m thick anodized surface (not according to the invention)
  • an approximately 500 nm thick plasma-polymer coating produced by a process of the prior art (not according to the invention) was applied to a felt plate loaded with a 1 kg weight.
  • TW Jelinek surface treatment of aluminum, Eugen G. Leuze Verlag, Saulgau, 1996)
  • a 4 ⁇ m thick plasma-polymer coating according to the invention were investigated.
  • the anodization surface was already visibly scratched after about 300 strokes after about 300 double strokes and the non-inventive plasma polymer coating after about 500 strokes.
  • no visually noticeable scratches could be detected even after 10,000 strokes.
  • D iegu ts Korros io nss chut adaptenschaften of the coating produced by plasma polymerization according to the invention are in the acid (20% sulfuric acid, 45 min, 65 0 C), such as in basic (NaOH, pH 14, 5 min, 3O 0 C) media. After these Corrosion tests showed no visible damage or no infiltration of coating edges.
  • Example 4 between Si-H and Si-CH 3 is about 1: 5.
  • the IR spectrum shows a small peak at 1360 cm-1. This band is correlated with a Si-CH 2 -Si vibration.
  • the hardness of the coating was determined according to Example 2. It is 3 GPa. The pencil hardness is 4H.
  • the coating is homogeneous in depth.
  • the proportions of carbon are about 10%, silicon about 10%, hydrogen about 30% and oxygen about 50%.
  • a more in fl uent co m p u c t i o n c e m e n t o f e a tio n the plasma polymer layer shows on the one hand a shaggy fracture known for brittle materials (glass) and on the other hand small step-like fractures expected for crystalline materials.
  • the experiment is performed as in Embodiment 5, but to increase the deposition rate and thus to shorten the process time, a plasma generator oscillating at a frequency of 27.12 MHz was used.
  • a plasma generator oscillating at a frequency of 27.12 MHz was used.
  • the deposition rate is increased by a factor of 1.5.
  • the coating properties change only insignificantly and are very similar to those of the coating of Example 5.
  • the dependence of the scratch and abrasion protection properties were determined as a function of the layer thickness.
  • the substrate used was 600 ⁇ m thick stainless steel sheet (1.4544).
  • the layer thickness was defined by the coating time.
  • the scratch protection was achieved by particle bombardment (50 ⁇ m corundum, speed 100 km / h, time 3 min, Particle flow 33 g / min / cm 2 ).
  • the coating parameters are shown in Table 3.
  • the coatings whose layer thickness is less than 10 microns are completely removed, i. the layer thickness after the scratch protection test was 0 nm. From a layer thickness of about 17 ⁇ m, no appreciable erosion could be detected, i. the layer thickness remained unchanged.
  • the thermal parameters were determined by the flash method. Its principle is to suddenly heat the front of a sample by a short pulse of light and then measure how much time the heat front reaches the back of the sample. Flash methods provide as a primary measure the thermal diffusivity ( ⁇ ) of the temperature, which can be converted from the heat (p) and heat capacity (Cp) into the thermal conductivity ( ⁇ ).
  • ⁇ thermal diffusivity
  • p heat
  • Cp heat capacity
  • the method can also be applied to multi-layered samples.
  • the thermal conductivity of an unknown layer can be determined if the thermophysical parameters ( ⁇ , Cp, p) of all other layers are known.
  • the layers measured here are particularly suitable for the coating of injection molds.
  • a brass door handle was equipped with a corrosion and scratch resistant coating.
  • the door handle has been switched as a cathode, so that during the
  • Coating time of 20 min and an HMDSO or O 2 flow of 66 sccm and 280 sccm was on the handle a transparent and interference-free layer of about 5 microns.
  • the color impression of the handle was unchanged.
  • the resistance of the coating to sweat was measured by immersion in artificial sweat for 96 hours.
  • the handle showed no visible change, the layer adhesion was not reduced.

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  • Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Plasma & Fusion (AREA)
  • Chemical Vapour Deposition (AREA)
  • Physical Vapour Deposition (AREA)
  • Laminated Bodies (AREA)

Abstract

L'invention concerne un procédé pour le revêtement de la surface d'un substrat métallique, présentant les étapes suivantes : A. mise à disposition du substrat métallique et éventuellement nettoyage de la surface de substrat à recouvrir, B. revêtement de la surface de substrat éventuellement nettoyée à l'étape A dans un réacteur de polymérisation au plasma au moyen de polymérisation au plasma, procédé dans lequel un ou plusieurs composés organosiliciés et (a) pas d'autres composés ou (b) d'autres composés sont utilisés à l'étape B comme précurseur(s) pour le plasma et le substrat métallique est disposé à l'étape B dans le réacteur de polymérisation au plasma de telle sorte que le substrat est branché comme capteur, caractérisé en ce que le procédé est guidé de telle sorte que le revêtement fabriqué par le procédé présente une extension jusqu'à la microfissure ≥ 1,5 %, de préférence ≥ 2,5 %, un index jaune (Yellow Index) déterminé selon ASTM D 1925 ≤ 4, de préférence ≤ 3, avec une préférence encore plus grande ≤ 2,5 et une dureté à mesurer par nanoindentation située entre 2,5 et 10 GPa, de préférence entre 3,1 et 10 GPa, avec une préférence encore plus grande entre 3,1 et 6 GPa et de préférence une conductibilité thermique ≤ 5 W/m°K, de préférence ≤ 2,5 w/m°K et/ou une rigidité diélectrique de 10 à 100 m°K, de préférence ≥ 40 kV/mm, à la condition que le substrat métallique ne soit pas un substrat de métal léger et à la condition que, dans le cas d'une extension allant jusqu'à la microfissure du revêtement ≤ 2,2 %, la dureté à mesurer par nanoindentation est ≥ 6 GPa.
EP10718958.1A 2009-04-30 2010-04-30 Substrats métalliques avec couche anticorrosion résistante aux rayures et extensible et procédé pour sa fabrication Active EP2424683B2 (fr)

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DE102009002780A DE102009002780A1 (de) 2009-04-30 2009-04-30 Metallsubstrate mit kratzfester und dehnbarer Korrosionsschutzschicht und Verfahren zu deren Herstellung
PCT/EP2010/055897 WO2010125178A1 (fr) 2009-04-30 2010-04-30 Substrats métalliques avec couche anticorrosion résistante aux rayures et extensible et procédé pour sa fabrication

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DE102013215912B3 (de) * 2013-08-12 2015-02-26 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Farbneutral beschichteter kupferhaltiger Gegenstand, Verfahren zu dessen Herstellung sowie Verwendung einer entsprechenden farbneutralen Beschichtung
DE102013215919B3 (de) * 2013-08-12 2015-02-05 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Farbneutral beschichteter metallhaltiger Gegenstand mit metallhaltiger oder Metall-Oberfläche, Verfahren zu dessen Herstellung sowie Verwendung einer entsprechenden farbneutralen Beschichtung
DE102013219337B3 (de) * 2013-09-25 2015-04-02 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Plasmapolymerer Festkörper, insbesondere plasmapolymere Schicht, deren Herstellung sowie deren Verwendung als Korrosionsschutz
DE102013219331B3 (de) * 2013-09-25 2015-03-19 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Plasmapolymerer Festkörper, insbesondere plasmapolymere Schicht, sowie deren Verwendung
EP3049193B1 (fr) * 2013-09-25 2021-09-08 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Corps solide de polymère de plasma (en particulier couche de polymère de plasma)
DE102014204937A1 (de) 2014-03-17 2015-09-17 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Verfahren zur Herstellung eines Polyurethanformteiles
DE102020109113A1 (de) 2020-04-01 2021-10-07 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung eingetragener Verein Gegenstand mit aktiv wirkender Anti-Haft Oberfläche

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EP2424683B1 (fr) 2016-03-02
EP2424683B2 (fr) 2021-10-27
DE102009002780A1 (de) 2010-11-11

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