EP2203258A2 - Couche anticorrosion antirayures et extensible pour substrats en métal léger - Google Patents

Couche anticorrosion antirayures et extensible pour substrats en métal léger

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Publication number
EP2203258A2
EP2203258A2 EP08844614A EP08844614A EP2203258A2 EP 2203258 A2 EP2203258 A2 EP 2203258A2 EP 08844614 A EP08844614 A EP 08844614A EP 08844614 A EP08844614 A EP 08844614A EP 2203258 A2 EP2203258 A2 EP 2203258A2
Authority
EP
European Patent Office
Prior art keywords
plasma
coating
light metal
metal substrate
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
EP08844614A
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German (de)
English (en)
Other versions
EP2203258B1 (fr
Inventor
Dirk Salz
Klaus-Dieter Vissing
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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Publication of EP2203258A2 publication Critical patent/EP2203258A2/fr
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Publication of EP2203258B1 publication Critical patent/EP2203258B1/fr
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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
    • B05D2202/20—Metallic substrate based on light metals
    • 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
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/14—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by electrical means
    • B05D3/141—Plasma treatment
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31652—Of asbestos
    • Y10T428/31663—As siloxane, silicone or silane

Definitions

  • the invention relates to a method for coating the surface of a light metal substrate, in particular aluminum and magnesium with a layer which is characterized by an advantageous combination of scratch resistance, ductility and corrosion protection effect, and coated light metal substrates.
  • Untreated surfaces of objects made of light metals, in particular aluminum (including aluminum alloys) or magnesium (including magnesium alloys), in particular in certain media, such as alkalis or acids, a strong corrosion susceptibility.
  • their mechanical stability is comparatively low. Therefore, in particular aluminum surfaces (if necessary refined by a chemical, electrochemical or mechanical pretreatment) are often treated by anodizing (anodization, anodization, anodization).
  • anodizing anodization, anodization, anodization
  • Corresponding anodized surfaces have a metallic luster due to the transparency of the oxide layer produced and are somewhat protected against corrosion and scratching compared to untreated surfaces.
  • Anodic coatings typically have an open-pored surface structure.
  • Dyes can optionally be incorporated into the pores. Frequently, the openings of the anodizing pores are closed by compaction. For this purpose, alumina hydrate is usually formed in the pore, which improves corrosion protection and longevity. Eloxal layers form an integral part of the aluminum and therefore do not peel off or burst.
  • a disadvantage of Eloxal harshen is their low ductility. Typical is crack-onset strain, elongation to microcracking of about 0.4%, which is thus worse than with untreated aluminum. This means in the processing of corresponding components of aluminum or aluminum alloys (aluminum substrates), for example in the case of automotive trims, a strong limitation.
  • the anodising improves the corrosion resistance of the surface of an aluminum substrate compared to the untreated aluminum substrate, it is not sufficient for all fields of application.
  • against the attack of strong bases (pH about 13.5 or higher) protect anodization only insufficient. This has resulted in anodizing surfaces being used in some technical applications such as e.g. the automotive industry no longer meet the current requirement profile.
  • the scratch resistance of an anodized surface is increased over the surface of an untreated aluminum substrate, it is not sufficient in all dimensions (e.g., not for moldings, covers, lamps, fittings and machine parts of food processing).
  • An example of a diverse surface load which often can not cope with a surface treated by an anodizing process, can again be found in the automotive sector, for example in the case of aluminum rims. If such rims, in order to obtain their metallic luster, are not to be painted after polishing, a process for producing coatings which hardly or not change the visual appearance, which provides good corrosion protection, is not necessary under mechanical pressure and tensile stress tend to cracking, have a high scratch resistance, are not undermined in local destruction, as insensitive to alkalis and cleaning agents, the surface imitate well and have a high temperature resistance and optionally a dirt-repellent surface behavior, so that, for example can not fix brake dust.
  • a protective layer should have an improved crack elongation.
  • improved chemical stability compared to alkaline media and generally an improved corrosion protection effect compared to anodized coatings is desirable.
  • such a layer should have an improved scratch resistance compared to anodized layers and can be produced in an economically advantageous process, in particular at a relatively high speed.
  • step B coating the optionally cleaned in step A substrate surface in a plasma polymerization reactor by plasma polymerization, wherein - in step B as a precursor (s) for the plasma one or more organosilicon and (a) no further or (b) other compounds are used and in step B, the light metal substrate in the plasma polymerization reactor is arranged to (i) be between the zone in which the plasma is formed and the cathode or (ii) to act as a cathode, characterized in that the process is conducted in that the coating produced by the method has a content of carbon which can be determined by measurement by means of XPS of 5 to 20 atom%, preferably 10 to 15 atom%, based on the total number of carbon, silicon and oxygen atoms contained in the coating according to ASTM D 1925 determined yellow index (Yellow Index) of ⁇ 3, preferably ⁇ 2.5 and one by nanoindentation to m having hardness of hardness in the range of 2.5 to 6 GPa, preferably 3.1 to 6 GPa.
  • step B as
  • Light metal in the context of the present invention is a metallic material having a specific density of at most 4.5 g / cm 3 .
  • These include in particular magnesium, aluminum, beryllium and titanium and their alloys.
  • Preferred light metal substrates are magnesium substrates and in particular aluminum substrates.
  • Coatings with a yellow index of 2.5 or below generally have no yellowing discernible to the human eye. However, for coatings intended to replace anodized coatings, even a minimal 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.
  • 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, the elongation at break and the corrosion protection properties are improved in comparison with the anodised aluminum layers typical for aluminum.
  • the scratch resistance of the layers is in many cases comparable to that of glass surfaces.
  • an anodizing surface may also be coated, which may be desirable, in particular in the case of colored anodising layers.
  • the scratch resistance and the corrosion protection properties are improved.
  • dirt-repellent (low-energy) surface properties can occur on the coating surface be set.
  • the achievable layer property function is not only of interest as an anodic additive, but also for the general coating of light metals.
  • DE 197 48 240 A1 discloses a process 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.
  • no information is given 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. Due to the low deposition rates, the process disclosed therein is not suitable for producing economically higher layer thicknesses, as are necessary for scratch-resistant coatings. In addition, 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 is surface-connected to the substrate, in which the molar ratios of O to Si and C to Si are each in certain ranges and easy to clean.
  • 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 extensibility that are inherent in the coating according to the invention. Furthermore, it is characterized by a high water absorption, comparable to that of organic coatings.
  • Domingues et al. contains no information regarding yellowing or carbon content. On the basis of the procedure (ratio of the gas flows of oxygen to the organosilicon precursor about 23: 1, for more details on the influence of these parameters see below), the method described 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 aluminum substrates
  • Thick film method e.g. The application of paints or sol-gel coatings, while the necessary corrosion resistance can achieve, but they change the visual appearance. This effect is exacerbated in the case of irregularities such as mechanical damage or poor adhesion of thick films.
  • the method according to the invention is able to meet the need for a cost-effective method for producing a thin layer which does not change the surface color of the aluminum (no intrinsic color and thus has a sufficiently high transmission in the visible range), which polishes the surface structure (eg. ground, frosted) so that there is no "glossy finish" which, in addition to a high corrosion resistance, has a high mechanical resistance (scratch resistance, extensibility) and which has a high layer thickness uniformity even with complex geometries.
  • the layer properties can be set within wide limits as described below.
  • the hardness 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. Generally, the scratch resistance of the layer is determined by the appropriate choice of layer thickness and composition. Preferred is a method according to the invention, which is conducted so that the coating produced by the method has a pencil hardness of 4H or higher, determined according to ASTM D 3362. 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 selected than for a low one. 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.
  • 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.
  • the light metal substrate in the plasma polymerization reactor is arranged so that it either (i) is located between the zone in which the plasma is formed and the cathode or (ii) acts as a cathode.
  • Alternative (ii) is preferred here.
  • the cathode the substrate acts when it is in direct electrically conductive contact with the part of the cathode which is distinguishable from the light metal substrate or when it is at a sufficiently small distance therefrom. This facilitates the achievement of a high rate of deposition of the positively charged ions of the plasma attracted to the negatively charged cathode. If the substrate itself acts as a cathode, the force is particularly increased, with which the positively charged ions impinge on the surface.
  • 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.
  • organic usually consisting mainly of C and H
  • Si and O 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.
  • 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 . In addition, 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.
  • placing the substrate in a manner to act as a cathode is generally not preferred because of the risk of forming indefinable organosilicon layers on the substrate and the desire for a relatively high level of organic groups in the layer runs counter.
  • the organic modification increases the flexibility and elasticity of the layer produced. In addition, it reduces its residual stresses (internal stress), which increases the crack elongation of the layer.
  • the bias bias is set on the substrate.
  • the dependence of the deposition rate and the layer properties on 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 if 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.
  • step B the light metal substrate is in spatial contact with (i) the cathode or (ii) a part of the cathode which is distinguishable from the light metal substrate.
  • Alternative (ii) in contrast to alternative (i), refers to the case where the substrate itself acts as a cathode.
  • An increase in the inflow of the organosilicon precursors or for the plasma, (in relation to optionally also flowing O 2 in particular under Keeping the total influx constant) generally causes lowering of hardness, increase of visible absorption (increase of yellow index), deterioration of anticorrosive effect, and improvement of 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 ascertained 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 reducing 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 ).
  • step B the plasma is supplied with oxygen (in the form of O 2 ) and preferably all the substances supplied to the plasma in step B are gaseous before they enter the plasma polymerization reactor.
  • oxygen in the form of O 2
  • An increase in the oxygen supply leads to an increase in hardness, a reduction in the 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 prior to entering the plasma polymerization reactor and the ratio of the gas flows of oxygen and further precursor supplied to the plasma in step B ( en) (in particular organosilicon precursors) in the range from 1: 1 to 6: 1, preferably 3: 1 to 5: 1.
  • the ratio of the gas flows of oxygen and further precursor supplied to the plasma in step B ( en) in particular organosilicon precursors
  • the ratio of the gas flows of oxygen and further precursor supplied to the plasma in step B ( en) in particular organosilicon precursors) in the range from 1: 1 to 6: 1, preferably 3: 1 to 5: 1.
  • the O 2 flux can be increased.
  • the inflow of the one or more organosilicon precursors or the self-bias can be reduced. If the coating is too hard and thus too brittle, the self-bias can be reduced or the inflow of the organic acid precursor (s) can be increased.
  • 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 in the inflow of HMDSO in relation to oxygen causes, inter alia, a reduction in the hardness, an increase in 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.
  • the plasma polymerization is preferably carried out at a temperature of less than 200 ° C., preferably less than 180 ° C. and / or a pressure of less than 1 mbar, preferably in the range from 10 -3 to 10 -1 mbar. If the pressure during the deposition is too high, unwanted powdering of the deposited material may occur. At a temperature greater than 180 0 C, the aluminum is increasingly softer, since the crystal structure changes. At a pressure of less than 10 3 mbar, the plasma can no longer be ignited.
  • step B is preferably carried out to a thickness of the deposited coating of greater than or equal to 2 ⁇ m, preferably greater than or equal to 4 ⁇ m.
  • a higher thickness increases the scratch resistance of a given coating.
  • 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. For example, 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 light metal substrate is an aluminum substrate selected from the group of substrates consisting of: aluminum or aluminum alloy with a cleaned, uncoated surface; Aluminum or aluminum alloy with superficial oxide layer; anodised (s) (anodized) aluminum or aluminum alloy with dyed or undyed, compacted or uncompacted oxide layer.
  • the aluminum or the aluminum alloy with a cleaned, uncoated surface is optionally mechanically and / or electrically glazed and / or luster-etched or finished by a chemical, electrochemical or mechanical pretreatment, for example, luster-pickled, electropolished or polished.
  • other light metals such as e.g. Magnesium and its alloys are preferred as substrates. Such substrates may also have been modified by smoothing or conversion processes prior to coating according to the invention.
  • step A the substrate surface to be coated is cleaned by means of a plasma.
  • a plasma cleaning improves the layer adhesion.
  • a gas or gas mixture is added to the plasma to carry out the plasma cleaning, 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 unfragmented organosilicon precursor (s) in the reactor after switching off the plasma source, thus giving the opportunity to react with the surface radicals 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.
  • a layer produced by the process 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 region is applied only after the steps essential to the invention have been carried out.
  • the plasma is preferably generated by means of high frequency (HF).
  • step B oxygen is supplied to the plasma; all substances supplied to the plasma in step B are gaseous before entering the plasma polymerization reactor; the ratio of the gas fluxes of oxygen and further precursor (s) supplied to the plasma in step B in the range from 1: 1 to 6: 1; during step B, a control is performed so that the self-bias on the substrate is in the range of 100 to 400 V, preferably such that the self-bias is constant; hexamethyldisiloxane (HMDSO), oxygen and preferably no further compound is used as precursor (s) for the plasma; in step B, the light metal substrate is in spatial contact with a portion of the cathode which is distinguishable from the light metal substrate; - The plasma polymerization is carried out at a temperature of less than 200 0 C and a pressure in the range of 10 "3 to 10 " 1 mbar; in step B, the deposition rate is set to a value of greater than or equal to 0.2 ⁇ m / min;
  • Step B is carried out to a thickness of the deposited coating of greater than or equal to 2 ⁇ m;
  • the light metal substrate is an aluminum substrate selected from the group of substrates consisting of: aluminum or aluminum alloy with a cleaned, uncoated surface; Aluminum or aluminum alloy with superficial oxide layer; anodized aluminum or aluminum alloy with colored or uncolored, compacted or uncompacted oxide layer, or the light metal substrate is a magnesium substrate selected from the group of substrates consisting of: magnesium or magnesium alloy with cleaned, uncoated surface; Magnesium or magnesium alloy with superficial oxide layer.
  • the substrate surface to be coated is cleaned by means of a plasma, wherein the plasma for performing the plasma cleaning, a gas or gas mixture is added, which is selected from the group consisting of: argon, argon-hydrogen mixture, oxygen; the plasma is generated by means of high frequency.
  • a gas or gas mixture which is selected from the group consisting of: argon, argon-hydrogen mixture, oxygen; the plasma is generated by means of high frequency.
  • the present invention also relates to a coated light metal substrate, preferably a magnesium or an aluminum substrate, preparable by the process according to the invention, preferably in one of the embodiments described above as preferred.
  • 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, as measured by XPS to the total number of carbon, silicon and oxygen atoms contained in the coating.
  • these atomic percent ranges the setting of the desired property combination is particularly well possible.
  • the dependence of the proportions of carbon, silicon and oxygen on the arrangement of the substrate and on the self-bias has already been explained above.
  • these proportions can be influenced by choosing suitable precursors.
  • 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 of 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 11335500 bbiiss 11337700 ccmm "" 11 ,, SSii - CCHH 33 --Deeffoorrmmaattiioonnsscchhwwiinngguunngg in the range of 1250 to 1280 cm “1 and Si-O vibration greater than or equal to 1 150 cm " 1 .
  • the position 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, 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.
  • a coated light 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.
  • a coated light metal substrate according to the invention Preference is given to a coated light metal substrate according to the invention, the coating having an absorption constant k.sub.30 nm of less than or equal to 0.05 and / or an absorption constant k.sub.4O.sub.n nm of less than or equal to 0.01.
  • absorption constant k.sub.30 nm of less than or equal to 0.05
  • absorption constant k.sub.4O.sub.n nm of less than or equal to 0.01.
  • the coating of a coated lightweight metal substrate according to the invention preferably has a surface energy in the range from 20 to 40 mN / m, preferably 25 to 35 mN / m.
  • the surface energy is determined by the proportions of organic groups and thus by the amount of self-bias, as stated above.
  • a coated light metal substrate according to the invention after 15 minutes of corrosive attack of NaOH at pH 14 and 30 0 C no visible to the naked eye on corrosion traces.
  • the coating has an elongation to microcracking (crack elongation) of greater than or equal to 1%, preferably greater than or equal to 1.5%.
  • the self-bias influences the layer thickness homogeneity in the above manner.
  • the gas flows are also of great importance.
  • 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 preferably 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 by a method according to the invention (in particular in a configuration designated as preferred) as a substitute for an anodized layer.
  • XPS measurements were carried out using the KRATOS AXIS Ultra spectrometer from Kratos Analytical. The calibration of the measuring device was carried out so that the aliphatic part of the C 1 s 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 Al K ⁇ radiation, an electron source as a 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 content of volatile constituents from: after 24 hours at 125 0 C and 10 "5 Torr vacuum was less than 0.01% flüch- current portions detected (according to ASTM E595-85 and NASA SP It was applied to a silicon wafer as a 40 or 50 nm thick layer using a spin-coating process using hexamethyldisiloxane as the solvent.
  • 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 coated aluminum sheet is stretched until optically visible cracks.
  • the crack extension limit is equal to the quotient of change in length to the total length of the aluminum.
  • 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 flat 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 the water could be seen in the IR spectrum, using an uncoated aluminum plate as reference.
  • 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.
  • An anodised aluminum trim strip as substrate is additionally provided with a transparent, stretchable 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 process according to the invention.
  • hexamethyldisiloxane HMDSO
  • the self-bias voltage is controlled to set a value of 100V, 250V, 300V and 400V respectively.
  • coatings 1 to 3 are transparent in the visible and UVA range. This is reflected in the very low absorption constant k at 300 or 400 nm. The absorption constants were calculated from the ellipsometric data according to the manual of the WVASE32 spectrometer from JA Woolam Co, Inc.
  • 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 (greater than 2%) was observed than with an anodized coating.
  • an eccentric apparatus (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 was 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.
  • the good corrosion protection properties of the coating produced by plasma polymerization according to the invention apply in acidic (20% sulfuric acid, 45 min, 65 ° C) as in basic (NaOH, pH 14, 5 min, 30 0 C) media. After these corrosion tests, no visible damage or no infiltration of coating edges could be detected.
  • the infrared spectrum of this coating is shown in FIG. 1.
  • 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 scanning electron microscopic examination of the fracture edge of the plasma polymer layer shows, on the one hand, a mussel-like fracture known for brittle materials (glass) and, on the other hand, small step-like fractures expected for crystalline materials.
  • the corrosion resistance was evaluated according to the following qualitative five-step scale:

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  • Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Plasma & Fusion (AREA)
  • Physical Vapour Deposition (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Chemical Vapour Deposition (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)

Abstract

L'invention concerne un procédé utilisé pour recouvrir la surface d'un substrat en métal léger, qui comprend les étapes suivantes: A) préparer le substrat en métal léger et nettoyer le cas échéant la surface du substrat à recouvrir, B) recouvrir la surface du substrat éventuellement nettoyée à l'étape A dans un réacteur de polymérisation plasma, par polymérisation plasma, le(s) précurseur(s) utilisé(s) pour le plasma à l'étape B étant un ou plusieurs composés organosiliciés, ainsi (a) qu'aucun autre composé ou (b) d'autres composés. A l'étape B, le substrat en métal léger est disposé dans le réacteur de polymérisation plasma de sorte à (i) se trouver entre la zone où le plasma est formé et la cathode ou (ii) à faire office de cathode. L'invention se caractérise en ce que le revêtement obtenu au moyen dudit procédé présente une proportion de carbone, pouvant être déterminée par mesure XPS, de l'ordre de 5 à 20% en atome, de préférence de l'ordre de 10 à 15% en atome, par rapport au poids total des atomes de carbone, de silicium et d'oxygène contenus dans le revêtement, un indice de jaune de 3, de préférence 2,5, déterminé selon ASTM D 1925, et une dureté à mesurer par nano-indentation, de l'ordre de 2,5 à 6 GPa, de préférence de l'ordre de 3,1 à 6 GPa.
EP20080844614 2007-10-31 2008-10-31 Couche anticorrosion antirayures et extensible pour substrats en métal léger Active EP2203258B1 (fr)

Applications Claiming Priority (2)

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DE200710000611 DE102007000611A1 (de) 2007-10-31 2007-10-31 Kratzfeste und dehnbare Korrosionsschutzschicht für Leichtmetallsubstrate
PCT/EP2008/064826 WO2009056635A2 (fr) 2007-10-31 2008-10-31 Couche anticorrosion antirayures et extensible pour substrats en métal léger

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EP2203258B1 EP2203258B1 (fr) 2012-05-30

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WO2009056635A2 (fr) 2009-05-07
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DE102007000611A1 (de) 2009-05-07
WO2009056635A3 (fr) 2009-07-30

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