MXPA05011229A - Method for coating substrates with a carbon-based material - Google Patents

Abstract

The invention relates to a method for coating substrates with a carbon-based material comprising the following steps:at least partial coating of a substrate with a polymer film on at least one external surface of the substrate;carbonisation of the polymer film in an atmosphere, which is essentially devoid of oxygen, at temperatures ranging from 200°C to 2500°C.

Description

METHOD FOR COATING SUBSTRATES WITH A CARBON-BASED MATERIAL FIELD OF THE INVENTION The present invention relates to a process for coating substrates with a carbon-based material by means of at least partial coating of a substrate with a polymeric film, applied on at least one of the outer surfaces of the substrate and Then the carbonization of the polymer film in an atmosphere, which is essentially free of oxygen, at temperatures in the range of 2002 C to 2500a C.

BACKGROUND OF THE INVENTION Pyrolytic carbon has been known for a long time as a solid material very resistant to wear with a high variability of its properties. Pyrolytic carbon due to its structure and composition is biocompatible, so that it has long been used as a raw material or coating material in medical technology, especially for the production of medical body implants is of all kinds. Pyrolytic carbon with a turbostratified structure, possibly including carbon microcrystals in P050 / 068-BMG alloy with silicon, is used for example to coat coronary spirals or also for the production of synthetic heart valves. For example, US Pat. No. 6,569,107 describes for example coated intraluminal coronary coils, in which the carbon material is applied by means of chemical or physical methods of separation of the vapor phases (CVD or PVD). DE 3902856 describes molded bodies containing pyro-carbon, which were produced by means of the coking of carbon fiber objects, pyro-carbon infiltration and subsequent sealing of the surface with CVD carbon. The separation of pyrolytic carbon under PVD or CVD conditions requires the proper selection of suitable carbon precursors in gaseous or evaporable form, which at high temperatures under plasma conditions in an atmosphere of inert gas or at high vacuum are separated and deposited. carbon on a substrate. Thus, in the state of the art, different high vacuum bombing processes are described to produce the pyrolytic carbon of different structure, see for example US 6,355,350. All these processes of the state of the art present the joint particularity that the separation of carbon substrate is carried out under P050 / 068-BMG extreme temperature and / or pressure conditions under careful and costly process control. Furthermore, due to the different coefficients of thermal expansion of the substrate material and the CVD carbon layer applied in the state of the art, only a reduced adherence of the layer to the substrate has been achieved, since fractures, tears and general damages occur. to the quality of the surface. Therefore, there is a need for simple and inexpensive methods for coating substrates with a carbon-based material, which can make available for example coatings of a carbon material or a substrate coated with carbon for microelectronic purposes.

SUMMARY OF THE INVENTION Therefore, the task of the present invention is therefore to present a method for the coating of substrate with carbon-based material, which can be produced with a wide variety of cheap raw materials and using preparation conditions easily controllable Another task of the present invention is to present a substrate coated with a carbon-based material for use in medical technology, especially P050 / 068-BMG for medical implants of different types, whose surface properties can be adjusted specifically for the purpose of use in question. Another task of the present invention is the presentation of a process for producing substrates coated with carbon for microelectronic purposes.

DESCRIPTION OF THE INVENTION The solution according to the invention consists of a process according to claim 1. Preferred embodiments according to the invention are given in the dependent subclaims. Within the framework of the present invention it was found that carbon-coated products can be easily produced, first by coating at least superficially a substrate with a polymeric film, which subsequently carbonizes or pyrolyzes at high temperatures in an oxygen-free atmosphere. . Under the term carbonization or pyrolysis in the context of the present invention is understood the thermal decomposition or coking of carbon-containing starting materials, usually hydrocarbon-based polymeric materials, which after high carbonization produce high fractions of amorphous carbon.

P050 / 068-BMG Substrates The substrates usable according to the invention can include essentially all temperature-resistant materials, that is, materials that are resistant and preferably stable to molding under the conditions of carbonization or pyrolysis used. Examples of substrates that can be used according to the invention are metals, alloys, ceramics, graphite, glass, stone, carbon fiber materials, carbon composite materials, minerals, bone substances and bone imitations based on calcium carbonate. and similar. It is also advantageously possible according to the invention to use as substrates ceramic raw bodies, since these in parallel during the carbonization of the coating the ceramic can be sintered. Thus, for example, nanocrystalline zirconium oxide and Al203 alpha or gamma-free bodies, or compressed amorphous nanometric ALOOH airgel, can be used, with which nanoporous carbon-coated shaped bodies can be produced at temperatures of approximately 500 to 20002, preferably however at 8002 C, obtaining coatings with porosities of approximately 10-100 nm. The method according to the invention P050 / 068-BMG leads to coatings with an extremely high mechanical resistance, and solves in particular the problem of the detachment of the existing coated substrates, which under heavy mechanical loads of torsion, traction and expansion tend to the detachment of the applied layers. high school. For the substrates coated according to the invention, especially also those for medicinal purposes, the materials used are all materials commonly used in the field of medicine and dentistry, for example metals such as titanium, platinum, palladium, gold, alloys such as, for example, cobalt-chromium alloys, low porous graphite, polymers, carbon fiber implants, ceramics such as calcium phosphate ceramics, zeolite, aluminum oxide, apatite ceramics and the like, these mentions are not considered to be exclusive of others. The substrates can have almost any desired exterior shape, as long as they can be coated with a polymer film on their external surface. Preferred examples of the substrates according to the invention are medical implants such as for example prostheses and substitutes for joints, bone implants, synthetic hip joints and implants for hip bones, intraluminal devices such as P050 / 068-BMG coronary spirals or stents, for example of metal, such as nitinol coronary spirals, of polymers, surgical-orthopedic aids such as bone screws, nails, plates and the like. In referred embodiments of the present invention, the substrates to be coated are coronary coils or stents, especially metallic ones. Other examples of the substrates which can be used according to the invention are components of the field of microelectronics and micromechanics, construction materials such as metal ceramics in glass and stone as well as carbon fiber composite materials, seal rings and Sulzer type packaging, cartridges and filtering, insulating materials and the like.

Polymeric Films According to the process according to the invention temperature-resistant substrates, at least the outer surfaces are at least partially coated with one or more polymer films, in certain preferred applications as for example in the case of medical devices by the 'regular' covers the entirety of its outer surface. The polymeric film in a preferred embodiment of the invention can be found in P050 / 068-BMG form a polymeric sheet that for example is applied to the substrate by means of a sheet shrinking process or it can be adhered. The thermoplastic polymer sheets can be applied in a strongly adhesive manner to most substrates when heated. Suitable sheets consist of homo- or copolymers of aliphatic or aromatic polyolefins such as polyethylene, polypropylene, polybutene, polyisobutene, polypentene; polybutadiene, polyvinyls such as polyvinyl chloride or polyvinyl alcohol; poly (meta) acrylic acid, polyacrylonitrile, polyamide, polyester polyurethane, polystyrene, polytetrafluoroethylene, waxes, paraffin waxes, Fischer-Tropsch waxes; mixtures and combinations of those homo- or copolymers and the like. In preferred embodiments, polymeric films and coatings based on foamable polymers, phenolic foams, polystyrene foams, foamed polyurethane, fluoropolymer foams and the like are advantageously used. These have the advantage that coatings with an adjustable porous structure depending on the porosity of the foam can be obtained in the carbonization step. In order to produce the foamy polymers, all the foaming processes customary in the state of the art can be used using the usual propellants as hydrocarbons P050 / 068-BMG halogenated hydrocarbons with low boiling point. According to another embodiment of the present invention, the polymeric film may also include a coating of the substrate that is selected from lacquers, laminates or coatings. Preferred covers can be obtained by parilenization of the substrates. For this the substrates are treated first at elevated temperatures, usually about 600 ° C with paracyclofan, for which a poly (p-xylylene) polymer film is formed on the substrate. This allows carbon to be transformed by means of one of the following stages of carbonization or pyrolysis. In preferred embodiments, the parison and carbonization sequence is repeated several times. Suitable polymers based on lacquer can, for example, be produced from a lacquer consisting of an alkyd resin binder base, chlorinated rubber, epoxy resin, acrylate resin, phenolic resin, amino resin, oil bases, nitro bases, polyester, polyurethane, tar, tar materials, pitch, bitumen, starches, cellulose, Schellack, organic materials and other growing raw materials or combinations thereof. In the method according to the invention P050 / 068-BMG can be applied several layers of the polymeric films on the implant, which are then carbonized together. By means of the use of different polymeric film materials optionally additives in the individual polymer films or films of different thicknesses, specific gradient coatings can be applied on the implant, for example with different porosity or adsorption profiles within the coatings. In addition, the coating sequence with the polymer film and the carbonization can be repeated one and possibly several times to obtain multilayer coatings containing carbon on the implant. For this, polymeric films or substrates can be pre-constructed or modified by means of additives. Post-processing steps can also be used as described below after each coating sequence with polymeric films and carbonization of the process according to the invention, such as, for example, an oxidizing treatment of the individual layers. Also the use by means of the polymeric films coated by means of the lacquers or coating solutions mentioned above for coating the implants advantageously using according to the invention for example lining techniques such as for example lining P050 / 068-BMG thermal, compressed under pressure, or wet. In preferred embodiments of the present invention the polymer film may be added with additives, which influence the carbonization form of the film and / or the macroscopic properties of the carbon based substrate coatings resulting from the process. Examples of suitable additives are fillers, pore formers, metals and metal powders, etc. Examples of the inorganic additives or fillers are silicon oxides or aluminum oxides, aluminum silicates, zeolites, zirconium oxides, titanium oxides, talc, graphite, soot, sands, clay materials, phyllosilicates, silisides, nitrides, metallic powder , especially of catalytically active transition metals such as copper, gold and silver, titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, rhenium, iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium or platinum. By means of these additives in the polymeric film, for example, the biological, mechanical and thermal properties of the film as well as the resultant carbon coatings can be varied and adjusted. Thus, for example, by means of the introduction of layered silicates, the coefficient of thermal expansion of the carbon layer can be compensated for.

P050 / 068-BMG a ceramic substrate, in such a way that the coating applied on the basis of carbon also adheres strongly in the case of strong temperature differences. Thus the addition of aluminum-based fillers leads to an increase in the coefficients of thermal expansion and the addition of fillers based on glass, graphite or quartz leads to a reduction of the coefficient of thermal expansion, so that by mixing the components in the polymer system can individually adjust the coefficient of thermal expansion. Another possible adjustment of the properties can be realized for example and not exclusively by means of the production of a fiber composite by means of the addition of carbon fibers, polymers, glass or other fibers in woven or non-woven form, which leads to a clear increase in the elasticity of the coating. Polymeric films have the advantage that they can be produced easily with almost all desired dimensions or can be obtained commercially. The polymeric sheets are easy to obtain, economical and can be applied simply on substrates of the most diverse types. The polymeric films used according to the invention, before or after being applied to the substrate, can be suitably structured by means of folding, punching, trimming, P050 / 068-BMG compressed, extruded, enrafiado, emptied by injection and similar. In this way, the carbon coatings produced with the process according to the invention can be constructed with certain structures of regular or irregular types. The polymeric films which can be used according to the invention of coatings in the form of lacquers or coatings can be applied to the substrate in liquid, semi-pasty or pasty form, for example by means of a process known, for example, by means of brush application, lacquering, coating by dispersion or melting, extrusion, casting, dipping or also hot melting, in solid form by means of powder coating, spraying, sintering or the like, according to methods known per se. Also the lining of adequately molded substrates with suitable polymeric materials or sheets is a method which can be used according to the invention to coat the substrate with a polymeric film. Especially during the coating of substrates with polymeric films it is preferred to apply the polymer or a solution thereof by means of a pressure process such as that described in DE 10351150, the description of which is included here. This procedure makes possible in particular an adjustment P050 / 068-B G accurate and reproducible of the thickness of the layer of polymeric material applied.

Carbonization The polymer film applied on the substrate is eventually dried and then subjected to decomposition by pyrolysis under carbonization conditions. For this purpose, the polymeric film covering the substrate is carbonized in an atmosphere essentially free of oxygen at an elevated temperature. The temperature of the carbonization step is preferably in the range of 2002 C to 2500a C and is selected by the technician depending on the specific temperature-dependent properties of the polymer films and substrates used. The preferred temperatures generally usable for the carbonization step of the process according to the invention are in the range of 2002 C to 12002 C. In some embodiments, temperatures in the range of 250 ° C to 700 ° C are preferred. it is selected from the temperature depending on the materials used, such that the polymer film can be completely transformed to a solid containing carbon. By means of the appropriate selection or control of the temperature of P050 / 068-BMG pyrolysis can specifically adjust the porosity, strength and stiffness of the material as well as other properties. Preferably according to the invention, porosity occurs in the layers of the implants by means of treatments such as those described in the DE 103 35 131 and PCT / EP04 / 00077, the description of which is included here. Through the use of very high temperatures of up to 2000 BC and more, carbon-based coatings in the form of graphite can be produced. A suitable selection of the carbonization temperature allows the specific adjustment of the crystallinity of the coatings from completely amorphous at low temperatures to highly crystalline at high temperatures. In this way, the mechanical properties of the coatings can also be adjusted and optimized specifically for the purpose of use. The atmosphere during the carbonization step of the process according to the invention is essentially free of oxygen. The use of atmospheres of inert gases such as nitrogen, noble gases such as argon, neon as well as other gases or mixtures of inert gases that do not react with the P050 / 068-B G carbon. Preferred are nitrogen and / or argon. The carbonization is carried out in the usual manner at normal pressure in the presence of inert gases such as those described above. Optionally, higher pressures of the inert gases can also be used with advantage. In certain embodiments of the process according to the invention, the carbonization can also be carried out at a sub-pressure or under vacuum.

BAKING PROCESS The pyrolysis step is preferably carried out in a continuous baking process. The polymer films optionally structured, coated or pretreated are introduced on one side of a furnace and are extracted on the other side of the furnace. In preferred embodiments, the polymer film or the objects formed with the polymeric films can be placed on a perforated plate, a screen or the like, so that the polymer film during the pyrolysis and / or the carbonization can be subjected to pressure. This allows not only the simple fixing of the object in the furnace but also an optimum extraction and flow of the films or objects constructed with inert gas during the pyrolysis and the carbonization. The oven can be divided into segments P050 / 068-BMG by means of the corresponding inert gas locks, where one or more stages of pyrolysis or carbonization can be carried out sequentially, possibly under different conditions of pyrolysis or carbonization such as for example different temperature levels, different inert gases or to the vacuum Furthermore, in the corresponding segments of the furnace, post-treatment steps may be carried out as post-activation by reaction or oxidation or impregnation with metallic salt solutions etc. Alternatively, pyrolysis / carbonization can also be carried out in a closed oven, which is especially preferred when pyrolysis and / or carbonization must be carried out under vacuum. While during the pyrolysis and / or carbonization in the process according to the invention there is a weight reduction of the polymer film of about 5 to 95%, preferably about 40 to 90%, especially 50 to 70%, depending on the the raw materials used and the treatment. Thus during the pyrolysis and / or carbonization in the process according to the invention there is usually a shrinkage of the polymeric film or of the structure or object produced with the polymeric films. The shrinkage can be of a magnitude of 0% at P050 / 068-BMG approximately 95%, preferably from 10% to 30%. In the process according to the invention, the electrical conductivity of the coating can be adjusted widely depending on the pyrolysis or carbonization temperature used and the type and amount of the additives or fillers used. This is especially advantageous for applications in microelectronics. Thus at temperatures in the range of 1000 to 2500 2C as a consequence of the graphite formation that occurs, the coating can reach a higher conductivity than at lower temperatures. In addition, the electrical conductivity can also be increased, for example by the addition of graphite to the polymer films, which can be pyrolyzed or carbonized at low temperatures. This type of modified coated substrates are suitable, for example, for the production of sensors. The carbon-based coating produced according to the invention has, depending on the raw material used, the quantity and type of the filling materials, a carbon content of at least 1% by weight, preferably at least 25%, optionally also at least 60% and especially at least 75%. Especially preferred coatings according to the invention have a carbon content of at least 50% by weight.

P050 / 068-BMG POS-TREATMENT In preferred embodiments of the process according to the invention, the physical and chemical properties of the carbon-containing coating of the substrate, after carbonization, can be modified and adjusted to the desired end of use by means of steps of post-treatment By coating one or both sides of the polymeric film with epoxy resins, phenolic resins, tar, pitch, bitumen, rubber, polychloroprene or poly (styrene-co-butadiene) latex materials, siloxanes, silicates, metal salts or solutions of metal salts, for example transition metal salts, soot, sands, activated carbon powder, carbon molecular sieves, perowskite, aluminum oxides, silicon oxides, silicon carbide, boron nitride, silicon nitride, powder of precious metals such as Pt, Pd, Au or Ag; as well as their combinations, or also by means of the special introduction of that type of materials in the structure of the polymeric film, the properties of the resulting carbon-based porous coatings after pyrolysis and / or carbonization, or also multilayer coatings. For example, through the introduction P050 / 068-BMG of layered silicates in the polymeric film or in the coating of the polymeric film with layered silicates, nanoparticles, inorganic nanocomposite metals, metal oxides and the like can modify the coefficient of thermal expansion of the resulting carbon coatings as well as their mechanical properties . During the production according to the invention of coated substrates, by means of the introduction of the aforementioned additives into the polymeric film there is the possibility of improving the adhesion of the applied layer on the substrate and for example adjusting the coefficients of thermal expansion of the substrate. the outer layer to those of the substrate, in such a way that the coated substrates are more resistant to fractures and coating tears. These coatings are therefore more durable and stable during concrete use as common products of that type. The application or introduction of metals or metal salts, especially also precious metals and transition metals, makes it possible to adapt the chemical, biological and adsorption properties of the resulting carbon based coatings, to the desired requirements, in such a way that the resulting coating for certain applications for example may also be provided with heterogeneous catalytic properties.

P050 / 068-BMG In preferred embodiments of the process according to the invention, the physical and chemical properties of the carbon-based coating after pyrolysis or carbonization can be further modified and adjusted for the desired purposes of use, by means of of post-treatment stages. Suitable post-treatments are, for example, stages of post-treatment reducing or oxidants, in which the treatment is carried out with suitable reduction or oxidation means, such as water, carbon dioxide, steam, oxygen, air, nitric acid and the like as well as eventually mixtures of those. The post-treatment steps can optionally be carried out at an elevated temperature, however below the pyrolysis temperature, for example from 402 ° C to 1000 ° C, preferably 70 ° C to 900 ° C, especially preferred from 100 ° C to 850 ° C, more especially preferred from 2002 ° C to 800 ° C. and especially at approximately 7002C. In especially preferred embodiments, the coating produced according to the invention is modified by reduction or by oxidation, or with a combination of those treatment steps at room temperature. Through treatment by oxidation or reduction, or also by the introduction of additives, P050 / 068-BMG fillers or functional materials can be influenced or modified in a specific way the surface properties of the coatings produced according to the invention. For example, by introducing nanoparticles or inorganic nanocomposites such as layered silicates, the surface properties of the coating can become hydrophilic or hydrophobic. Furthermore, by means of ion implantation, the surface properties of the coated substrate can be modified. Thus, by means of nitrogen implantation, nitride, carbonitride or oxynitride phases can be formed with the transition metals present, which clearly increases the chemical resistance and the mechanical resistance capacity of the carbon-containing coatings. The implantation of carbon ions can be used to increase the mechanical strength of the coatings as well as for the subsequent compaction of the porous layers. The coatings produced according to the invention can also be provided with biocompatible surfaces by the subsequent introduction of suitable additives, and eventually used as biological reactors or drug carriers. For this, drugs or enzymes can be introduced into the material, these being eventually released from P050 / 068-BMG controlled form by means of suitable properties of retardation and / or selective permeate of the coatings. Furthermore, in certain embodiments, it is preferred to treat the coatings produced according to the invention with fluorine, so that, for example, the surface-coated coronary coils can receive lipophilic substances or materials. Also according to the invention the coating can be modified specifically on the substrate, for example by means of the variation of the pore sizes by means of suitable post-treatment stages, in such a way that the carbon-based coating facilitates or promotes the growth of microorganisms or living cells. Correspondingly coated substrates can, for example, serve in biological reactors as a growth medium for microorganisms. Advantageously, the porosity of the coating can be adjusted in such a way that the supply of food to the cells or microorganisms that have been established on the outer surface can be ensured by means of food or active substance deposits that are inside or on the outside. substrate, reaching the food to the surface microorganism colony by means of permeation through the carbon based coating.

P050 / 068-BMG The carbonised coating can eventually be used in another advantageous step of the CVD process (Chemical Vapor Deposition), chemical separation of gas phases), to further modify the surface or pore structures and their properties. For this, the carbonized coating is treated with suitable precursor gases at high temperatures. This type of procedures have been known for a long time in the state of the art. Suitable carbon separating precursors are almost all saturated or unsaturated hydrocarbons with sufficient volatility under the CVD conditions. Examples of these are methane, ethane, ethylene, acetylene, alkanes, alkenes and linear and branched alkynes with a number of Cx to C20 carbon atoms, aromatic hydrocarbons such as benzene, naphthalene, etc., as well as mono- or polysubstituted aromatics with alkyl, alkenyl and alkynyl such as toluene, xylene, cresol, styrene, etc. As ceramic precursors can be used BC13, NH3, silanes such as tetraethoxysilane (TEOS), SiH4, dichlorodimethylsilane (DDS), methyltrichlorosilane (MTS), trichlorosilyldichloroborane (TDADB), hexadicloromethylsilyl oxide (HDMSO), A1C13, TiCl3 or mixtures thereof. These precursors are used in the procedure P050 / 068-BMG CVD mainly in a reduced concentration of 0.5 to 15% by volume, in mixture with an inert gas, such as nitrogen, argon or similar. The addition of hydrogen to the corresponding mixtures of detached gases is also possible. At temperatures between 500 and 2000a C, preferably 500 and 15002 C and in particular 700 to 13002 C, the mentioned compounds dissociate the hydrocarbon or carbon fragments or the ceramic precursors, so that in the porous systems of the pyrolyzed coating they precipitate in a substantially uniformly distributed manner, there they modify the porous structure and in the sense of a subsequent optimization, they lead to a pore size and an essentially homogeneous pore distribution. The carbon-containing coatings produced according to the invention have an extremely good mechanical strength. The coatings according to the invention made of stainless steel (for example 316 L) usually show modulus of elasticity of about 10-30 GPa, hardness of about 200 to 600 according to Viclers, typically of about 400, and friction coefficients of approximately 0.03 to 0.2 typically approximately 0.14, the layer fractures are only observed at approximately 30-60 rriN (Scratch Adhesion), the P050 / 068-BMG abrasion from approximately 40 to 400 iriN. Pyrolytic carbon is usually a biologically tolerable material, which can be used in medical applications for example as the outer coating of implants. The biological compatibility of the coated substrate according to the invention can be specifically influenced or modified by the addition of the addition of additives, fillers, proteins or functional materials and / or drugs in the polymer films before carbonization. With this, the phenomena of corporal rejection of the implants produced according to the invention can be reduced or completely avoided. In particularly preferred embodiments, the carbon-coated medical implants produced according to the invention by means of the specific adjustment of the porosity of the applied carbon layer can be used in the external zones, for the controlled delivery of the active substances of the substrate. In this way, for example, medical implants can be used as carriers of drugs with a deposit effect, and the carbon-based coating of the implant can be used as a release-regulating membrane. Drugs can also be applied to biologically tolerable coatings. This is especially useful when the active substances can not be applied P050 / 068-BMG directly on the substrate, as in the case of metals. Furthermore, the coatings produced according to the invention in a further process step can be loaded with drugs or medicaments, or also with markers, contrast media for the location of the implants coated in the body, or also with therapeutic or diagnostic quantities of radioactive radiation. For the latter, the carbon-based coatings according to the invention are particularly suitable since, unlike the carbon layers, they can not be modified or attacked by means of radioactive radiation. In the field of medicine, the implants coated according to the invention have proved to be long-lasting, since the carbon-based coatings, in addition to their high strength, are also sufficiently elastic and flexible, so that they can follow the movement of the implant. implant especially in the case of very used joints, without there being the danger that fractures are formed or that the layers come off. The invention will now be described in more detail with the help of the following examples, which represent the preferred embodiments, P050 / 068-B G which do not have the necessary limitations of the invention described in the claims: EXAMPLES Example 1: Carbon A carbon material coated according to the invention is produced in the following way: On a paper with a surface weight of 38 g / m2 as the base body a polymeric film was applied, coating the paper several times with a lacquer of expoxylated phenolic resin applied with a trowel and allowed to dry at room temperature. The dry weight was 125 g / m2. Pyrolysis at 8002 C for 48 hours under nitrogen produced a shrinkage of 20% and a weight loss of 57% produces a carbon leaf asymmetrically with the following measures: total thickness 50 microns, with 10 microns of a compact layer that contains carbon according to the invention on an open-pore carbon carrier with a thickness of 40 microns, which is formed in situ from the paper under the conditions of pyrolysis. The absorption capacity of the coated carbon material was up to 18 grams of ethanol per m2 ' Example 2: Glass Duroplan® Glass is subjected for 15 minutes to an ultrasonic purification in a water bath that P050 / 068-BMG contains a surfactant, it is rinsed with distilled water and acetone and dried. This material is coated with a commercial packaging lacquer based on phenolic resin with an application weight of 2.0 * 10"4 g / cm2, after the subsequent carbonization at 800a C for 48 hours under nitrogen a weight loss of the coating up to 0.33 * 10 ~ 4 g / cm2 The previously colorless coating turns shiny black and is no longer transparent after carbonization During a hardness test of the coating with a pencil, it is passed over the coated surface an angle of 452 and a weight of 1 kg, with a hardness of up to 5H there is no optically perceptible damage to the surface.

Example 3: glass, CVD coating (comparative example) Duroplan® glass is subjected to ultrasonic purification for 15 minutes, rinsed with distilled water and acetone and dried. This material is covered by means of vapor separation (CVD) with 0.05 * 10"* g / cm2 of carbon, for this benzene at 30 ° C, bubbling through a flow of nitrogen, it is contacted for 30 minutes with the surface of the hot glass at 1000a C and is deposited as a film on the surface of the glass.The surface of the previously colorless glass becomes bright gray and after evaporation is transparent.

P050 / Q68-BMG During a test of the hardness of the coating with a pencil, which is passed over the coated surface at an angle of 452 and a weight of 1 kg, with a hardness of up to 6B there is no optically noticeable damage of the surface.

Example 4: Glass Fibers Duroplan® glass fibers with a diameter of 200 microns are subjected for 15 minutes to an ultrasonic purification, rinsed with distilled water and acetone and dried. This material is coated by means of immersion with a commercial pack lacquer with an application weight of 2.0 * 10 ~ 4 g / cm2. After the subsequent pyrolysis with carbonization at 800 ° C for 48 hours a weight loss of the coating is presented up to 0.33 * 10 ~ 4 g / cm2. The previously colorless coating turns shiny black and is no longer transparent after carbonization. A test of the adhesion of the coating by means of bending at the radius of 1802 shows no tears, that is, no optically perceptible damage to the surface.

Example 5: Stainless steel 1.4301 stainless steel film with a thickness of 0.1 mm (Goodfellow) is subjected for 15 minutes to a P050 / 068-BMG ultrasonic purification, rinse with distilled water and acetone and dry. This material is coated by immersion with a commercial packaging lacquer with an application weight of 2.0 * 10 ~ 4 g / cm2. After the subsequent pyrolysis with carbonization at 800 ° C for 48 hours, a weight loss of the coating is observed up to 0.49 * 10"4 g / cm2., it becomes matt black. During a test of the hardness of the coating with a pencil, which is passed over the coated surface at an angle of 45a and a weight of 1 kg, with a hardness of up to 4B there is no optically perceptible damage to the surface. A detachment test is made with strips of adhesive tape, during which strips of Tesa® adhesive tape of at least a length of 3 cm. they are stuck with the thumbs for 60 seconds on the surface and subsequently they are removed at an angle of 902 with the surface, with which there are no adhesions.

Example 6: Stainless steel, CVD coating (Comparative example) Stainless steel 1.4301 film with a thickness of 0.1 mm (Goodfellow) is subjected for 15 minutes to an ultrasonic purification, rinsed with distilled water and acetone and dried. This material is covered by means of P050 / 068-BMG vapor separation (CVD) with 0.20 * 10 ~ 4 g / cm2 carbon, for this benzene at 302 C bubbling through a flow of nitrogen, it is contacted for 30 minutes with the glass surface hot to 10002 C and deposited in film form on the surface of the glass. The pre-metallic surface turns shiny black after deposition. During a hardness test of the coating with a pencil, which is passed over the coated surface at an angle of 452 and a weight of 1 kg, with a hardness of up to 4B there is no optically perceptible damage to the surface. A stripping test is performed with strips of adhesive tape, during which strips of Tesa® adhesive tape of at least a length of 3 cm are glued with the thumbs for 60 seconds on the surface and subsequently removed at an angle of 902 with the surface, with which gray adhesions are clearly visible.

Example 7: Titanium Film of 99.6% titanium with a thickness of 0.1 mm (Goodfellow) is subjected for 15 minutes to an ultrasonic purification, rinsed with distilled water and acetone and dried. This material is covered by immersion with a commercial packaging lacquer with a weight of P050 / 068-BMG application of 2.2 * 10 ~ 4 g / cm2. After the subsequent pyrolysis with carbonization at 800 ° C for 48 hours, a weight loss of the coating is presented up to 0.73 * 10 ~ 4 g / cm2. The previously colorless coating becomes matt with a gray-black sheen. During a test of the hardness of the coating with a pencil, which is passed over the coated surface at an angle of 45 - and a weight of 1 kg, with a hardness of up to 8H there is no optically perceptible damage to the surface. For example, the coating can not be scratched with office staples either. A stripping test is performed with strips of adhesive tape, during which strips of Tesa® adhesive tape of at least a length of 3 cm are stuck with the thumbs for 60 seconds on the surface and subsequently removed at an angle of 90a with the surface, with which there are no adhesions.

Example 8: Titanium enriched with CVD Film of 99.6% titanium with a thickness of 0.1 mm (Goodfellow) is subjected for 15 minutes to an ultrasonic purification, rinsed with distilled water and acetone and dried. This material is coated by immersion with a commercial packaging lacquer with an application weight of 2.2 * 10 ~ 4 g / cm2. After the subsequent pyrolysis with carbonization at 8002 C for 48 hours P050 / 068-BMG presents a loss of coating weight up to 0.73 * 10 ~ 4 g / cm2. This material is covered by means of vapor separation (CVD) with 0.10 * 10 ~ 4 g / cm2 of carbon, for this benzene at 30 a C bubbling through a flow of nitrogen, it is contacted for 30 minutes with the surface of the hot glass at 1000a C, it is deposited, decomposed and separated as a film on the surface of the glass. The pre-metallic surface turns shiny black after deposition. After cooling to 4002 C, the surface is oxidized by air conduction for a period of 3 hours. During a test of the hardness of the coating with a pencil, which is passed over the coated surface at an angle of 452 and a weight of 1 kg, with a hardness of up to 8H there is no optically perceptible damage to the surface. A detachment test is made with strips of adhesive tape, during which strips of Tesa® adhesive tape of at least a length of 3 cm. they are stuck with the thumbs for 60 seconds on the surface and subsequently removed at an angle of 902 with the surface, with which gray adhesions appear.

P050 / 068-B G

Claims (12)

1. CLAIMS 1. A process for coating substrates with carbon-based material including the following steps: coating at least partially a substrate with a polymeric film, applied on at least one of the outer surfaces of the substrate, carbonizing the polymeric film in an atmosphere, which in essence is free of oxygen, at temperatures in the range of 2002 C to 2500a C.
2. 2. The method according to claim 1, characterized in that the polymeric film includes additives selected from the group of fillers, formers of pores, metals, extenders, lubricants and pigments.
3. 3. The process according to claim 2, characterized in that the additives are selected from among silicon oxides, aluminum oxides, aluminum silicates, zirconium oxides, titanium oxides, talc, graphite, soot, zeolite, clay materials. , phyllosilicates, sands, catalysts, metals and metal compounds and the like. .
4. The process according to one of the preceding claims, characterized in that the polymer films include selected sheets of ho- P050 / 068-BMG or copolymers of aliphatic or aromatic polyolefins such as polyethylene, polypropylene, polybutene, polyisobutene, polypentene; polybutadiene, polyvinyls such as polyvinyl chloride or polyvinyl alcohol; poly (meta) acrylic acid, polyacrylonitrile, polyamide, polyester polyurethane, polystyrene, polytetrafluoroethylene, waxes, paraffin waxes, Fischer-Tropsch waxes; mixtures and combinations of those homo- or copolymers.
5. The process according to one of claims 1 to 3, characterized in that the polymer film has a coating selected from lacquers, laminates or coatings.
6. 6. The process according to claim 5, characterized in that the polymeric film is a lacquer film produced from a lacquer with an alkyd resin binder base, chlorinated rubber, epoxy resin, acrylate resin, phenolic resin, amino resin , oil bases, nitro bases, polyester, polyurethane, tar, tar materials, pitch, bitumen, starches, cellulose, Schellack, organic materials and other growing raw materials or combinations thereof.
7. The process according to one of the preceding claims, characterized in that the carbon-based material after carbonization is P050 / 068-BMG undergoes a subsequent treatment by oxidation and / or reduction, as well as eventually a CVD process for carbon and / or ceramic separation.
8. The method according to one of the preceding claims, characterized in that the substrate is selected from metals, alloys, ceramics, graphite, glass, stone, sand, carbon fiber materials, carbon composites, bone substances and materials similar to bones, minerals, promoters and raw ceramic bodies, as well as their combinations.
9. The method according to one of the preceding claims, characterized in that the substrate is selected from medical implants, coronary coils or catalyst carriers.
10. The process according to one of the preceding claims, characterized in that the coated substrate is loaded with active substances or with microorganisms.
11. 11. The process according to claim 10, characterized in that the applied active substances are specifically released in the area of use.
12. 12. A substrate coated with carbon, characterized in that it can be produced according to the process according to the preceding claims. P050 / 068-BMG