Pigmented and finely structured tribological composite material

专利摘要:

公开号:ES2606878T9
申请号:ES12812953T
申请日:2012-12-20
公开日:2019-06-11
发明作者:Carsten Becker-Willinger；Frank Hollmann；Christoph Kasper
申请人:Leibniz Institut fuer Neue Materialien Gemeinnuetzige GmbH；
IPC主号:

专利说明:

[0001]
[0002] Pigmented and finely structured tribological composite material
[0003]
[0004] To avoid friction in the case of a relative movement of two surfaces together, fats and oils are generally used as lubricants. This so-called hydrodynamic lubrication leads to very low coefficients of sliding, clearly below p = 0.05. Since the grease, under the surface pressure that manifests itself, is displaced in the course of time of the contact surface between the two surfaces or can be resinified by oxidation and dirt processes, the corresponding surfaces must be greased regularly, with the In order to maintain the lubricating effect. This determines a high maintenance complexity and an additional cost factor in the case of the installations, as well as, in the case of a non-regular maintenance, possibly the deterioration of the components. Alternatively, coatings that reduce sliding friction consisting of a polymeric binder and solid lubricants may be employed. However, decisive drawbacks are, as a rule, high sliding coefficients with values of p = 0.1 - 0.2 and the need for the balance between a friction slip as low as possible and a controllable abrasion behavior of the layers in relation to the configuration of the transfer film, important for lubrication. In the case of corrosive substrates, sufficient protection against corrosion must also be ensured, since by renouncing the grease the hydrophobic protective function in the overall structure is suppressed and, as a result, electrolytes as well as oxygen can have an access easier to the surface of the substrate. The introduction of an abrasion resistance and a protection against corrosion takes place, as a rule, through the incorporation by dispersion of suitable inorganic particles which, in their presently available forms, certainly fulfill their protective function, but together with they exert a negative influence on the lubricating effect of the stratified system, which makes the resulting compositions uninteresting in most cases for a practical application.
[0005]
[0006] US 4694038 A (Boeing) claims a sliding friction reducing coating consisting of a polyurethane binder and 20-40% by weight of amorphous graphite particles suitable for the surface endowment with elastomers. The use of a polyurethane binder makes it possible to achieve a good adhesion with the substrate. However, the disadvantage is that the graphite particles are uniformly distributed along the thickness of the coating material. As a result, the desired low friction friction towards the outer face of the coating, but at the same time the presence of the graphite in the vicinity of the boundary layer towards the surface, is certainly achieved - because the graphite can come off in the form of layers -. background leads to a reduction of the adhesion of the layers towards the substrate material which can only be controlled in some way by the use of correspondingly reactive binders (polyurethane). In addition, the laminated systems soften relatively due to the high content of solid lubricant which, in the case of high surface pressures, can easily lead to failures of the layers by micro-plowing.
[0007]
[0008] With a similar principle of uniform distribution of particles through the binder matrix, US 5789523 A (Du-Pont) claims a polyimide composition with incorporated soft phyllosilicates (Mohs 1-5 hardness) and carbon fibers, as well as optionally contained solid lubricants with improved slip friction and improved wear resistance to generate injection castings with built-in tribological effect. Phyllosilicates should improve the stability of composite materials. At the same time, the uniform distribution of the inorganic additives along the organic polyimide matrix and the high levels of additive loading necessary at the same time to achieve adequate tribological properties of the surface also clearly influence the bulk properties mechanical and thermal elements of the molded part produced such as, eg, For example, the E module or the coefficient of thermal expansion, which in some applications can be absolutely undesirable.
[0009]
[0010] Unlike the aforementioned documents, in which the particles in the form of plates are only mechanically dispersed using shear forces, in the case of WO 2002005293 A2 (EMTEC Magnetic) an electrically conductive layer based on graphite is claimed. and a binder, to which is added a polyurethane dispersion resin carrying at least one polar functional group along the polymer backbone, which can interact with the surface of the graphite filler material in the form of small plates. and it is also able to form corresponding graphite intercalation compounds. This type of modification also leads to a uniform distribution of the particles along the binder matrix, with a distribution, as a rule, of finer particle size than in the case of purely mechanical dispersion through shear forces . A morphology of this type is also desired in order to achieve a good electrical conductivity. However, tribological properties are not claimed.
[0011] Also, lubricant varnishes of this type based on solid lubricants and polymeric binders are often provided with particles of hard material for mechanical reinforcement (US 20040229759 A1 (Jet-Lube Inc.). However, it is problematic that the particles of hard material exert, in a high concentration, as a rule, an abrasive effect on the tribological system when transferred during the formation of the transfer film to the body. opposite and can lead, in the subsequent friction process, to a higher wear in the tribological layer US 4898905 A (Taiho Kogyo) also claims a lubricating varnish composition based on a polyimide matrix, solid lubricants in the form of plates, silicone additives in the form of plates and oil. Neither in this case is any particular precaution intended to generate a pre-established arrangement of the particles through the binder matrix, nor is it reached. A hydrodynamic lubricant component is incorporated into the system through the oil used, which can influence, in particular, the initial friction behavior and the level of friction coefficient of sliding. The disadvantage is that the oil can diffuse into the layer and, over time, can be expelled from the system. With this, the active effect does not last long.
[0012] US 3809442 (3M), EP 1350817 A1 (Ford Motor Comp.) And WO 2005010107 A1 (TNO) claim lubricating lacquers based on combinations of different solid lubricants with binders that are intended for low temperature applications and coating of substrates sensitive to temperature. WO 2005010107 A1 requires, in addition, an additional lubricant additive based on polysiloxane, polyolefin wax or PTFE. In this case, for the effectiveness of the additive it is necessary that it does not interact with the solid lubricants and can spread unimpeded to the layer / air phase limit. A particular morphological distribution of the particulate components for the effectiveness of the coating is not decisive. The additive leads only to a hydrodynamic component in relation to the lubrication analogously as described above.
[0013] Polymeric matrix composite materials with reinforcing particles are also described for abrasion resistant non-stick coatings.
[0014] EP 1718690 claims abrasion resistant low energy layers with increased stability against alkalis. The material composition comprises a hardenable organic binder system, at least one functionalized fluorinated oligomer polymer, which is reactive with the binder, as well as inorganic particles.
[0015] Due to the abrasiveness of the hard material particles, tribological properties can not be deduced and are not claimed either. Likewise, no solid inorganic lubricants are described.
[0016] By means of the present invention, it was possible to provide a tribologically effective layered system which, conditioned by its particular structure, compensates for the aforementioned drawbacks of conventional lubricant lacquers.
[0017] The object of the present invention was to provide a pigmented and finely structured tribological composite material which combined a low friction coefficient of sliding with excellent adhesion to the bottom and an extraordinary resistance to abrasion and wear, combined with a function of high barrier against the diffusion of water vapor and gases, as well as corrosive media.
[0018] Solution
[0019] This problem is solved by the invention with the features of the independent claims. Advantageous refinements of the inventions are characterized in the dependent claims. The wording of all the claims is thus referenced with respect to the content of this description. The inventions also include all convenient combinations and, particularly, all mentioned combinations of independent and / or dependent claims.
[0020] The approach to the problem could be solved by providing a composition comprising at least one solid lubricant in the form of plates, at least one type of inorganic pigment particles in the form of plates, where the pigment particles have a thickness of 0, 5 pm to 2 pm and an average aspect ratio> 10, at least one surfactant compound, wherein the surfactant compound is selected from the group comprising alkyl ammonium compounds, alkyl phosphonium compounds, alkyl sulfonium compounds, imidazolinium compounds, pyridinium compounds, pyrrolidinium compounds, ionic liquids, functionalized fluorinated polymers, polyesters and functionalized polysiloxanes, and a hardenable binder system comprising at least one organic polymer or oligomer with one or more functional groups or a precursor thereof.
[0021] The solid lubricant consists of particles in the form of plates. By "platelet" is meant a particle having a ratio of average diameter to thickness greater than 3: 1, preferably between 2: 1 and 1000: 1. All lengths can be measured with TEM.
[0022] In a preferred refinement of the invention, the solid lubricant has a thickness between 50 nm and 1000 nm and an aspect ratio of> 5, preferably an aspect ratio of 5 to 20.
[0023] The solid lubricant particles have a size of 50 nm to 20 pm, preferably 700 nm to 5 pm.
[0024] The solid lubricant can in this case be a usual solid lubricant. These may be solid lubricants such as natural graphite, synthetic graphite, graphene, hexagonal boron nitride, turbo-stratified boron nitride, molybdenum disulfide and / or tungsten disulfide.
[0025] Furthermore, purely organic solid lubricants such as perfluorinated polymer, polytetrafluoroethylene (PTFE) and / or polyethylene can also be added in addition. These can affect the resting-sliding behavior of the hardened coating.
[0026] A preferred solid lubricant is hexagonal boron nitride.
[0027] The at least one solid lubricant is preferably used in a proportion of 1 to 40% by weight, preferably 20-30% by weight, the% by weight referring to all components, with the exception of the solvent.
[0028] The composition according to the invention further comprises at least one type of inorganic pigment particle in the form of plates.
[0029] The plates can be composed of usual materials. These can be metals, metal oxides or other inorganic compounds. The plates can also be composed of organic materials. In this case, it is important that the plates present only a small variation in relation to their thickness.
[0030] Examples of support materials are mica, glass, silicon dioxide, titanium dioxide and aluminum oxide.
[0031] The pigment particles can also be coated.
[0032] The pigment particles have an aspect ratio similar to that described for solid lubricants. In a preferred refinement of the invention, the pigment particles have an aspect ratio of> 10, preferably between 10: 1 and 50: 1.
[0033] In a preferred refinement of the invention, the average diameter of the pigment particles is between 1 and 500 μm, preferably between 5 and 200 μm, particularly preferably between 10 and 150 μm.
[0034] Pigment particles with a diameter between 1 and 100 μm, preferably between 5 and 60 μm, particularly preferably between 1 and 15 μm can also be used.
[0035] The average thickness of the pigment particles ranges between 0.1 and 5 μm, preferably between 0.5 and 2 μm.
[0036] The pigment particles have an aspect ratio of> 10, preferably between 10: 1 and 50: 1, and a thickness of 0.5 pm to 2 pm.
[0037] The at least one type of pigment particles in the form of plates is preferably used in a proportion of 1 to 40% by weight, preferably 2-10% by weight, the% by weight referring to all the components, with the exception of the solvent .
[0038] In a preferred refinement of the invention, the surface of the pigment particles is composed, at least in part, of a transition metal oxide. Preferably, at least the surfaces of the two flat faces of the pigments are composed of a transition metal oxide.
[0039] This can be achieved because the whole pigment particle is composed of the transition metal oxide or because a support material is coated with this transition metal oxide. Various different transition metal oxides may also be present.
[0040] In a preferred refinement of the invention, the transition metal oxide is selected from the group comprising TiO2, ZrO2, ZnO and FeOx.
[0041] In the case that the pigment particles are coated, the transition metal oxide layer has a thickness between 10 nm and 1000 nm, preferably between 50 nm and 300 nm.
[0042] The composition further contains at least one surfactant compound having at least one hydrophobic group and at least one hydrophilic group.
[0043] Surfactant compounds are compounds that have both a hydrophobic group and a hydrophilic group. Therefore, they are able to accumulate in the boundary surfaces. In the case of a hydrophobic surface, for example the hydrophobic group of the surfactant compound would interact with this surface and, for example, react through van der Waals forces with this surface. By the hydrophilic groups of the surfactant compound, the surface coated in this way would thus be more hydrophilic. In the case of a hydrophilic surface, the opposite is valid.
[0044] In the case of the invention, the at least one surfactant compound reacts with the surface of the solid lubricant. These solid lubricants are often rather hydrophobic, such as, for example, boron nitride or graphite. By means of the surfactant compound it is possible to improve the compatibility of the solid lubricant with a hydrophilic environment.
[0045] By this modification of the solid lubricants and / or the pigment particles by the compound With the action of low shear forces, a deep sequence of solid lubricant units in the form of inorganic layers and inserts in the finished polymer composite is achieved. In particular, when the pigment particles contain transition metal oxides, they can be added with provisional complex bonds to the hydrophilic group of the surfactant compound, so that in the intermediate layers between the particles of solid lubricant and the inorganic particles a film is formed. of quasi-transfer. The overall system ultimately slides on the plurality of the quasi-transfer films which are superimposed in vertical direction with respect to the surface of the layer.
[0046] The surfactant compound has at least one hydrophilic group. A group of this type can be, for example, a hydroxyl group, an ether group, an ester group, a carboxylic acid, amino, ammonium, guanidinium, imidazolium, pyridinium, pyrrolidinium, phosphonium or sulfonium group.
[0047] The surfactant compound also has a hydrophobic group. This can be substituted or unsubstituted, branched or unbranched alkyl groups, preferably with 4 to 30 carbon atoms. They can also contain double bonds. It can also be polyether compounds, as well as polysiloxanes which can also be substituted.
[0048] The hydrophobic group can also have aromatic radicals that can interact with the surface of the solid lubricant.
[0049] The surfactant compound can also be a polymer or oligomer having the mentioned groups. The surfactant compound can react, through the hydrophobic or hydrophilic groups already present or at least through other types of groups, with the binder system and thus be integrated into the polymer matrix. The surfactant compound is selected from the group comprising ammonium alkyl compounds, phosphonium alkyls, sulfonium alkyls, imidazolium alkyl, pyridinium alkyl, pyrrolidinium, ionic liquids, functionalized fluorinated polymers, functionalized polyethers and polysiloxanes.
[0050] The fluorinated polymers comprise at least one fluorinated polymer or oligomer with at least one hydrophilic group. These are preferably oligomers, in particular functional short-chain fluoro-oligomers, wherein the functional group is preferably a carboxyl group and particularly preferably a hydroxyl group. All polymers or oligomers which are fluorinated and which have at least one hydrophilic group are suitable. The hydrophilic group can also be used for binding to the binder system.
[0051] In this case, fluorinated polyethers, in particular perfluoropolyethers, are suitable. Other examples are fluorinated epoxides and fluorinated polyurethanes. An example of a monomer which is suitable for the introduction of fluorine atoms in epoxy resin or polyurethane systems is the diglycidyl ether of 1,3,5-fluoroalkylbenzene.
[0052] In addition, copolymers can be used, wherein one type of monomer is fluorinated, e.g. g., customary fluoromonomers such as tetrafluoroethylene, perfluoropropylene, trifluoroethylene, vinylidene fluoride and hexafluoropropylene and can be copolymerized therewith a type of monomer and comprises a functional group such as, eg. eg, vinyl compounds having a functional group such as vinyl ethers, vinyl esters, vinyl alcohols, vinyl acetates, vinylamines having a functional group and substituted therewith. An example is a fluoroethylene-alkylvinyl ether copolymer, wherein the alkyl group (e.g., straight or branched C 1 -C 8 alkyl such as methyl, ethyl, n-propyl, isopropyl or n-, sec- or tert.- butyl) with a suitable functional group such as, p. eg, OH, COOH or oxyalkyl ([-O- (CH2) n] x-OH, where n is the same or different and is 1 to 8 and x is 1 to 3). The fluoroethylene can be, e. eg, tetrafluoroethylene or trifluoroethylene. An alkyl vinyl ether or different alkyl vinyl ethers can be contained in the copolymer, e.g. eg, those with a functional group and those without a functional group. Copolymers of tetrafluoroethylene and perfluoroalkyl vinyl ethers can also be found.
[0053] It is also possible to introduce sulfonic acid or phosphonic acid groups, e.g. eg, by copolymerization of tetrafluoroethylene with trifluorovinyl sulfochloride or perfluorovinylether fluorides. Polytetrafluoroethylene can also be functionalized by graft polymerization with vinyl compounds or acrylic acids mentioned above.
[0054] Fluorinated polymers or oligomers of this type with functional groups are commercially available, e.g. ex. Lumifon® by Asahi Glass Co. Ltd. or Fluorolink® by Solvay Solexis. Preferred fluorinated polymers or oligomers with at least one functional group are fluorinated polyethers, preferably perfluoropolyethers and perfluoroethylene-alkyl vinyl ether copolymers, fluoroethylene preferably being tetrafluoroethylene and / or trifluoromonochloroethylene. The fluorinated polymer or oligomer can have one or more functional groups. Suitable functional groups are, in principle, hydroxy, amino, carboxyl, acid anhydride, epoxide, isocyanate groups, acid chloride groups, nitrile, isonitrile and SH groups. In addition, -SO3H groups and -PO3H groups are also suitable. Amino, hydroxy and carboxy groups are preferred, carboxy groups being preferred and hydroxy groups being particularly preferred.
[0055] Polysiloxanes are synthetic polymeric compounds in which silicon atoms are bonded as chain and / or network through oxygen atoms, and the remaining valences of silicon are saturated by hydrocarbon radicals (most often methyl groups, rare groups ethyl, propyl, phenyl, among others). Compounds of this type are also referred to as polyorganosiloxanes by virtue of the organic radicals. A preferred compound are polyorganosiloxanes which are terminated with hydrophilic groups. Suitable groups of this type are, in principle, hydroxy, amino, carboxyl, acid anhydride, epoxide, isocyanate groups, acid chloride groups, nitrile, isonitrile and SH groups. In addition, -SO3H groups and -PO3H groups are also suitable. Amino, hydroxy and carboxy groups are preferred, carboxy groups being preferred and hydroxy groups being particularly preferred.
[0056] Preferred polyorganosiloxanes are polydimethylsiloxanes, polyphenylmethylsiloxanes or polydialkoxydimethylsiloxanes.
[0057] Other preferred compounds are polyether compounds which can also be terminated with the mentioned groups. These are polymers or oligomers containing ether groups. As a general rule, they are composed of straight or branched chain C2-C8 units that are linked together through oxygen atoms. Preferably, each of the units is linked with the additional unit through exactly 2 oxygen atoms, so that a linear chain results. Examples of units of this type are ethylene, n-propylene, isopropylene, butylene, isobutylene, pentylene, isopentylene, hexylene, isohexylene, heptylene, isoheptylene. The different units can carry or be substituted also with other functional groups, p. eg, with chlorine or fluorine atoms. A polyether compound may also contain several different units, e.g. eg, in the case of a block polymer.
[0058] Preferred polyether compounds are polyether compounds with ethylene (PEG), propylene and / or isopropylene (PPG) units.
[0059] Preferred compounds are polyoxyethylene-polyoxypropylene block polymers (CAS-N ° 9003-11-6) with the following structure
[0060] HO (CH2CH2O) x - (- CH (CH3) CH2O-) y- (CH2CH2O) zH
[0061] wherein x, y and z represent integers of the range of 2 to 130, in particular of 15 to 100, and x and z are equal, but are chosen independently of y.
[0062] The molecular weight of the surfactant compounds can vary within wide ranges. Insofar as oligomers are used, p. eg, often a convenient molecular weight (weight average) can be in the range of at least 100, conveniently at least 500 or preferably at least 600, and independently thereof, up to 5,000, conveniently up to 3,000 and preferably up to 1,500 or up to 1,000
[0063] In the case of polyorganosiloxanes, these are compounds with 3 to 20 siloxane units, preferably 5 to 10 siloxane units. As a general rule, a mixture based on several polyorganosiloxanes of different length is used.
[0064] The at least one surfactant compound is preferably used in a proportion of 0.2 to 15% by weight, preferably 5-10% by weight, the percentages by weight referring to all components, with the exception of the solvent.
[0065] The composition further comprises a hardenable binder system comprising at least one organic polymer or oligomer with one or more functional groups or a precursor thereof. In this case, it can be usual binder systems used for coating compositions or for molding compositions. The binder systems comprise, in particular, the customary organic resins. The binder systems can be systems that harden physically or, preferably, chemically. It can be systems that harden oxidatively, harden by cold or harden thermally or by radiation. It can be one-component or two-component varnishes. Preferably, these are binder systems that are chemically hardenable or crosslinkable. Such hardenable binder systems are common to the person skilled in the art.
[0066] In the case of the binder systems or varnishes that can be used or of the precursor polymers or oligomers used for this, it is, for example, g., of the usual binding systems known from the prior art, as described, e.g. eg, in Ullmanns Encyklopadie der technischen Chemie, volume 15, 4th ed. 1978, p. 489 and following. In particular, they are polymers, oligomers or organic precursors thereof. The precursors of the polymers or oligomers are the monomers or low molecular weight polymerization, condensation or addition products formed therefrom, from which the polymers or oligomers are derived.
[0067] Examples of binder systems or varnishes or of the organic polymers or oligomers used for them are oil varnishes containing oils such as, for example. eg, flaxseed oil, wood oil or soybean oil that are eventually modified with polybutadiene oils; nitrocellulose varnishes that contain nitrocelluloses; varnishes of cellulose esters of organic acids such as esters of cellulose with acetic acid or butyric acid or the anhydrides thereof, finding application, e.g. eg, cellulose acetate-butyrates also in polyurethane varnishes; rubber varnishes containing, p. eg, polyisoprene, polypropylene or chlorinated polyethylene, varnishes based on polyvinyl compounds or polyvinyl resins such as polyolefins, e.g. polyethylene, copolymers of ethylene and vinyl acetate and copolymers of ethylene and (anhydride) maleic acid, PVC, polyvinylidene chloride, polyvinyl alcohol, polyvinylacetals, e.g. eg, polyvinyl butyral, polyvinyl ethers, p. eg, methyl- or ethyl-ether, polyvinyl esters, e.g. eg, poly (vinyl acetate) (PVA) and poly (ethylene terephthalate), polyvinylpyrrolidone, polystyrene, styrene-acrylonitrile (SAN) copolymers, acrylonitrile-butadiene-styrene (ABS) copolymers, styrene-ester copolymers of the maleic acid, styrene-butadiene copolymers and maleic acid styrene-anhydride copolymers; varnishes based on acrylic resins such as polyacrylic acid, polymethacrylic acid, polyacrylamide, acrylic esters or methacrylic esters, p. eg, polymethyl (meth) acrylate, alkyd resins containing dibasic acids or anhydrides such as Italic acid and Italic acid anhydride, and polyols or condensation products thereof which are modified with oleic or fatty acids; saturated polyester resin varnishes containing saturated polyesters based on saturated monomers with two or more functional groups (OH and / or COOH groups); polyurethane varnishes which are often used as bi-component systems containing blocked or unblocked polyisocyanates and polyvinylhydroxyl compounds; varnishes of epoxy resins such as bisphenol A resins, bisphenol F resins, aliphatic and heterocyclic epoxy resins or thermoplastic epoxy resin resins; silicone resin varnishes, urea resin varnishes, melamine, phenoxy and phenol; as well as polyesters, polyarylates, polyamides, polyethers, polyimides, polyamide-imides, polybenzimidazoles, polyurea and polycarbonates. It is also possible to use combinations of these varnishes or of these polymers. Precursors such as, e.g. eg, the monomers of the aforementioned polymers or oligomers.
[0068] Preferred binder systems are polyurethane resin varnishes and polyepoxy resin varnishes. In addition, polyamides, polyimides, polyamide-imides or polybenzimidazoles or their precursors are also preferred, in particular since it is possible to obtain particularly stable systems at high temperature, with those containing aromatic groups being preferred. The aromatic groups can interact with the inserts of the solid lubricant by virtue of their flat structure and their delocalized n- electron system and, therefore, they are particularly advantageous for the tribological properties of the composite material, since they favor its fine distribution as length of the matrix and the formation of the transfer film.
[0069] The binder comprises an organic polymer or oligomer or a precursor thereof with one or more functional groups. Examples of suitable functional groups are C-C double bonds, hydroxy, amino, carboxyl, acid anhydride, epoxide and / or isocyanate groups. Other examples are acid chloride groups, nitrile groups, isonitrile and SH. Of course, the functional groups are chosen so that the desired hardening reactions can take place. Only one functional group that is reactive with itself, or two or more groups that are reactive with each other may be present. The groups can be present in the same or in different polymers, oligomers or precursors thereof or they can be introduced through a hardener or by crosslinking. The relationships are known to the person skilled in the art. The binder system also comprises the hardeners or crosslinking agents optionally employed. Preferred is one of these functional groups that is reactive with a functional group of fluorinated polymer or oligomer. However, it can also be a functional group independent thereof that is only reactive with the functional group of the fluorinated polymer or oligomer.
[0070] Polymers or oligomers or precursors of the same organic compounds, such as monomers used in particular, are polyepoxides, polyols, unblocked or, in particular, blocked polyisocyanates, polyesters, polyamines, polycarboxylic acids or anhydrides of polycarboxylic acids which in each case contain two or more functional groups . In this case, the term "poly" refers to the functional group and not to the degree of polymerization. Correspondingly, the polyols possess two or more hydroxy groups, and can be a monomer, oligomer or polymer (eg, a polyurethane). Concrete components are explained by way of example in what follows in preferred binder systems.
[0071] Polyisocyanates are used, p. eg, for polyurethane resins. The polyisocyanate can have two or more isocyanate groups. It can be, p. eg, aliphatic, alicyclic, aromatic or heterocyclic, monocyclic or polycyclic.
[0072] Customary polyisocyanates, e.g. eg, monomeric polyisocyanates, polyisocyanate adducts, so-called modified polyisocyanates or mixtures thereof. These are known to the person skilled in the art and can be purchased commercially and described, e.g. eg, in G. Oertel, Polyurethane Handbook, Hanser-Verlag 1993 and in "Methoden der organischen Chemie" (Houben-Weyl), Volume 14/2, Thieme Publishing House, 1963. Adducts can present, eg. eg, an average NCO functionality of 2 to 6, preferably of 2.4 to 4.
[0073] In the case of the polyisocyanate adducts, it is discussed, e.g. eg, those that are commonly used as hardeners for bicomponent urethane varnishes and are described in "Lackharze: Chemie, Eingenschaften und Arwendungen", Comp. D. Stoye, W. Freitag, Hanser Publishing House, Munich, Vienna, 1996.
[0074] Examples of suitable polyisocyanates are the known diisocyanates of polyurethane chemistry such as, for example, eg, 1,3-diisocyanatobenzene, 2,4- and 2,6-toluylene diisocyanate (TDI), 1,6-hexamethylene diisocyanate (HMDI), 4,4'and 2,4-diphenylmethane diisocyanate (MDI), naphthylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate, paraphenyl diisocyanate, dicyclohexylmethane diisocyanate, cyclohexyl diisocyanate, polymethylpolyphenyl diisocyanate, 1,6- diisocyanate dodecamethylene, 1,4-bis (isocyanatocyclohexyl) methane, pentamethylene diisocyanate, trimethylene diisocyanate, triphenylmethane diisocyanate, as well as the high molecular weight polyisocyanates derived from these diisocyanates, e.g. eg, based on isocyanurate, uretdione, allophanate and biuret. The isocyanates can be purchased, e.g. eg, under the commercial names Desmodur® and Baymidur® (from Bayer), CARADATE® (from Schell), TEDIMON® (from Enichem) and LUPRANAT® (from BASF). Examples of monomeric polyisocyanates with more than two isocyanate groups are, e.g. 4-isocyanatomethyl 1,8-octandiisocyanate and aromatic polyisocyanates such as 4,4 ', 4 "triphenylmethane triisocyanate or polyphenylenepolymethylene polyisocyanates.
[0075] The polyisocyanate can be used in blocked form in order to prevent an uncontrolled rapid reaction from being initiated and only becoming reactive after deblocking, e.g. ex. by heating. The blocking of isocyanates is a process known to those skilled in the art for reversibly reducing the reactivity of isocyanates. For the blocking of isocyanates, all customary blocking agents, such as, eg, can be used. eg, acetonoxime, cyclohexane oxime, methyl ethyl ketoxime, acetophenone oxime, benzofenoxime, 3,5-dimethylpyrazole, 1,2,4-triazole, malonic acid ethyl ester, acetoacetic acid ethyl ester, " -caprolactam, phenol or ethanol.
[0076]
[0077] As the polyol component, di-, tri- or poly-alcohols such as, eg, can be used. eg, ethylene glycol, trimethylolpropane or partially saponified fatty acid glycerides. However, these are usually used only as the starting base for high molecular weight polyhydroxyl compounds. In this case, it can be treated, p. eg, polyester polyols resulting in more or less branched dicarboxylic acids (Desmophen® types) or polyether polyols resulting by reaction by the addition of epoxides (Desmophen U® types). Other examples are hydroxy-functional acrylic resins (Desmophen A® types).
[0078]
[0079] Polyurethane resin varnishes can be formed from polyisocyanates and polyols. Of course, especially in the case of unblocked polyisocyanates, it may be necessary to mix the components together only shortly before use. The polyisocyanates can also be reacted with compounds with other functional groups containing active hydrogen. Examples of these groups are thiol groups (-SH), primary or secondary amino groups (-NHR ', where R' can be, eg, H, alkyl, cycloalkyl, aryl and corresponding aralkyl and alkaryl groups) or groups carboxyl (-COOH). Reaction products are formed in the case of the reaction with isocyanates, urethanes (in the case of hydroxyl and carboxyl), thiourethanes (in the case of thiol) or ureas (in the case of amine).
[0080]
[0081] Examples of polyepoxides are bisphenol-A resins (eg, condensation products based on bisphenol A and epichlorohydrin), bisphenol F resins (eg, condensation products based on bisphenol F and epichlorohydrin), resins aliphatic epoxides (eg low viscous glycidyl ether), cycloaliphatic epoxy resins and heterocyclic epoxy resins (eg, triglycidyl isocyanurate) or thermoplastic epoxy resin varnishes. Often, polyepoxy resins are mixed for the formation of the film with hardeners in order to achieve crosslinking. Suitable hardeners are organic or inorganic compounds with reactive hydrogen which can react with epoxide or hydroxyl groups. Examples of hardeners used are polyamines, polyaminoamide resins, polyisocyanates, synthetic resins with hydroxyl content such as resins of urea, melamine, phenoxy and phenol, fatty acids and organic acids with reactive double bonds such as acrylic acid or methacrylic acid. In the case of using the aforementioned hardeners, the crosslinking can also take place by means of electron radiation.
[0082]
[0083] The polyamides are condensation products of di-, tri- or tetra-amines and di- or tetra-carboxylic acids or their derivatives, it being possible to use aliphatic and / or aromatic compounds. Polyamides with aromatic units are particularly interesting for interaction with solid lubricants. Also preferred are polyimides, e.g. eg, polycondensates based on aromatic diamines such as benzidine, 4,4-diaminodiphenylether or 4,4'-bis (3-aminophenoxy) diphenylsulfone, and aromatic tetracarboxylic acids or their derivatives such as 4,4'-benzophenone tetracarboxylic acid dianhydride or dianhydride of pyromellitic acid, and polybenzimidazoles, which represent condensation products based on aromatic tetraamines and dicarboxylic acids or their derivatives. In the composition according to the invention, the corresponding monomers or condensation products of low molecular weight can be used for the aforementioned synthetic materials.
[0084]
[0085] The binder system is preferably used in a proportion of 40 to 80% by weight, preferably 40-60% by weight, the% by weight referring to all the components, with the exception of the solvent.
[0086]
[0087] In a refinement of the invention, the composition comprises inorganic particles. Virtually all ceramic and vitreous systems are suitable for the particles, but also eventually metals, semiconductors and usual charges. It is preferably ceramic particles. Often, oxides, nitrides, carbides, carbonitrides, silicides or borides are used. Mixtures of different particles can also be used. Preferably, abrasive particles or hard substances are used, particularly preferably sparingly abrasive particles with a universal hardness between 1000 MPa and 3500 MPa. The particles may be modified on the surface or unmodified.
[0088] In the case of particles, it is treated, p. eg metal-based particles, including metal alloys, semimetal (eg, B, Si and Ge) or metallic compounds, in particular metal halides, particularly preferably oxides and sulphides, nitrides, carbides, silicides and borides. A type of particle or a mixture can be used.
[0089] Examples are oxides (optionally hydrated) such as ZnO, CdO, SiO2, GeO2, TiO2, ZrO2, CeO2, SnO2, A ^ O3 (eg, amperite, boehmite, AlO (OH), also in the form of aluminum hydroxide) ), B2O3, In2O3, La2O3, Fe2O3 (eg, hematite), Fe3O4, Cu2O, Ta2O5, Nb2O5, V2O5, MoO3 or WO3; other calcohalogenides such as, p. eg, sulfides (eg, CdS, ZnS, PbS and Ag2S), selenides (eg, GaSe, CdSe and ZnSe) and teluros (eg, ZnTe or CdTe); halides such as AgCl, AgBr, AgI, CuCl, CuBr, CdI2 and PbI2; carbides such as CdC2, B4C or SiC; arsenides such as AlAs, GaAs and GeAs; antimonides such InSb; nitrides such as Si3N4 and Ti3N4; phosphides such as GaP, InP, Zn3P2 and Cd3P2; phosphates, silicates, zirconates, aluminates, stannates and the corresponding mixed oxides (eg, indium-tin oxide (ITO), antimony-tin oxide (ATO), fluorine-containing tin oxide (FTO), light pigments) with compounds containing Y or Eu, spinels, ferrites or mixed oxides with perovskite structure such as BaTiO3 and PbTiO3).
[0090] Preferably, hard powders are used for the particles. Examples of hard powders are diamond powders, garnet, pumice, tripole, silicon carbide, emery, aluminum oxides such as p. eg, amperite and corundum, silicon oxides such as diatomaceous earth, quartz or polishing sands, gypsum, boron carbide and other oxides, borides, silicides, carbides, carbonitrides and nitrides.
[0091] Preferably, the inorganic particles are composed of Si3N4, SiC, B4C, A ^ O3 and / or SO2.
[0092] The particle size of the particles is not particularly limited. Conveniently, the average particle diameter is found, e.g. in the range of at least 5 nm, preferably at least 10 nm to not more than 100 | jm, preferably not more than 50 jm and particularly preferably not more than 20 jm or 10 jm. Mixtures of particles of different particle size can also be used. For example, SiC UF-10 can be used with coarser UF-05 and finer UF-15 in combination.
[0093] In a preferred refinement, the average particle size ranges between 0.1 and 3 jm.
[0094] The average particle diameter refers to the determined numerical average. The particle sizes were determined by scanning electron microscopy.
[0095] The inorganic particles are preferably used in a proportion of 1 to 15% by weight, preferably 2-10% by weight, the% by weight referring to all the components, with the exception of the solvent.
[0096] In a further development of the invention, the inorganic particles have a hardness of 1,000 MPa at 3,500 MPa, preferably between 1,200 MPa and 2,000 MPa, measured as universal hardness (HU).
[0097] In this case, it may be necessary to adapt the hardness of the inorganic particles to the other components, in particular, the pigment particles. With this, the stability of the hardened coating can be improved, since the inorganic particles can not exert any abrasive effect on the pigment particles.
[0098] In the composite material obtained in this way, the inorganic particles are incorporated in the intermediate layers and lead to an additional support of the overall structure in order to prevent in this way a micro-elevation of the opposite body. In order to optimally fulfill this function, the particles of hard material must not act in an abrasive manner against the inorganic plates and must be chosen in a suitable way to their hardness.
[0099] By means of the fine structuring of the laminated materials in the described sense, composite materials with an additional high barrier function are obtained which offer a good protection of the substrate against corrosive attack. In addition, the surfactant compounds, through their interaction with the inorganic pigment particles and / or possibly inorganic particles, orientate these tendentially towards the hydrophobic face in the air, whereby the tribological functions on the surface of the layer are reached and the layers present at the same time, due to the accumulation of reactive matrix components in the direction of the substrate, a good adherence with respect to the background as a necessary support of a good protection against corrosion. The inorganic solid lubricants are then arranged in the form of layers between the pigment plates. The composition usually contains at least one solvent in which the components are dissolved or suspended.
[0100] As solvents (dispersing agents), e.g. eg, usual solvents for coatings. A suitable solvent is water. Suitable organic solvents are polar solvents as well as non-polar and aprotic solvents. Examples thereof are alcohols, preferably lower aliphatic alcohols (C 1 -C 8 alcohols) such as methanol, ethanol, 1-propanol, i-propanol and 1-butanol, ketones, preferably aliphatic ketones such as acetone, methyl ketone and methyl isobutyl ketone, esters such as 2-methoxypropyl acetate, butyl acetate and ethyl acetate, ethers, preferably lower dialkyl ethers such as diethyl ether, cyclic ethers such as dioxane or THF, or monoethers of diols such as ethylene glycol or propylene glycol, with C1-C8 alcohols, aromatic or aliphatic hydrocarbons such as hexane, heptane, petroleum ether, toluene and xylene, amides such as dimethylformamide and mixtures thereof. If blocked isocyanates are used, the protic solvents must have a boiling point below the blocking temperature of the blocked isocyanate in order to minimize side reactions. Examples are aliphatic alcohols with 1 to 4 carbon atoms. High-boiling solvents such as methyl-2-pyrrolidone (NMP) or Y-butyrolactone (GBL) are also suitable. Usually, solvents and / or mixtures based on different solvents are added up to solid contents of the composition between 10 and 70% by weight, preferably between 20% by weight and 50% by weight. The final amount is oriented, among others, depending on the subsequent method of application.
[0101] In a preferred refinement of the invention, the composition contains the following components:
[0102] 1-40% by weight of at least one solid lubricant in the form of plates;
[0103] 0.2-15% by weight of a surfactant compound;
[0104] - 29-97.8% by weight of a hardenable binder system;
[0105] - 1-40% by weight of inorganic pigment particles in the form of plates;
[0106] - 0-15% by weight of inorganic particles.
[0107] The composition may also contain other additives in the range of 0-5% by weight. The data in% by weight refer to the components mentioned without the solvent of the composition and a total of up to 100% by weight are completed.
[0108] In a preferred refinement of the invention, the composition contains the following components:
[0109] - 20-30% by weight of at least one solid lubricant in the form of plates;
[0110] 5-10% by weight of a surfactant compound;
[0111] - 40-71% by weight of a hardenable binder system;
[0112] 2-10% by weight of inorganic pigment particles in the form of plates;
[0113] - 2-10% by weight of inorganic particles.
[0114] The composition may also contain other additives in the range of 0-5% by weight. The data in% by weight refer to the components mentioned without the solvent of the composition and a total of up to 100% by weight are completed.
[0115] The invention also relates to a process for the production of a tribological composite material.
[0116] In the following, different stages of the procedure are described in greater detail. The steps do not necessarily have to be carried out in the indicated sequence, and the method to be explained may also have other steps not mentioned.
[0117] In a first step, the composition is applied on a substrate. This can take place in any usual way. All common coating processes can be used. Examples are coating by centrifugation, coating by (electro) dip, doctor blade application, spraying, injection, casting, brush application, watering paint, knife casting, slit coating, meniscus coating, curtain coating and roller application. .
[0118] All common materials can be coated. Examples of a suitable substrate are metal substrates, semiconductors, glass, ceramic material, including porous ceramic materials, glass ceramic, synthetic material, wood, paper, building materials or inorganic-organic composite materials. The substrates can be pre-treated, e.g. by means of a corona treatment or they can be provided with a precoating such as a varnishing (varnished surfaces), an enameling, a painting or a metallized surface or by impregnation.
[0119] As examples of metal substrates may be mentioned, e.g. Copper, aluminum, brass, iron, steel and zinc. Examples of semiconductors are silicon, p. eg, in the form of wafers, and indium-tin oxide layers (ITO layers) on glass. All common types of glass can be used as glass (eg amorphous silica, borosilicate glass or soda lime silicate glass). Examples of substrates of synthetic materials are polycarbonate, poly (methyl methacrylate), polyacrylates, poly (ethylene terephthalate), polyamide, polyetherketone (PEK), polyetheretherketone (PEEK) or polyoxymethylene. in particular for optical or opto-electronic applications, transparent substrates are suitable, e.g. eg, glass or synthetic material. Examples of construction materials are stones, concrete, tiles, drywall or tiles.
[0120] After that, hardening takes place. Since hardening depends essentially on the binding systems used, special approaches can not be applied. The person skilled in the art is aware of which hardening conditions are suitable for the respective known binder systems. As said, these can be hardenable systems of oxidative form, hardenable by cold or systems curable thermally or by radiation.
[0121] Depending on the particle size of the particles added, the properties can be modified at different intervals. If particles are used in the pm range, the refractive index of the matrix is not adapted to the particles, so that layers of opaque to translucent are achieved. By choosing the starting components, in particular the matrix material and the proportion of aromatic components (high refraction) and aliphatic components, the value of the refraction can be adapted to different powders used with average particle diameters in the interval of pm. Also here, the refractive index of the powders plays a role, in which there is a relatively large choice, starting with SiO2 with very low refractive indices through aluminum oxide, silicon carbide and zirconium dioxide with indices of higher refraction.
[0122] In a preferred refinement of the process, the composition is prepared in such a way that a mixture based on at least one solid lubricant in the form of plates and a surfactant compound in a suitable solvent for crosslinkable polymers is first prepared. In this case, the at least one solid lubricant is surface modified with the surfactant compound.
[0123] Only in a next step are the hardenable binder system and the at least one type of inorganic pigment particles in the form of plates added. In this step, the inorganic particles are also added optionally. The hardenable binder system can also be dissolved in one or more solvents. The pigment particles can also be added in the form of a suspension.
[0124] Special features and additional features result from the following description of preferred embodiments in conjunction with the dependent claims. In this case, the respective features can be implemented on their own or in several in combination with each other. The possibilities of solving the problem are not limited to the realization examples. Thus, for example, interval data always cover all intermediate values - not mentioned - and all partial intervals imaginable.
[0125] Fig. 1 comparison of different pigment particles in terms of their influence on the coefficient of friction p in the case of a concentration of pigments of 5% by weight (BN 110: 30% by weight, SiC 5% by weight); A 65: comparative sample without pigment;
[0126] Fig. 2 comparison of different pigment particles in terms of their influence on the coefficient of friction p in the case of a concentration of pigments of 5% by weight (BN 110: 30% by weight, SiC 5% by weight); AM: Autumn Mystery, LS: Lapis Sunlight); A 65: comparative sample without pigment;
[0127] Fig. 3 Variation of SiC UF-10 in the case of 5% Lpis S and 10% FL;
[0128] Fig. 4 Variation of Lapis S in the SiC system;
[0129] Fig. 5 Systematic structure of the SiC system; A193 = composition according to the invention; A113, A119, A274 and A65 = comparative examples;
[0130] Fig. 6 Variation of the content of Si3N4 nano70;
[0131] Fig. 7 Variation of Si3N4 E05;
[0132] Fig. 8 Variation of Si3N4 E03;
[0133] Fig. 9 Variation of the content of Si3N4 M11-A (broad distribution);
[0134] Fig. 10 Variation of content of Si3N4B7 (3.0 pm);
[0135] Fig. 11 Variation of FL D10H content in the system without urea;
[0136] Fig. 12 Variation of content of FL D10H in the Si3N4 B7 system (3.0 pm);
[0137] Fig. 13 Systematic structure of Si3N4 M11-A in a system without BN;
[0138] Fig. 14 Systematic structure Si3N4 M11-A-system with BN;
[0139] Fig. 15 REM photograph of Hebofil BN 110;
[0140] Fig. 16 REM photograph of SiC;
[0141] Fig. 17 REM photograph of the particles of hard material YES3N4 EO5;
[0142] Fig. 18 REM photograph of the particles of hard material SÍ3N4 EO3;
[0143] Fig. 19 REM photograph of hard material particles Si3N4 M11-A;
[0144] Fig. 20 REM photography of the pigment particles Autumn Mystery with FeO2;
[0145] Fig. 21 REM photograph of the Lapis Sunlight pigment particles with TO2;
[0146] Fig. 22 REM photograph seen in plan of A219;
[0147] Fig. 23 Photograph REM cross section of A219;
[0148] Fig. 24 Spray test with neutral salt after 312 h.
[0149] Numerous variations and refinements of the described embodiments can be implemented. Execution examples:
[0150] General procedure for the synthesis:
[0151] In a Dispermat device 10-40% of the solvent used is dispersed, dispersion glass beads, the solid lubricant and the surfactant compound with at least one hydrophilic group and at least one hydrophobic group at 50 ° C and 2000 rpm. After 15 minutes, the matrix components are added, as well as, if necessary, the hard material particles and dispersed for another 90 min at 50 ° C and 2000 rpm. The glass beads are separated from the crude product by filtration. The subsequent dispersion of the pigment particles in the total mixture takes place by means of a dissolving disc over 30 min at 25 ° C and 1000 rpm.
[0152] Application:
[0153] The obtained reaction mixture can be applied by technically customary applications such as, e.g. eg, application by immersion or spray application. The hardening takes place at 150 ° C-250 ° C for 1h - 2h. Compositions according to the invention
[0154] Example 1: Base system without urea (A200)
[0155] 5.94 g of BN 110 boron nitride (Henze) are mixed over 15 min with 35 ml of N-methyl-2-pyrrolidone (NMP) and 1.98 g of Fluorolink D10H (Solvay) in a Dispermat device at 50 ° C and 2000 rpm. Then, 3.37 g of pyromellitic dianhydride (PMDA) and 7.51 g of bis [4- (3-aminophenoxy) phenyl] sulfone (BAPPS) are added and dispersed for another 90 min at 50 ° C and 2000 rpm. After the separation of the glass beads, 0.99 g of Lapis Sunlight T20-04-WNT (Merck) are added and the total mixture obtained is combined by means of a dissolving disc over 30 min at 25 ° C and 1000 rpm. A homogenous liquid reaction mixture of a light brown color is obtained. Example 2: analogously to Example 1 with 1.25% SiC (A201)
[0156] 6.08 g of BN 110 boron nitride (Henze) are mixed over 15 min with 35 ml of NMP and 2.03 g of Fluorolink D10H (Solvay) in a Dispermat device at 50 ° C and 2000 rpm. Next, 3.37 g of PMDA, 7.51 g of BApPS and 0.25 g of SiC UF10H (Hc Starck) are added and dispersed for another 90 min at 50 ° C and 2000 rpm. After separation of the glass beads, 1.01 g of Lapis Sunlight T20-04-WNT (Merck) are added and the total mixture obtained is combined by means of a dissolving disc over 30 min at 25 ° C and 1000 rpm. A homogenous liquid reaction mixture of a light brown color is obtained.
[0157] Example 3: analogously to Example 1 with 2.5% SiC (A202)
[0158] 6.22 g of BN 110 boron nitride (Henze) are mixed over 15 min with 35 ml of NMP and 2.07 g of Fluorolink D10H (Solvay) in a Dispermat device at 50 ° C and 2000 rpm. Next, 3.37 g of PMDA, 7.51 g of BAPPS and 0.52 g of SiC UF10H (H ^c Starck) are added and dispersed for another 90 min at 50 ° C and 2000 rpm. After separation of the glass beads, 1.04 g of Lapis Sunlight T20-04-WNT (Merck) are added and the total mixture obtained is combined by means of a dissolving disk over 30 min at 25 ° C and 1000 rpm. A homogenous liquid reaction mixture of a light brown color is obtained.
[0159] Example 4: analogously to Example 1 with 5% SiC (A189 / A193)
[0160] 6.53 g of BN 110 boron nitride (Henze) are mixed over 15 min with 35 ml of NMP and 2.18 g of Fluorolink D10H (Solvay) in a Dispermat device at 50 ° C and 2000 rpm. Next, 3.37 g of PMDA, 7.51 g of BAPPS and 1.09 g of SiC UF10H (Hc Starck) are added and dispersed for another 90 min at 50 ° C and 2000 rpm. After separation of the glass beads, 1.09 g of Lapis Sunlight T20-04-WNT (Merck) are added and the total mixture obtained is combined by a dissolving disc over 30 min at 25 ° C and 1000 rpm. You get a mixture of homogenous liquid reaction of a light brown color.
[0161] Example 5: analogously to Example 1 with 10% SiC (A204)
[0162] 7.26 g of BN 110 boron nitride (Henze) are mixed over 15 min with 35 ml of NMP and 2.42 g of Fluorolink D10H (Solvay) in a Dispermat device at 50 ° C and 2000 rpm. Then, 3.37 g of PMDA, 7.51 g of BApPS and 2.42 g of SiC UF10H (H ^c Starck) are added and dispersed for another 90 min at 50 ° C and 2000 rpm. After the separation of the glass beads, 1.21 g of Lapis Sunlight T20-04-WNT (Merck) are added and the total mixture obtained is combined by means of a dissolving disc for 30 min at 25 ° C and 1000 rpm. A homogenous liquid reaction mixture of a light brown color is obtained.
[0163] Example 6: analogously to Example 1 with 15% SiC (A205)
[0164] 8.16 g of BN 110 boron nitride (Henze) are mixed over 15 min with 35 ml of NMP and 2.72 g of Fluorolink D10H (Solvay) in a Dispermat device at 50 ° C and 2000 rpm. Next, 3.37 g of PMDA, 7.51 g of BApPS and 4.08 g of SiC UF10H (H ^c Starck) are added and dispersed for another 90 min at 50 ° C and 2000 rpm. After separation of the glass beads, 1.36 g of Lapis Sunlight T20-04-WNT (Merck) are added and the total mixture obtained is combined by means of a dissolving disk over 30 min at 25 ° C and 1000 rpm. A homogenous liquid reaction mixture of a light brown color is obtained.
[0165] Example 7: analogously to Example 1 with 20% SiC (A206)
[0166] 9.33 g of BN 110 boron nitride (Henze) are mixed over 15 min with 35 ml of NMP and 3.11 g of Fluorolink D10H (Solvay) in a Dispermat device at 50 ° C and 2000 rpm. Next, 3.37 g of PMDA, 7.51 g of BAPPS and 6.22 g of SiC UF10H (H ^c Starck) are added and dispersed for another 90 min at 50 ° C and 2000 rpm. After separation of the glass beads, 1.55 g of Lapis Sunlight T20-04-WNT (Merck) are added and the total mixture obtained is combined by means of a dissolving disk over 30 min at 25 ° C and 1000 rpm. A homogenous liquid reaction mixture of a light brown color is obtained.
[0167] Example 8: analogously to Example 2 with 1.25% Si3N4 E05 (A233)
[0168] 6.08 g of boron nitride BN 110 (Henze), 35 ml of NMP, 2.03 g of Fluorolink D10H (Solvay), 3.37 g of PMDA, 7.51 g of BAPPS, 0.25 g of Si3N E05 ( UBE), 1.01 g of Lapis Sunlight T20-04-WNT (Merck).
[0169] Example 9: analogously to Example 3 with 2.5% Si3N4 E05 (A234)
[0170] 6.22 g of boron nitride BN 110 (Henze), 35 ml of NMP, 2.07 g of Fluorolink D10H (Solvay), 3.37 g of PMDA, 7.51 g of BAPPS, 0.52 g of SiaN4 E05 ( UBE), 1.04 g of Lapis Sunlight T20-04-WNT (Merck).
[0171] Example 10: analogously to Example 4 with 5% Si3N4 E05 (A235)
[0172] 6.53 g of boron nitride BN 110 (Henze), 35 ml of NMP, 2.18 g of Fluorolink D10H (Solvay), 3.37 g of PMDA, 7.51 g of BAPPS, 1.09 g of SiaN4 E05 ( UBE), 1.09 g of Lapis Sunlight T20-04-WNT (Merck).
[0173] Example 11: analogously to Example 5 with 10% S ^ N4 E05 (A236)
[0174] 7.26 g of boron nitride BN 110 (Henze), 35 ml of NMP, 2.42 g of Fluorolink D10H (Solvay), 3.37 g of PMDA, 7.51 g of BAPPS, 2.42 g of Si3N E05 ( UBE), 1.21 g of Lapis Sunlight T20-04-WNT (Merck).
[0175] Example 12: analogously to Example 6 with 15% S ^ N4 E05 (A237)
[0176] 8.16 g of boron nitride BN 110 (Henze), 35 ml of NMP, 2.72 g of Fluorolink D10H (Solvay), 3.37 g of PMDA, 7.51 g of BAPPS, 4.08 g of Si3N E05 ( UBE), 1.36 g of Lapis Sunlight T20-04-WNT (Merck).
[0177] Example 13: analogously to Example 2 with 1.25% of S ^ N4 E03 (A238)
[0178] 6.08 g of boron nitride BN 110 (Henze), 35 ml of NMP, 2.03 g of Fluorolink D10H (Solvay), 3.37 g of PMDA, 7.51 g of BAPPS, 0.25 g of Si3N E03 ( UBE), 1.01 g of Lapis Sunlight T20-04-WNT (Merck).
[0179] Example 14: analogously to Example 3 with 2.5% S ^ N4 E03 (A239)
[0180] 6.22 g of boron nitride BN 110 (Henze), 35 ml of NMP, 2.07 g of Fluorolink D10H (Solvay), 3.37 g of PMDA, 7.51 g of BAPPS, 0.52 g of Si3N E03 ( UBE), 1.04 g of Lapis Sunlight T20-04-WNT (Merck).
[0181] Example 15: analogously to Example 4 with 5% S ^ N4 E03 (A240)
[0182] 6.53 g of BN 110 boron nitride (Henze), 35 ml of NMP, 2.18 g of Fluorolink D10H (Solvay), 3.37 g of PMDA, 7.51 g of BAPPS, 1.09 g of Si3N E03 ( UBE), 1.09 g of Lapis Sunlight T20-04-WNT (Merck).
[0183] Example 16: analogously to Example 5 with 10% S ^ N4 E03 (A241)
[0184] 7.26 g of boron nitride BN 110 (Henze), 35 ml of NMP, 2.42 g of Fluorolink D10H (Solvay), 3.37 g of PMDA, 7.51 g of BAPPS, 2.42 g of Si3N E03 ( UBE), 1.21 g of Lapis Sunlight T20-04-WNT (Merck).
[0185] Example 17: analogously to Example 6 with 15% Si3N4 E03 (A242)
[0186] 8.16 g of boron nitride BN 110 (Henze), 35 ml of NMP, 2.72 g of Fluorolink D10H (Solvay), 3.37 g of PMDA, 7.51 g of BAPPS, 4.08 g of Si3N E03 ( UBE), 1.36 g of Lapis Sunlight T20-04-WNT (Merck).
[0187] Example 18: analogously to Example 2 with 1.25% of Si3N4 M11-A (A218)
[0188] 6.08 g of boron nitride BN 110 (Henze), 35 ml of NMP, 2.03 g of Fluorolink D10H (Solvay), 3.37 g of PMDA, 7.51 g of BAPPS, 0.25 g of Si3N4 M11- A (HC Starck), 1.01 g of Lapis Sunlight T20-04-WNT (Merck).
[0189] Example 19: analogously to Example 3 with 2.5% Si3N4 M11-A (A219)
[0190] 6.22 g of boron nitride BN 110 (Henze), 35 ml of NMP, 2.07 g of Fluorolink D10H (Solvay), 3.37 g of PMDA, 7.51 g of BAPPS, 0.52 g of Si3N4 M11- A (HC Starck), 1.04 g of Lapis Sunlight T20-04-WNT (Merck).
[0191] Example 20: analogously to Example 4 with 5% Si3N4 M11-A (A220)
[0192] 6.53 g of boron nitride BN 110 (Henze), 35 ml of NMP, 2.18 g of Fluorolink D10H (Solvay), 3.37 g of PMDA, 7.51 g of BAPPS, 1.09 g of Si3N4 M11- A (HC Starck), 1.09 g of Lapis Sunlight T20-04-WNT (Merck).
[0193] Example 21: analogously to Example 5 with 10% Si3N4 M11-A (A221)
[0194] 7.26 g of boron nitride BN 110 (Henze), 35 ml of NMP, 2.42 g of Fluorolink D10H (Solvay), 3.37 g of PMDA, 7.51 g of BAPPS, 2.42 g of Si3N4 M11- A (HC Starck), 1.21 g of Lapis Sunlight T20-04-WNT (Merck).
[0195] Example 22: analogously to Example 6 with 15% Si3N4 M11-A (A222)
[0196] 8.16 g of boron nitride BN 110 (Henze), 35 ml of NMP, 2.72 g of Fluorolink D10H (Solvay), 3.37 g of PMDA, 7.51 g of BAPPS, 4.08 g of Si3N4 M11- A (HC Starck), 1.36 g of Lapis Sunlight T20-04-WNT (Merck).
[0197] Example 23: analogously to Example 2 with 1.25% Si3N4 B7 (A223)
[0198] 6.08 g of boron nitride BN 110 (Henze), 35 ml of NMP, 2.03 g of Fluorolink D10H (Solvay), 3.37 g of PMDA, 7.51 g of BAPPS, 0.25 g of Si3N4 B7 ( HC Starck), 1.01 g of Lapis Sunlight T20-04-WNT (Merck).
[0199] Example 24: analogously to Example 3 with 2.5% Si3N4 B7 (A224)
[0200] 6.22 g of boron nitride BN 110 (Henze), 35 ml of NMP, 2.07 g of Fluorolink D10H (Solvay), 3.37 g of PMDA, 7.51 g of BAPPS, 0.52 g of Si3N4 B7 ( HC Starck), 1.04 g of Lapis Sunlight T20-04-WNT (Merck).
[0201] Example 25: analogously to Example 4 with 5% Si3N4 B7 (A225)
[0202] 6.53 g of boron nitride BN 110 (Henze), 35 ml of NMP, 2.18 g of Fluorolink D10H (Solvay), 3.37 g of PMDA, 7.51 g of BAPPS, 1.09 g of Si3N4 B7 ( HC Starck), 1.09 g of Lapis Sunlight T20-04-WNT (Merck).
[0203] Example 26: analogously to Example 5 with 10% Si3N4 B7 (A226)
[0204] 7.26 g of boron nitride BN 110 (Henze), 35 ml of NMP, 2.42 g of Fluorolink D10H (Solvay), 3.37 g of PMDA, 7.51 g of BAPPS, 2.42 g of Si3N4 B7 ( HC Starck), 1.21 g of Lapis Sunlight T20-04-WNT (Merck).
[0205] Example 27: analogously to Example 6 with 15% Si3N4 B7 (A227)
[0206] 8.16 g of boron nitride BN 110 (Henze), 35 ml of NMP, 2.42 g of Fluorolink D10H (Solvay), 3.37 g of PMDA, 7.51 g of BAPPS, 4.08 g of Si3N4 B7 ( HC Starck), 1.36 g of Lapis Sunlight T20-04-WNT (Merck).
[0207] Example 28: analogously to Example 2 with 1.25% of Si3N4 nano70 (A228)
[0208] 6.08 g of boron nitride BN 110 (Henze), 35 ml of NMP, 2.03 g of Fluorolink D10H (Solvay), 3.37 g of PMDA, 7.51 g of BAPPS, 0.25 g of Si3N4 nano70 ( Aldrich), 1.01 g of Lapis Sunlight T20-04-WNT (Merck).
[0209] Example 29: analogously to Example 3 with 2.5% Si3N4 nano70 (A229)
[0210] 6.22 g of boron nitride BN 110 (Henze), 35 ml of NMP, 2.07 g of Fluorolink D10H (Solvay), 3.37 g of PMDA, 7.51 g of BAPPS, 0.52 g of Si3N4 nano70 ( Aldrich), 1.04 g of Lapis Sunlight T20-04-WNT (Merck).
[0211] Example 30: analogously to Example 4 with 5% Si3N4 nano70 (A230)
[0212] 6.53 g of boron nitride BN 110 (Henze), 35 ml of NMP, 2.18 g of Fluorolink D10H (Solvay), 3.37 g of PMDA, 7.51 g of BAPPS, 1.09 g of SÍ3N4 nano70 (Aldrich), 1.09 g of Lapis Sunlight T20-04-WNT (Merck).
[0213] Example 31: analogously to Example 5 with 10% of SÍ3N4 nano70 (A231)
[0214] 7.26 g of boron nitride BN 110 (Henze), 35 ml of NMP, 2.42 g of Fluorolink D10H (Solvay), 3.37 g of PMDA, 7.51 g of BAPPS, 2.42 g of Si3N4 nano70 (Aldrich), 1.21 g of Lapis Sunlight T20-04-WNT (Merck).
[0215] Example 32: analogously to Example 6 with 15% Si3N4 nano70 (A232)
[0216] 8.16 g of BN 110 boron nitride (Henze), 35 ml of NMP, 2.72 g of Fluorolink D10H (Solvay), 3.37 g of PMDA, 7.51 g of BAPPS, 4.08 g of Si3N4 nano70 (Aldrich), 1.36 g of Lapis Sunlight T20-04-WNT (Merck).
[0217] Example 33: analogously to Example 23 with 1.25% FL D10H (A243)
[0218] 5.22 g of BN 110 boron nitride (Henze), 35 ml of NMP, 0.22 g of Fluorolink D10H (Solvay), 3.37 g of PMDA, 7.51 g of BAPPS, 0.22 g of Si3N4 B7 ( HC Starck), 0.87 g of Lapis Sunlight T20-04-WNT (Merck).
[0219] Example 34: analogously to Example 23 with 2.5% FL D10H (A244)
[0220] 5.33 g of boron nitride BN 110 (Henze), 35 ml of NMP, 0.44 g of Fluorolink D10H (Solvay), 3.37 g of PMDA, 7.51 g of BAPPS, 0.22 g of Si3N4 B7 (HC Starck), 0.89 g of Lapis Sunlight T20-04-WNT (Merck).
[0221] Example 35: analogously to Example 23 with 5% FL D10H (A245)
[0222] 5.56 g of boron nitride BN 110 (Henze), 35 ml of NMP, 0.93 g of Fluorolink D10H (Solvay), 3.37 g of PMDA, 7.51 g of BAPPS, 0.23 g of Si3N4 B7 (HC Starck), 0.93 g of Lapis Sunlight T20-04-WNT (Merck).
[0223] Example 36: analogously to Example 23 with 7.5% FL D10H (A246)
[0224] 5.81 g of boron nitride BN 110 (Henze), 35 ml of NMP, 1.45 g of Fluorolink D10H (Solvay), 3.37 g of PMDA, 7.51 g of BAPPS, 0.24 g of Si3N4 B7 (HC Starck), 0.97 g of Lapis Sunlight T20-04-WNT (Merck).
[0225] Example 37: analogously to Example 23 with 15% FL D10H (A247)
[0226] 6.70 g of boron nitride BN 110 (Henze), 35 ml of NMP, 3.35 g of Fluorolink D10H (Solvay), 3.37 g of PMDA, 7.51 g of BAPPS, 0.28 g of Si3N4 B7 (HC Starck), 1.12 g of Lapis Sunlight T20-04-WNT (Merck).
[0227] Example 38: analogously to Example 25 with 10% PDMS-Diol-700 instead of 10% FL D10H (A225-PDMS-Diol-700)
[0228] 6.53 g of BN 110 boron nitride (Henze) are mixed over 15 min with 35 ml of NMP and 2.18 g of PDMS-Diol-700 (Aldrich CAS: 70131-67-8) poly (dimethylsiloxane) ), hydroxy terminated: Mn - 550, chain length, 7-8 Si units, C-mH4408 SI7 Weight Mol .: 537.09 C16H50OgSi8 Mol Weight: 611.25) in a Dispermat device at 50 ° C and 2000 rpm. Then, 3.37 g of PMDA, 7.51 g of BAPPS and 1.09 g of Si3N4 B7 (HC Starck) are added and dispersed for another 90 min at 50 ° C and 2000 rpm. After separation of the glass beads, 1.09 g of Lapis Sunlight T20-04-WNT (Merck) are added and the total mixture obtained is combined by a dissolving disc over 30 min at 25 ° C and 1000 rpm. A homogenous liquid reaction mixture of a light brown color is obtained. Example 39: analogously to Example 19 with 10% PEG-block-PPG-block-PEG instead of 10% FL D10H (A219-PEG-b-PPG-b-PEG)
[0229] 6.22 g of boron nitride BN 110 (Henze) are mixed over 15 min with 35 ml of NMP and 2.07 g of poly (ethylene glycol) -block-poly (propylene glycol) -block-poly (ethylene glycol) (Aldrich 435406 CAS: [9003-11-6] Mn - 1,100, HO (C2H4O) m (C3H6O) n (C2H40) mH) in a Dispermat device at 50 ° C and 2000 rpm. Next, 3.37 g of PMDA, 7.51 g of BAPPS and 0.52 g of Si3N4 M11-A (HC Starck) are added and dispersed for another 90 min at 50 ° C and 2000 rpm. After separation of the glass beads, 1.04 g of Lapis Sunlight T20-04-WNT (Merck) are added and the total mixture obtained is combined by means of a dissolving disk over 30 min at 25 ° C and 1000 rpm. A homogenous liquid reaction mixture of a light brown color is obtained.
[0230] Comparative compositions without lubricant
[0231] Comparative Example 1: Without lubricant, without pigment, without urea, without surfactant compound (A265)
[0232] 3.37 g of PMDA and 7.51 g of BAPPS are mixed with 35 ml of NMP in a Dispermat device at 50 ° C and 2000 rpm for 115 min. After separation of the glass beads, a homogeneous and liquid reaction mixture of a brownish color is obtained.
[0233] Comparative Example 2: Without lubricant, without pigment, without urea, with surfactant compound (A119)
[0234] 3.37 g of PMDA, 7.51 g of BAPPS and 2.09 g of Fluorolink D10H (Solvay) are mixed with 35 ml of NMP in a Dispermat device at 50 ° C and 2000 rpm for 115 min. After separation of the glass beads, a homogeneous and liquid reaction mixture of a brownish color is obtained.
[0235] Comparative Example 3: Without lubricant, with pigment, without urea, with surfactant compound (A219-14)
[0236] 3.37 g of PMDA, 7.51 g of BAPPS and 2.07 g of Fluorolink D10H (Solvay) are mixed with 35 ml of NMP in a Dispermat device at 50 ° C and 2000 rpm for 115 min. After separation of the glass beads, 1.04 g of Lapis Sunlight T20-04-WNT (Merck) are added and the total mixture obtained is combined by means of a dissolving disk over 30 min at 25 ° C and 1000 rpm. A homogenous liquid reaction mixture of a light brown color is obtained.
[0237] Comparative Example 4: Without lubricant, with pigment, with urea, with surfactant compound (A219-12)
[0238] 3.37 g of PMDA, 7.51 g of BAPPS are mixed with 35 ml of NMP and 2.07 g of Fluorolink D10H (Solvay) in a Dispermat device at 50 ° C and 2000 rpm for 115 min. Then, 0.52 g of Si3N4 M11-A (HC Starck) is added and dispersed for another 90 min at 50 ° C and 2000 rpm. After separation of the glass beads, 1.04 g of Lapis Sunlight T20-04-WNT (Merck) are added and the total mixture obtained is combined by means of a dissolving disk over 30 min at 25 ° C and 1000 rpm. A homogenous liquid reaction mixture of a light brown color is obtained.
[0239] Comparative compositions with lubricant
[0240] Comparative Example 5: With lubricant, without pigment, without urea, without surfactant compound (A269)
[0241] 6.22 g of BN 110 boron nitride (Henze) are mixed over 15 min with 35 ml of NMP in a Dispermat device at 50 ° C and 2000 rpm. Next, 3.37 g of PMDA and 7.51 g of BAPPS are added and dispersed for another 90 min at 50 ° C and 2000 rpm. After separation of the glass beads, a homogeneous liquid reaction mixture of a light brown color is obtained.
[0242] Comparative Example 6: With lubricant, with pigment, without urea, without surfactant compound (A219-16)
[0243] 6.22 g of BN 110 boron nitride (Henze) are mixed over 15 min with 35 ml of NMP in a Dispermat device at 50 ° C and 2000 rpm. Next, 3.37 g of PMDA and 7.51 g of BAPPS are added and dispersed for another 90 min at 50 ° C and 2000 rpm. After separation of the glass beads, 1.04 g of Lapis Sunlight T20-04-WNT (Merck) are added and the total mixture obtained is combined by means of a dissolving disk over 30 min at 25 ° C and 1000 rpm. A homogenous liquid reaction mixture of a light brown color is obtained.
[0244] Comparative Example 7: With lubricant, with pigment, with urea, without surfactant compound (A219-15)
[0245] 6.22 g of BN 110 boron nitride (Henze) are mixed over 15 min with 35 ml of NMP in a Dispermat device at 50 ° C and 2000 rpm. Then, 3.37 g of PMDA, 7.51 g of BAPPS and 0.52 g of Si3N M11-A (HC Starck) are added and dispersed for another 90 min at 50 ° C and 2000 rpm. After separation of the glass beads, 1.04 g of Lapis Sunlight T20-04-WNT (Merck) are added and the total mixture obtained is combined by means of a dissolving disk over 30 min at 25 ° C and 1000 rpm. A homogenous liquid reaction mixture of a light brown color is obtained.
[0246] Comparative Example 8: With lubricant, without pigment, without urea, with surfactant compound (A274)
[0247] 6.22 g of BN 110 boron nitride (Henze) are mixed over 15 min with 35 ml of NMP and 2.07 g of Fluorolink D10H (Solvay) in a Dispermat device at 50 ° C and 2000 rpm. Next, 3.37 g of PMDA and 7.51 g of BAPPS are added and dispersed for another 90 min at 50 ° C and 2000 rpm. After separation of the glass beads, a homogeneous liquid reaction mixture of a light brown color is obtained.
[0248] Comparative Example 9: With lubricant, without pigment, with urea, with surfactant compound (A65)
[0249] 6.53 g of BN 110 boron nitride (Henze) are mixed over 15 min with 35 ml of NMP and 2.18 g of Fluorolink D10H (Solvay) in a Dispermat device at 50 ° C and 2000 rpm. Next, 3.37 g of PMDA and 7.51 g of BAPPS and 1.09 g of SiC UF10 (HC Starck) are added and dispersed for another 90 min at 50 ° C and 2000 rpm. After separation of the glass beads, a homogeneous liquid reaction mixture of a light brown color is obtained. Figure 22 and Figure 23 show by way of example the structure of the composite material A219. Tribology The generated compositions were applied on stainless steel plates and thermally hardened as described. The layer thickness amounted to 20-25 pm. Next, the samples were measured in the ball-disk tribometer. The measurements were carried out under the following load group:
[0250] Disc-sphere trimometer (DIN 50324 standard), under-air measurement, 100Cr6 dial with a diameter of 4 mm, radius of the circle: 16 mm, supporting force: 2 N, band speed: 10 cm / s, distance Load: 1 km.
[0251] Figure 1 shows the influence of different pigment particles (5% by weight) on the sliding coefficient in the system with 5% by weight of SiC hard material particles and 30% by weight of BN 110 particles. 16 and Figure 15 show representative REM photographs of the SiC or BN 110 particles used.
[0252] In this case it is remarkable that obviously many different pigment types cooperate in a reduction of the coefficient of friction in the initial phase of the measurement over 3000-4000 rounds versus the comparative composition without a corresponding pigment. Since the aspect ratio of the pigment particles to each other is relatively similar, the chemistry of the surface plays a decisive role in relation to the magnitude of the reduction in friction. In order to highlight the effect even more clearly, Figure 2 shows the composite materials with Lapis Sunlight as well as Autumn Mystery as pigments compared to the pigment-free composite. The REM photographs of the two pigments are shown in Figure 20 and Figure 21.
[0253] Autumn Mystery reduces the coefficient of friction along a sliding path of 2000 rounds, Lapis Sunlight shows the positive effect even over 9000 rounds.
[0254] In summary, it is to be retained, by virtue of particular importance, that the addition of an initially tribologically inactive filler material in the form of pigment particles leads to a lubricant coating system consisting of a polymeric matrix, a solid lubricant and a hard material to an additional reduction of friction. This discovery represents the key point of the invention mentioned above. The effect found can not be explained in this case only through a new morphology hitherto not described in the state of the art, in the formed composite material. The compositions described in the following serve to delimit the relevant compositions.
[0255] It is expected that a hard material of a very high hardness in the tribological experiment can lead, from a certain concentration, to a destruction of the relatively softer pigment particles. For this, in the system with SiC as a hard material and the particle of pigment Lapis Sunlight with the best reduction of friction the concentration of SiC was increased stepwise. The compositions are shown in Table 1. The results of the measurements in the tribometer are shown in Figure 3. Figure 16 shows a representative REM photograph of SiC. The morphology of the particles must be designated as amorphous-angled. The particle size distribution is wide and covers particles with approx. 50 nm to approx. 2 pm
[0256] Accordingly, the addition of SiC as hard material from approx. 10% by weight provides a negative influence on the friction coefficient of sliding.
[0257] In addition, it was interesting to know what influence the concentration of Lapis Sunlight has in the case of a constant concentration of SiC hard material. Table 2 and Figure 4 show the compositions of the composite materials, as well as the corresponding results in the measurements in the tribometer.
[0258] The results of the measurement show that, only from concentrations of pigment above approx.
[0259] 10% by weight, a favorable effect is no longer manifested.
[0260] In addition, it was of interest to further systematically establish the composition of the system in relation to the individual components, in order to have corresponding comparative examples. This systematic structure in the sense of a staggered combination of components was first carried out in the system containing SiC as hard material. Table 3 shows the compositions of interest. The composition according to the invention is A193. It is the reproduction of A169 and is identical with this one in its composition. All other compositions are comparative examples.
[0261] The corresponding tribological measurements are shown in Figure 5.
[0262] The pure matrix with 35% by weight of BN 110 (A113) shows with p = 0.22 a relatively high sliding coefficient for a lubricant varnish, however, a good constancy over the distance of 10000 rounds. The addition of FL D10H to the pure matrix without BN 110 (A119) leads to very low initial friction values of less than p = 0.05 which phenomenologically point rather to a hydrodynamic lubrication. This suggests that FL D10H is not eventually bound completely in the polyimide matrix. The slope of the further course of the curve points to a higher wear rate in this system. Shortly before reaching 10000 rounds, a stratus failure manifests itself, as can be seen in the strong oscillations of the mean value. If BN 110 and FL D10H (A274) are combined, then initial friction values are also obtained low, but the layer wears even more quickly than in the case of additives in the particular case. This suggests that the layer has become very soft overall due to the two additives. The addition of additional SiC hard material particles (A 65) shows that the sliding coefficient can be equalized over the entire measuring distance to p values between 0.15 and 0.18. This is the classic case of the effect of a hard material on the sliding behavior. By adjusting the composition according to the invention, with additional insert-shaped pigment particles (A193), a further reduction of the sliding coefficient is achieved through the equalization, in particular in the initial phase of the load.
[0263] Overall, the course of the curve for A193 points, however, to that wear still manifests notorious. As a result of this, SiC hard material particles can be taken into account which can exert an abrasive effect on the overall system when they are expelled from the surface of the layer by the opposite body. By reducing the hardness of the hard material particles the wear problem can be minimized. In this regard, the silicon nitride (universal hardness HU: about 2500 MPa) is available as a replacement for silicon carbide (universal hardness HU: about 2500 MPa). The Tables, (Table 4, Table 5, Table 6, Table 7, Table 8) and the Figures (Figure 6, Figure 7, Figure 8, Figure 9, Figure 10) show in this respect the dependence of the lubricant behavior of the concentration of hard material for different types of silicon nitride with different distributions of the particle size and morphology in combination in each case with fixed concentrations of BN 100, Lapis S and FL D10H. In most cases, these systems show a uniform course of the slip coefficient below 0.13 with only a slight increase above the stress section. In some cases, the sliding coefficient runs over the entire duration of the measurement even below p = 0.1.
[0264] Table 4 and Figure 6 show the influence of Si3N4 nano70 hard material with nanoscale particles. The granulometry of the particles is between 10 nm and 200 nm. Seen from a morphological point of view, the shape of the particle can be described as amorphous until spherical.
[0265] The nano-scale Si3N4 particles seem to be conveniently used only up to approx. 5% by weight. In the case of higher concentrations, a failure of the layers is observed.
[0266] Table 5 and Figure 7 show the influence of hard material Si3N4 E05 with coarser nanoscale particles. The granulometry of the particles ranges between 300 nm and 800 nm. From a morphological point of view, the shape of the particle can be described as cube-shaped. Figure 17 shows a representative scanning electron microscope photograph.
[0267] Coarse Si3N4 particles in the nanometer range provide systems with a certainly unitary course of up to approx. 15% by weight and a markedly lower increase than in the case of SiC as a hard material.
[0268] Table 5 and Figure 8 show the influence of the hard material Si3N4 E03 with particles at a scale below the micron. The granulometry of the particles ranges between 400 nm and 900 nm. From a morphological point of view, the shape of the particle can be described as cube-shaped. Figure 18 shows a representative scanning electron microscope photograph.
[0269] Particles of Si3N4 in the interval below the micron provide systems with a certainly unitary course of up to approx. 10% by weight and a markedly lower increase than in the case of SiC as a hard material.
[0270] Table 7 and Figure 9 show the influence of Si3N4 M11-A hard material with particles at a scale of less than micron to micron. The granulometry of the particles is wide and ranges between 100 nm and 2 pm. From a morphological point of view, the shape of the particle can be described as amorphous. Figure 19 shows a representative scanning electron microscope photograph.
[0271] Systems with a granulometry of the wide particles of Si3N4 hard material also provide a good equalization of the sliding coefficient along the entire load section.
[0272] Table 8 and Figure 10 show the influence of Si3N4 B7 hard material with particles on a micrometric scale. Up to approx. 10% by weight, the series of the system with Si3N4 B7 behaves analogously to the series with E05 and E03. In summary, it can be verified that the silicon nitrides, due to their hardness, which is not extremely high in comparison with silicon carbide, act less abrasively in the configuration of the transfer film, with which an intensification of the lower slip coefficient along a long load section. Due to the lower abrasive effect, the pigment particles are also not destroyed and can exert their tribological effect in the sense described above, according to the invention.
[0273] The system series with Si3N4 B7 shows a balanced behavior in the case of a constant 10% by weight FL D10H content. In order to find the optimum concentration of this component in relation to the tribological properties, a variation of the content in FL D10H was made based on a Si3N4 B7 concentration of 1.25% by weight (Table 10, Figure 12) .
[0274] It is shown that in this series of the system, from 10% by weight of FL D10H (A223) the desired tribological effect is initiated. In order to exclude a purely hydrodynamic lubricating effect of the FL D10H, systematically individual components were added to the material of the starting polymer matrix for the series of parallel systems with Si3N4 M11-A as a hard material compared to the A219 system (analogous composition). to A223). Tables 10 and 11 and Figures 12 and 13 show the influence of certain individual components that come together to form the overall composite material in a systematic manner.
[0275] These comparative series show an analogous image to the one previously observed in the case of SiC as Hard material. The combination of FL with Lapis S leads to a clear reduction of the initial friction value, but without a particular wear resistance (A274). The additional activation with solid lubricant BN 110 leads to a clear reduction of wear with a low initial friction value (A200). The best balance in relation to the friction coefficient of sliding and wear is obtained by the additional combination of Si3N4 as hard material (A219).
[0276] Cross-linking and abrasion behavior
[0277] Tables 13 to 16 show additive properties of the tribological composites such as the wetting behavior, the abrasion resistance depending on the content of hard material particles and the protective effect against corrosion, in particular depending on the content of plates.
[0278] From the data shown it can be seen that the systems show both hydrophobic and oleophobic properties, that is, their surface modified components for the particles used accumulate on the air side of the coatings. Therefore, a part of the plaquitas is dragged to the surface of the layer by means of the modification of the hydrophobic surface. This is confirmed in Figure 22.
[0279] Corrosion
[0280] Figure 24 shows the results of a neutral salt spray test.
[0281] The examples shown confirm the protective effect against corrosion of the tribological layers generated. There is no bubble formation on the surface. At the cracked edge of the cross crack no infiltration of the coating occurs. Causally, the finally structured structure of the overall composite material (barrier effect) and the excellent adhesion to the bottom may be responsible for this.
[0282] Table 1: Variation of SIC UF-10 to 5% of Lapis S and 10% of FL
[0283]
[0284]
[0285]
[0286]
[0287] Table 2: Variation of Lapis S in the SiC system
[0288]
[0289]
[0290] Table 3: Systematic structure of the SiC system; A193 = composition according to the invention; A113, A119, A274 and A65 = comparative examples
[0291]
[0292]
[0293]
[0294] Table 4: Variation of the content of Si3N4 nano70
[0295]
[0296]
[0297]
[0298] Table 5: Variation of Si3N4 E05
[0299]
[0300]
[0301]
[0302] Table 6: Variation of Si3N4 E03
[0303]
[0304]
[0305] Table 7: Variation of the content of SÍ3N4 M11-A (wide distribution)
[0306]
[0307]
[0308] Table 8: Variation of the content of SÍ3N4 B7 (3,0 | jm)
[0309]
[0310]
[0311] Table 9: Variation of FL D10H content in the system without urea
[0312]
[0313] Table 10: Variation of the content of FL D10H in the system SÍ3N4 B7 (3,0 | jm)
[0314]
[0315]
[0316]
[0317] Table 11: Systematic structure of SÍ3N4 M11-A - system without BN
[0318]
[0319]
[0320]
[0321] Table 12: Systematic structure of Si3N4 M11-A - system with BN
[0322]
[0323]
[0324]
[0325] Table 13: Lapis S at 5% by weight, BN 110 at 30% by weight, FL D10H at 10% by weight
[0326]
[0327]
[0328] Table 14: 5% by weight of Lapis S, 30% of BN 110, 10% of FL D10H
[0329]
[0330]
[0331]
[0332]
[0333] Table 15: 5% by weight of SiC, 30% of BN, 10% of FL D10H
[0334]
[0335]
[0336]
[0337]
[0338] Table 16: Comparative systems
[0339]
[0340]
[0341]
[0342]
[0343] Bibliography cited
[0344] US46944038A
[0345] US5789523A
[0346] WO2002005293A2
[0347] US20040229759A1
[0348] US4898905A US3809442 EP1350817A1 WO2005010107A1 WO2005010107A1 EP1718690

权利要求:
Claims (13)
[1]
1. Composition for producing a tribological composite material, comprising
a) at least one solid lubricant in the form of plates;
b) at least one type of inorganic pigment particles in the form of plates, wherein the pigment particles have a thickness of 0.5 μm to 2 μm and an average aspect ratio> 10;
c) at least one surfactant having at least one hydrophilic group and at least one hydrophobic group, the surfactant compound of the group comprising alkyl ammonium compounds, alkyl phosphonium compounds, alkyl sulfonium compounds, imidazolinium compounds, compounds of pyridinium, pyrrolidinium compounds, ionic liquids, functionalized fluorinated polymers, polyesters and functionalized polysiloxanes;
d) a hardenable binder system comprising at least one organic polymer or oligomer with one or more functional groups or a precursor thereof.
[2]
Composition according to Claim 1, characterized in that the solid lubricant has a thickness between 100 nm and 1000 nm and an aspect ratio> 5.
[3]
Composition according to one of claims 1 to 2, characterized in that the composition contains inorganic particles as other components.
[4]
Composition according to claim 3, characterized in that the inorganic particles have a hardness of 1,000 MPa at 3,500 MPa.
[5]
Composition according to one of Claims 1 to 4, characterized in that the solid lubricant is chosen from the group comprising natural graphite, synthetic graphite, graphene, hexagonal boron nitride, turbo-stratified boron nitride, molybdenum disulfide and / or disulphide wolfram
[6]
Composition according to one of Claims 1 to 5, characterized in that an organic solid lubricant selected from the group comprising perfluoropolymers, polytetrafluoroethylene (PTFE) and / or polyethylene is additionally added.
[7]
Composition according to one of claims 1 to 6, characterized in that the surface of the pigment particles is composed, at least in part, of a transition metal oxide.
[8]
8. Composition according to claim 3, characterized in that the transition metal oxide is selected from the group comprising TiO2, ZrO2, ZnO and FeOx.
[9]
Composition according to one of claims 1 to 8, characterized in that the binder system comprises an epoxy resin, phenolic resin, phenoxy resin, polyol, a blocked or unblocked polyisocyanate, a polyimide, a polyamide-imide, polyamide, polybenzimidazole, a polyester, polyurea, polyurethane, a polyepoxide, a polyamine and / or a polyacrylate or precursors thereof.
[10]
Composition according to one of Claims 1 to 9, characterized in that the binder system comprises a di- or tetra-carboxylic acid, its anhydride or other derivative thereof as a carboxylic acid component and a di-, tri- or tetra-amine as an amine component, wherein at least one component is aromatic.
[11]
11. Process for producing a tribological composite material, comprising the following steps:
a) application of a composition according to one of claims 1 to 10 on a substrate;
b) thermal and / or photochemical hardening of the composition.
[12]
Method according to claim 11, characterized in that the composition according to step a) is obtained with a process comprising the following steps:
a1) preparing a mixture based on at least one solid lubricant in the form of plates a surfactant in a solvent suitable for the binder system;
a2) adding the hardenable binder system and at least one type of inorganic pigment particles in the form of plates;
a3) apply the mixture obtained on a substrate.
[13]
Substrate with a tribological composite coating based on a hardened composition according to one of claims 1 to 10.

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同族专利:

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公开号 | 公开日

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MX2014007576A|2015-02-12|

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BR112014013522A2|2017-06-13|

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WO2013092835A1|2013-06-27|

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US10246662B2|2019-04-02|

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JP2015507665A|2015-03-12|

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CA2862012A1|2013-12-30|

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KR101926903B1|2018-12-07|

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JP5926817B2|2016-05-25|

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MX365187B|2019-05-27|

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BR112014013522A8|2017-06-13|

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AR089352A1|2014-08-20|

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EP2794769B9|2019-03-20|

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DE102011056761A1|2013-08-08|

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EP2794769B1|2016-09-14|

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US20140329729A1|2014-11-06|

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KR20140109985A|2014-09-16|

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ES2606878T3|2017-03-28|

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EP2794769A1|2014-10-29|

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法律状态:

优先权:

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申请号 | 申请日 | 专利标题

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DE102011056761|2011-12-21|

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DE102011056761A|DE102011056761A1|2011-12-21|2011-12-21|Pigmented, finely structured tribological composite material|

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PCT/EP2012/076343|WO2013092835A1|2011-12-21|2012-12-20|Pigmented, fine-structured, tribological composite material|

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