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    • 专利摘要:
    Anticorrosive enamel of carbonaceous material, its obtaining procedure and its use. The present invention describes a continuous anti-corrosive enamel coating characterized in that it comprises a carbonaceous vitreous enamel with an amorphous structure, with a carbon atom content greater than 40% with respect to the total number of atoms and where said carbon atoms present sp <hybridization sup> 2 and sp3, and has a uniform thickness on the surface of the substrate that can vary between 1 nm and 100 nm. Another object of the present invention is the process for obtaining said continuous anti-corrosive enamel coating, and its use to form, on the surface of a substrate, a continuous layer resistant to corrosion, chemical and environmental oxidation. (Machine-translation by Google Translate, not legally binding)
    公开号:ES2843743A1
    申请号:ES202030035
    申请日:2020-01-20
    公开日:2021-07-20
    发明作者:Lleo Juan Ramon Llobell；Mondria Regina Maria Garcia
    申请人:Primalchit Solutions S L；
    IPC主号:
    专利说明:

    [0002] ANTICORROSIVE ENAMEL OF CARBONOUS MATERIAL, ITS PROCEDURE
    [0004] TECHNICAL SECTOR
    [0006] The present invention describes continuous anti-corrosive enamel coatings made up of a thin film of amorphous carbonaceous vitreous material that may or may not incorporate particulate components and suitable processes that allow the coating with this enamel of objects of any spatial shape and size.
    [0008] STATE OF THE ART
    [0010] There are materials that suffer corrosion and deterioration of their properties when exposed for prolonged periods to environmental conditions in both land and marine environments, or due to being immersed in special environments and environments. To slow down deterioration and corrosion as much as possible, materials can be covered with special micrometric thin layers that protect them from the negative effect of environmental agents (Sorensen, PA, et al. Anticorrosive coatings: a raviaw. Journal of Coatings Technology and Research . 2009. 6 (2): 135176). Examples of materials that undergo surface treatments to prevent corrosion are iron and other metal-based objects, as well as building elements.
    [0012] Anticorrosive treatments create a continuous layer, generally several microns thick, and typically between 1 and 10 microns, which is intended to coat the material to be protected and avoid direct contact of the material with the atmosphere or the environment. One of the most widely used types of anticorrosive coatings consists of a dispersion in suitable proportions of different particles that are suspended in water or in other media containing organic solvents (Hare, CH and SJ Wright. Anti-corrosive primers based on zinc flake. 1982 , url: https://trid.trb.org/view/416244, access date December 11, 2019). The particles present in the dispersion have sizes between 100 nm and several microns. The larger particles have generally flat shapes that facilitate the formation of the protective layer. In the composition of these coatings Common commercial ones are found in higher percentages of metallic particles of elements such as Zn, Al, Ni and / or others, in addition to metallic oxides such as TiO2, Al2O3, SiO2 among others. Other additives can be metal alkoxides, among which can be alkoxysilanes and alkoxides of titanium or aluminum.
    [0014] The mission that the components of commercial coatings must fulfill is to create a continuous barrier on the substrate that avoids its contact with the environment and to protect against the redox or acid / base chemical process that causes corrosion. Thus, some metallic particles, such as those of Zn or Ni, have the mission of acting as sacrificial agents, undergoing chemical oxidation more easily than the substrate they cover, so when they oxidize in preference to the substrate they protect, they avoid the corrosion of it. On the other hand, metal oxides and metal alkoxides can act as binders, filling the gap and creating a continuous barrier that prevents exposure of the coated substrate surface to the environment. In addition to being sacrificial and barrier agents, other common functions of coating components are aesthetics, adhesion promoters, ion sequestrants, etc.
    [0016] These types of coatings may contain little or no carbon compounds, such as polymer particles, which help seal the surface and prevent barrier corrosion.
    [0018] Other types of anticorrosive coatings commonly used are based on coating the material to be protected with an organic polymer of a defined nature, which may or may not contain additives that enhance its action (Sorensen, PA, et al. Anticorrosive coatings: a review. Journal of Coatings Technology and Research.
    [0019] 2009. 6 (2): 135-176). This polymer can be synthetic such as polyaniline or it can be of natural origin such as chitosan (Deng, Y.-q., et al. "Development of the research in polyaniline anti-corrosion coatings." Corrosion and protection-nanchang.
    [0020] 2003. 24 (8): 333-336; El-Fattah, MA, et al. "Improvement of corrosion resistance, antimicrobial activity, mechanical and chemical properties of epoxy coating by loading chitosan as a natural renewable resource." Progress in Organic Coatings. 2016. 101: 288-296). These polymers can incorporate antioxidant additives that protect the substrate they coat from the redox chemical process. However, many of these organic coatings have the disadvantage that they are attacked by solvents, including water at different pH values.
    [0021] On the other hand, plastic precursor polymers can also have disadvantages such as anticorrosive coatings, among which are the presence of porosity, attack by water in a certain range of pH values or attack by organic solvents, as well as aging and degradation by exposure to the sunlight or other environmental conditions, in addition to the adhesion to the substrate is often insufficient.
    [0023] In usual practice, anticorrosive treatments are carried out by applying the coatings described above on previously cleaned and pre-treated surfaces following different procedures such as immersing the object in a suspension, spraying the object with an aerosol or applying the coating by painting. of the object. Subsequently, the treatment is completed with an annealing or heat treatment step that promotes adhesion between the substrate and the coating layer, but does not change the chemical composition of the coating. For large objects, annealing is not possible.
    [0025] As mentioned, the current coatings do not have or have a low percentage of carbon and that is why when subjected to physical treatments there is no modification of them, which makes them different from the invention described here. As indicated below, the disadvantages of the coatings currently used in current practice are largely overcome if these organic plastic coatings are transformed into carbonaceous vitreous enamels.
    [0027] That is why this document describes a series of coatings that, through proper treatment, undergo a severe alteration of their initial chemical structure, notably varying their elemental composition so that the percentage of carbon significantly increases with respect to the initial values and exponentially improving its adhesion to the substrate and completely covering the surface of the substrate, presenting without cracks, regardless of the geometric shape and size of said substrate.
    [0029] The present invention, therefore, is presented as a very advantageous alternative with respect to the anticorrosive enamels that currently exist on the market. Said invention is a carbonaceous vitreous enamel that is based on the ability of some polymers to form continuous films on three-dimensional objects, and that surprisingly and unexpectedly, are transformed into carbonaceous vitreous enamels without discontinuity or breakage in the transformation process of the precursor film.
    [0031] DESCRIPTION OF THE INVENTION
    [0033] The present invention describes an amorphous carbonaceous anticorrosive coating with a glassy appearance, which is synthesized from the suitable precursors to achieve these coatings. Likewise, the present invention also has as its object the process by which said anticorrosive coating is obtained and its use to form a continuous layer on materials of any geometry, nature or size.
    [0035] Therefore, a first object of the present invention is a carbonaceous anticorrosive coating to cover a substrate characterized in that:
    [0036] to. It comprises a carbonaceous vitreous enamel with an amorphous structure, with a carbon atom content greater than 40% with respect to the total number of atoms and where said carbon atoms present sp2 and sp3 hybridization; b. it has a uniform thickness on the surface of the substrate that can vary between 1 nm and 100 nm.
    [0038] Within the scope of the present invention, a carbonaceous anticorrosive coating is understood to be a layer of submicron thickness, with a carbon percentage greater than 40%, preferably greater than 60% and even more preferably 80% or greater. The thickness of the coating described herein can be a few nanometers and typically less than 100 nanometers (nm). The minimum thickness of the coating can be 1 nm. In the context of the present invention, said coating is continuous over the entire surface of the substrate or material on which it is deposited in order to protect said material from the erosive or corrosive action of environmental or chemical agents.
    [0040] By vitreous enamel, or enamel in the present document, it is understood an amorphous coating material with an undefined chemical structure that exhibits gloss and that is obtained by heat treatment that causes the transformation of a precursor polymer into a vitreous carbonaceous material, which is what presents adherence and anticorrosive properties as described herein.
    [0042] In embodiments of the present invention, the content of atoms that the anticorrosive coating comprises is given as a percentage by weight with respect to the total.
    [0044] The anticorrosive coating object of the present invention, having an amorphous chemical structure, can be characterized by electron microscopy and atomic force techniques. Scanning electron microscopy can be coupled with fast ion bombardment that allows excavation of the material surface down to tens of microns. By means of this combination of ion bombardment scanning microscopy it is possible to determine with a precision of tens of nanometers the thickness of the coating layer and the presence and size of particles that may be contained in it. This technique may require manipulation of the object and the cutting of a certain part of it so that it can be inserted into the microscope chamber.
    [0046] Atomic force microscopy makes it possible to determine the thickness of the coating layer with nanometric resolution. This may require adapting the specimen to be measured to the microscopy equipment, such as cutting a part of the piece. The thickness is determined by comparing the height of the microscope tip on the coating and on a part of the part where the coating has been removed, for example by making a cut in the film with a sharp object.
    [0048] The vibrational Raman spectroscopy for the coating described here generally presents three broad bands that appear on 2700-2950, 1590 and 1350 cm "1 and which are known as 2D, G and D bands in carbonaceous materials. The width and relative intensity of These bands can vary from one coating to another depending on the nature of the precursor, the range of values between the intensity of the G band on the D being between 0.8 and 1.5. This Raman spectroscopy provides spectra of the coated surface which can be considered as the common fingerprint for the carbonaceous vitreous coatings described in the present invention By way of illustration, Figure 2 herein provides a Raman spectrum of one of the coatings of the present invention.
    [0050] X-ray photoelectron spectroscopy (XPS) makes it possible to establish the relative atomic ratio on the surface of the elements present in the coating. This technique also indicates the distribution of each element in different chemical families depending on the percentages of each atom that have different coordination environments. Thus, the XPS analysis of the coatings of the present invention reveals the presence of the C1s peak at a binding value around 285 eV with different components, including sp2 graphitic carbon atoms, carbon attached to carbon atoms. oxygen with single double and triple bonds. Oxygen is another element that is also generally present in carbonaceous enamels and is characterized by the O1s peak that appears at a binding energy value of around 533 eV.
    [0052] In one embodiment of the present invention, the anti-corrosion coating may comprise hereto atoms or additives or a combination of both, as described later herein. In said preferred embodiments of the invention, the presence of heteroatoms in carbonaceous enamel, such as N and P, can also be detected in XPS, by observing the peaks corresponding to these elements. If the coating contains additives such as Zn or Ni nanoparticles, the constituent elements of these additives are also detectable in XPS. The relative intensity of the XPS peaks makes it possible to quantify the atomic ratio of these elements present on the enamel surface.
    [0054] The adhesion of the enamels on the support can be determined by the standard methods applicable to coatings. One simple way is to test the adhesive tape on the previously gridded coating. The adhesion of coatings to substrates depends on several factors, including the nature of the substrate and its pre-treatments prior to coating the precursor.
    [0056] The anticorrosive property of carbonaceous vitreous enamel described here derives from the chemical nature of enamel, which is resistant to oxidation due to exposure to the atmosphere and / or aggressive environments and its ability to completely cover a three-dimensional object of any size without cracks, holes. or discontinuity in the coating.
    [0058] In this way, the carbonaceous vitreous enamel described here creates a protective inert barrier that covers the substrate. Other properties derived from the nature of the coating object of the invention that can play a role in corrosion protection are its hydrophobic nature, its absorption in the ultraviolet region, its possible ability to sequester ions and their possible electrical and thermal conductivity.
    [0060] These carbonaceous vitreous enamels, in addition to the barrier effect, can have anticorrosive properties that make the coated substrate protected from environmental corrosion, even in highly aggressive media. In this way, the present invention describes the nature of these enamels, the suitable organic polymeric precursors and processes that make it possible to transform a thin film of these precursors into a continuous coating made up of a corrosion-protective carbonaceous vitreous enamel.
    [0062] The coating object of the invention is obtained from polymers that are referred to in this document as precursor polymers. Said precursor polymers are already described in the state of the art as anticorrosive coatings. But in a novel and unexpected way, the present invention describes an anticorrosive coating that is obtained from some of these precursor polymers which, through a transformation, give rise to continuous anticorrosive carbonaceous enamels where there has been a change in the chemical structure of said precursor polymer to an amorphous material with an indefinite structure that presents a greater anti-corrosion protection and adherence. The structural change described here is such that any of the spectroscopic properties that characterize the polymer are no longer observed and the spectra undergo drastic changes when the transformation of the precursor polymers into carbonaceous vitreous enamel occurs.
    [0064] In embodiments of the present invention, transformation of the precursor polymers is by thermal transformation.
    [0066] The polymeric precursors suitable for the present invention are those that meet the following requirements: i) they form continuous and conformal thin films on the substrates, without cracks or holes, ii) they can be transformed into continuous carbonaceous vitreous films without suffering cracks, breakage of films, and iii) possess resistance to oxidation.
    [0068] Only some of the plastic polymers adequately fulfill the above properties. Among the natural polymers, those that meet the requirements of the present invention are chitosan, alginates soluble in aqueous medium such as sodium and ammonium, carrageenans and gelatins. Plastic polymers include acrylonitrile and polystyrenes. In all cases, the structure of the resulting coating after transformation is different from the precursor polymer and, therefore, it is a different material from that of the starting precursor. Generally the transformation described herein takes place with a marked shrinkage in the thickness of the precursor films. By way of example, 30 nm sodium alginate films shrink to between 5 and 10 nm when transformed into the carbonaceous coating described herein.
    [0070] Among the precursor polymers that give rise to the anticorrosive coating object of the invention, there are those that are of natural or synthetic origin.
    [0072] In embodiments of the present invention where the precursor polymers are naturally occurring polymers, these can be polysaccharides and natural proteins such as alginate, chitosan, carrageenan, gelatins, and combinations of the foregoing. In other embodiments of the present invention where the precursor polymers are of synthetic origin, said polymers can be polystyrene, soluble substituted polystyrenes, polyacrylonitrile, and combinations of the foregoing.
    [0074] The process for obtaining the coating object of the invention is based on the transformation, preferably thermal transformation, of the precursor polymers described above, producing an increase in the carbon content, giving rise, in some embodiments of the present invention, to obtaining of an enamel with a carbon content greater than 40%, in a preferred embodiment, greater than 70% and, in other even more preferred embodiments, greater than 80%.
    [0076] As previously mentioned, the vitreous carbonaceous enamel object of the invention is also characterized by containing sp2 and sp3 atomic hybridized carbons, presenting structural domains of condensed aromatic rings and residual functional groups in undefined and randomly distributed proportions. . Furthermore, the chemical structure of the carbonaceous antioxidant coating is totally different from that of the precursor polymer. These characteristics determine that the carbonaceous vitreous coatings described here cannot be considered identical to the initial plastic polymers.
    [0078] In addition, the resistance to oxidation of the carbonaceous vitreous enamels described here, which is a property of great importance in anticorrosive protection, increases with the presence of heteroatoms, which in a preferred embodiment comprising between 0 to 10% with respect to the total atoms of the anticorrosive coating that are selected from the group consisting of Nitrogen (N), Phosphorus (P), Silicon (Si) , Boron (B) or combination thereof and in an even more preferred embodiment, comprises nitrogen atoms in a content of less than 10% in the carbonaceous enamel. This improvement in properties is unexpected, since the films of many materials tend to undergo cracking and rupture of their continuity when they undergo transformation in their composition due to thermal and structural stresses.
    [0080] In embodiments of the present invention, the content of heteroatoms that the anticorrosive coating comprises is given as a percentage by weight with respect to the total.
    [0082] Another object of the present invention is the method by which the anticorrosive coating described in this document is obtained, characterized in that it comprises:
    [0083] to. depositing by immersion, painting or aerosol a precursor polymer of natural or synthetic origin a thickness between 1nm and 100nm on the surface of a substrate, and
    [0084] b. transforming the precursor polymer into carbonaceous vitreous enamel, by means of - term treatment by electric or gas furnace at a temperature between 350 ° C and 900 ° C for a period of 45 to 90 minutes; or
    [0085] - microwave irradiation at a power between 400W to 800W for a period between 30 to 90 seconds, followed by a period of rest of 3 to 6 minutes, repeating the interval of treatment and rest between 2 to 6 times; or - magnetic induction at a temperature between 400 ° C to 750 ° C for a period of between 1 to 8 minutes, followed by a rest period of between 8 to 11 minutes, in the absence of oxygen, repeating the treatment interval and rest 4 to 10 times; or
    [0086] - continuous laser irradiation for 30 seconds or pulsed laser irradiation by means of 10 pulses per second for 30 seconds at a wavelength comprised between 255 to 1200 nm, the irradiation being repeated up to a maximum of 10 times with rest intervals of one minute; or
    [0087] - by exposure to plasma gases at atmospheric pressure for an interval of between 12 to 18 minutes followed by periods of rest of the same interval of time.
    [0088] In some embodiments of the present invention, the transformation of the precursor is carried out in the absence of oxygen which, within the scope of the present invention, can be carried out by means of an inert atmosphere that consists of displacing, within the work area, the oxygen by a gas inert. As is known in the state of the art, said inert gas can be argon or helium.
    [0090] As indicated, the arrangement of the polymeric precursor on the surface of the substrate can be carried out by dipping, painting or spraying, forming a thin layer that covers the entire surface of said material.
    [0092] Prior to the formation of the precursor layer, the method object of the invention may comprise an additional step which is a pretreatment of the substrate surface by which the adhesion of the carbonaceous anticorrosive coating described herein is subsequently promoted. It is recommended but not essential that the object to be coated is clean. In the case of metallic objects, these are subjected to etching by acid treatments in order to eliminate surface oxides. In addition, the objects can be subjected to mechanical blows and different forms of shot blasting in order to create on the surface of the material to be protected the appropriate roughness that allows a better adhesion of the coating.
    [0094] The preparation of the carbonaceous vitreous coating requires the prior obtaining of coatings of the precursor that is later transformed into the anticorrosive coating. An important requirement in the formation of the anticorrosive coatings described herein is the continuity of the precursor film on the substrate and the absence of spots, holes or breaks therein. A thin layer of the precursor is formed on the cleaned and treated surface of the object to be coated. This film can be conveniently formed by immersing the object to be protected in a solution of the precursor, by painting, by deposition of the precursor as an aerosol or in any other way. The application temperature can be room temperature or higher than this because the application is carried out in a thermostatted chamber or closed room.
    [0096] In a preferred embodiment of the present invention, the transformation of the precursor can be carried out, when the substrate allows it, by means of a heat treatment in the absence of oxygen at temperatures between 350 ° C and 900 ° C. In other preferred embodiments, the temperature of the heat treatment is comprised between 375 ° C to 850 ° C, and in other even more preferred embodiments, the temperature is between 400 ° C to 600 ° C. The time to which said treatment is submitted is between 45 minutes to 90 minutes, being in a more preferred embodiment, a range between 50 minutes to 75 minutes. The heating that transforms the precursor can also be carried out in electric or gas ovens both statically and by moving the objects through the oven. The heating rate can be very high, producing a sudden increase in temperature from room temperature, which can be between 18 to 24 °, and in preferred embodiments, 20 ° C to the desired temperature, which is the indicated heat treatment temperature. above, and in a time interval of a few seconds, being in a preferred embodiment an interval of 5 to 30 seconds and in a more preferred embodiment of between 15 to 20 seconds. This fact makes it possible to shorten the treatment times and can make it possible to apply this process to substrates that do not tolerate prolonged heating. This ultra-fast heat treatment can, depending on the precursor, be carried out even in the presence of air. In general, prolonged heating to the indicated temperatures in the presence of air results in the combustion of the precursor polymer, without any anticorrosive layer of carbonaceous vitreous enamel remaining. However, the shortening of the heating times and the proper selection of the treatment temperature, may not make it necessary to remove all or part of the air.
    [0098] Heating can also be carried out by various procedures, including microwave treatment or magnetic induction for short periods of time.
    [0100] When in a preferred embodiment of the present invention, the coating heating is carried out by means of microwaves, the treatment consists in radiating said surface during a time interval of between 30 seconds to 90 seconds, being even more preferred during a period of 60 seconds, at a power between 400W to 800W, being even more preferred at a power between 500W and 700W, followed by a period of rest of between 3 to 6 minutes. This microwave treatment cycle is repeated "n" times until the desired coating is achieved, being in a preferred embodiment, a number "n" comprised between 2 to 6 repetitions of the treatment cycle, and even more preferred, between 2 to 4 repetitions. of the treatment cycle. The microwave equipment used can be fixed, operating by loads or continuously by means of belts that move inside. Alternatively, for objects to To coat large, the microwave can be portable and operated by an operator.
    [0102] In another preferred embodiment when the treatment is by magnetic induction, the treatment consists of subjecting said surface for a time interval of between 1 minute to 8 minutes, being even more preferred for a period of 1 to 5 minutes, at a temperature between 400 ° C to 750 ° C, being even more preferred at a power between 500 ° C and 600 ° C, followed by a period of rest of between 8 to 11 minutes, in the absence of oxygen. This microwave treatment cycle is repeated "n" times until the desired coating is achieved, being in a preferred embodiment, a number "n" comprised between 2 to 10 repetitions of the treatment cycle, and even more preferred, between 2 to 4 repetitions. of the treatment cycle.
    [0104] In an even more preferred embodiment of the present invention, in microwave or magnetic induction treatment, the precursor layer may contain particles that act as susceptible or inductive centers where radiation is absorbed or where magnetic induction changes occur and originate localized heating of the precursor layer, without modifying the properties of the object they cover.
    [0106] The transformation of the precursor can be carried out by other physical procedures such as irradiation of infrared light, visible light or ultraviolet light. A variant is the exposure of the coating to laser pulses of different wavelengths that can range from infrared to ultraviolet. In certain cases, it is necessary to modify the precursor polymer by adding a component that acts as a photon collector, depending on the wavelength. A suitable combination is the use of zinc phthalocyanines as additive and, in a preferred embodiment, a laser with a visible wavelength between 450 nm to 800 nm is used, a more preferred embodiment being between 500 to 650 nm, and in an even more preferred embodiment, at a wavelength of 532 nm to induce the change. The efficiency of this process may depend on the nature of the material to be coated, with the use of lasers being more efficient in cases where the precursor is coating metals or quartz. The process can preferably be carried out in an inert atmosphere or, depending on the precursor, also in air. The control of the laser power and the shape of the beam can determine the penetration of the treatment zone, being able to occur selectively in the precursor film without affecting the substrate.
    [0107] In embodiments of the present invention, it can be a laser of any wavelength. In a preferred embodiment of the present invention, if the coating does not have a colorant as an additive, the CO2 laser is more appropriate. In another preferred embodiment of the invention, in which the coating precursor has colorant in its composition, the most appropriate wavelength is that which radiates the colorant.
    [0109] Other processes for transforming the precursor into carbonaceous enamel that may also be suitable are the action of plasmas, including those of atmospheric pressure, or electric discharges.
    [0111] In a preferred embodiment of the present invention, where the transformation of the precursor is done by means of plasma, the treatment consists of using cold plasma of different gases, being in a more preferred embodiment the plasma of hydrogen or methane, at atmospheric pressure requiring cycles where alternates exposure to plasma over a 12 to 18 minute interval with rest periods of the same time interval, in an even more preferred embodiment a period of time between 13 to 16 minutes, and in an even more preferred embodiment a period of time 15 minutes. In the present document, cold plasma of different gases is indicated since the present treatment is carried out at a cold temperature close to room temperature, being in the context of the present invention a temperature between 15 ° C to 25 ° C, being even more preferred at a temperature between 16 to 19 ° C.
    [0113] In the context of the present invention, atmospheric pressure is understood as the weight that the air column has on a particular point on the earth's surface, and in the scope of the present invention it has an atmospheric pressure value of 101.325 kPa.
    [0115] These films of precursors that are transformed into carbonaceous vitreous enamels can comprise in their composition from 0.1 to 10% by weight with respect to the total of at least one additive that provides certain properties to the coating, and that can be observed in the matrix. glazes when they are analyzed by electron microscopy. These additives are classified within the scope of protection of the present invention into additives with a certain function, on the basis of which they receive the following denomination in this document:
    [0116] • sacrificial agent,
    [0117] • pigmenting function, or
    [0118] • promoting function of the transformation of the precursor polymer.
    [0120] In a preferred embodiment of the present invention, where the additive has the function of a sacrificial agent, said additives undergo preferential oxidation on the surface of the substrate where they are deposited and is selected from the group consisting of nanoparticles of zinc, nickel or a combination of the above .
    [0122] In a preferred embodiment of the present invention, where the additive has aesthetic function, which in the present document is also called pigmenting function and are aluminum nanoparticles or metal oxides which is preferably selected from the group consisting of titanium oxides, oxides of iron, transition metal oxides or a combination of the above, some of them being pigments that modify the visual appearance of the enamel.
    [0124] Within the scope of the present invention, it should be noted that carbonaceous vitreous enamels have a resistance to chemical oxidation by environmental or chemical agents that depends on the residual presence of heteroatoms in the material. Specifically, it has been observed that the presence of N or P in the composition in a percentage between 0.1 and 10% and more specifically around 5% makes carbonaceous materials remarkably resistant to chemical oxidation. Thus, it is not possible to oxidize carbonaceous materials containing 5% N by potassium permanganate in sulfuric acid. This high stability against oxidizing agents, together with the barrier effect of the continuous film are the causes of the anticorrosive protection of the coating.
    [0126] Finally, the use of the anticorrosive coating described in the present document is also an object of the invention to form on the surface of a substrate a continuous layer resistant to corrosion, chemical and environmental oxidation.
    [0128] Based on the technical characteristics of the carbonaceous anticorrosive coating of the present invention, the following advantages are derived:
    [0129] - the coating constitutes a continuous film without cracks or holes that completely covers;
    [0130] - they adapt in a conformal manner, faithfully following the shape of an object of any geometric figure, shape or size that it covers;
    [0131] -withstanding extreme environmental conditions, or if it includes hereto atoms in its composition, it also improves its resistance to oxidizing agents and corrosive;
    [0132] - creates a protective inert barrier that covers the substrate;
    [0133] - thanks to its hydrophobic nature, it has the ability to sequester ions - they have high electrical and thermal conductivity;
    [0134] - They have a resistance to chemical oxidation by environmental or chemical agents that depends on the residual presence of heteroatoms.
    [0136] BRIEF DESCRIPTION OF THE FIGURES
    [0138] Figure 1. Diagram of the preparation procedure of the carbonaceous enamel anticorrosive coatings of the present invention
    [0140] Figure 2. Raman vibrational spectrum of a carbonaceous vitreous enamel recorded by excitation with a 514 nm laser. Raman spectra can be considered as the fingerprint of the type of carbonaceous anticorrosive coatings described in the present invention.
    [0142] DESCRIPTION OF EXAMPLES OF THE PRESENT INVENTION
    [0144] In order to contribute to a better understanding of the invention, and in accordance with a practical embodiment thereof, a series of examples of preferred embodiments of the present invention are attached as an integral part of this description.
    [0146] Having presented in a general way the conditions that the precursors must meet, the way to apply these precursors and how these precursors can be transformed into carbonaceous vitreous anticorrosive coatings, some representative examples of the present invention are described below in order to illustrate the substrates that are capable of being coated, the precursors and additives that they may contain and the processes that transform the precursor into carbonaceous enamel.
    [0148] Example 1. Preparation of a carbonaceous glassy coating on stainless steel from chitosan.
    [0149] 100 mL of 200 mg aqueous solution of commercial chitosan (degree of deacetylation> 90%) are prepared using 200 pL acetic acid to facilitate the process. The steel object to be coated is subjected to a cleaning which may include a detergent formulation, followed by a treatment with 0.05 M hydrochloric acid at room temperature for 1 hour. Subsequently, the object is washed with distilled water, dried with hot forced air and subjected to abrasive blasting in order to adapt the surface of the object to be coated and promote the subsequent adhesion of the carbonaceous antioxidant vitreous enamel. The steel object pretreated in the above manner is dipped into the chitosan solution at room temperature for ten minutes. The object is removed from the solution and dried. Alternatively, depending on the shape of the object, the deposition of the chitosan layer can be carried out by introducing the object into a chamber that completely sprays the surface of the object with an aerosol of the chitosan solution prepared above. The chamber may be at a temperature above ambient, in particular 60 ° C. Another way of deposition of the chitosan layer can be by smearing or painting the surface. Typical thicknesses of the chitosan coating under the conditions indicated are between 30 and 100 nm. After the deposition of the chitosan layer on the steel object to be coated, it is subjected to microwave heating inside a suitable sarcophagus with a power of 500 W for 40 seconds, which produces the transformation of the chitosan in carbonaceous enamel. An alternative heating procedure is to place the object on a moving belt or support through an area where the temperature is 700 ° C or higher and oxygen is absent or in low concentration. The length of the furnace can be one linear meter, the atmosphere can be depleted in oxygen and the speed of the object inside it can be 10 cm * min-1. Alternatively the object can also be statically heated in a closed container within an electric or gas oven. The chemical analysis of the enamel indicates that the carbon content of this enamel is 78%, oxygen being present in a percentage of 17% by weight and N in 5%. This enamel is adhered according to the grid method with a sharp object to the surface and try to detach the enamel from a grid with adhesive tape. This enamel protects the steel from corrosion by immersion with 0.1 M hydrochloric acid at a temperature of 20 oC for 5 h.
    [0151] Example 2. Preparation of a carbonaceous vitreous coating on stainless steel from chitosan containing zinc nanoparticles.
    [0152] Proceed as in the previous example with the difference that the chitosan concentration is higher when dissolving 300 mg of chitosan and 400 pL of acetic acid in 100 mL of distilled water. After dissolution is complete, zinc nanoparticles with an average size of 50 nm are suspended with a weight percentage relative to chitosan of 2%. Other nanoparticles that can be used as additives are aluminum, nickel, silica and TiO2 with a percentage by weight for each of them that can vary between 0.1 and 5%. Mixtures in suitable proportions of several of these nanoparticles can also be dispersed in a total percentage of less than 5% by weight. The viscous suspension is maintained, homogenized by mechanical or ultrasonic means and used to form the precursor film of the antioxidant coating. The rest of the steps indicated in Figure 1 are carried out as mentioned in Example 1.
    [0154] Example 3. Preparation of carbonaceous glass coating on stainless steel from alginate.
    [0155] The procedure is as in Example 1 but using sodium alginate as a precursor for the carbonaceous antioxidant enamel. For this, the solution of sodium alginate in water is prepared by dissolving milliQ in 100 mL of water, whose pH has previously been adjusted to a value of 7 using 10 "2 M NaOH, 250 mg of sodium alginate. This solution can be filtered. under pressure if undissolved particles are observed in suspension. The surface of the object to be coated can be pretreated as indicated in example 1. The coating of the steel object and its transformation into the carbonaceous antioxidant enamel can be carried out carried out by any of the procedures indicated in Example 1. The carbon content of the enamel is 81%, the oxygen content being 18%.
    [0157] Example 4. Preparation of a carbonaceous glass coating on stainless steel from gelatin.
    [0158] The procedure is as in Example 1, but using as a precursor of the carbonaceous antioxidant coating a solution of 100 mL of distilled water containing 200 mg of gelatin of animal origin.
    [0160] Example 5. Preparation of a carbonaceous glassy coating on stainless steel from carrageenan.
    [0161] The procedure is as in example 1, but using as a precursor of the carbonaceous antioxidant coating a solution of 100 mL of distilled water containing 200 mg of carrageenan, preferably its kappa variety. Elemental analysis of enamel reveals that the carbon content is 68%, sulfur being present in the composition in a percentage by weight of 7% and oxygen in 25%.
    [0163] Example 6. Preparation of a carbonaceous glass coating on stainless steel from polystyrene.
    [0164] Unlike the previous examples, the use of polystyrene requires organic solvents. In this way, 200 mg of polystyrene with an average molecular weight of 150,000 are dissolved in 100 mL of dichloromethane. The stainless steel object is cleaned following the procedures used in Example 1. The clean object is immersed in the solution containing polystyrene for 10 minutes. After this time, the object is recovered and allowed to dry by evaporation of the solvent. The antioxidant coating can be carried out by any of the treatments indicated above.
    [0166] Example 7. Preparation of a carbonaceous glassy coating on stainless steel from polyacrylonitrile.
    [0167] 200 mg of low molecular weight polyacrylonitrile are dissolved in 100 ml of dimethylformamide heating to 60 ° C to aid the process. This solution is used to form a coating of stainless steel with polyacrylonitrile as a precursor that is transformed by heating, following any of the indicated procedures, into a carbonaceous vitreous enamel with a high nitrogen content.
    [0169] Example 8. Preparation of a carbonaceous vitreous coating from chitosan on a titanium or copper or other metal object.
    [0171] The procedure indicated in Example 1 is followed, but using a metallic object other than stainless steel and which can be made of titanium, copper or another metal, including (semi) noble metals such as silver or nickel. Cleaning of the surface can be carried out as indicated in Example 1. The coated metallic object passes the adhesion test by adhesive tape and withstands the corrosion of 0.1 M hydrochloric acid by immersion for 5 h.
    [0173] Example 9. Preparation of a carbonaceous glass coating on a ceramic object from chitosan.
    [0175] A solution of chitosan in water is prepared as indicated in the example 1. The surface of the ceramic object can be subjected to mechanical abrasion methods to increase its roughness. The ceramic object to be coated is then mechanically cleaned, followed by washing with detergents. The surface is then coated with the chitosan layer. If the object is flat, a suitable coating procedure is by advancing the object at a constant speed through a dissolution curtain, followed by passage of a mechanical device that controls the thickness of the dissolution layer that remains on the flat surface. The transformation of the chitosan film can be carried out by placing the ceramic object in an electric oven at 700 ° C for 60 minutes. The furnace atmosphere is purged with a flow of nitrogen, to discourage the entry of oxygen into the process.
    [0177] Example 10. Preparation of a carbonaceous vitreous coating on a wooden object from chitosan by irradiation with an infrared laser.
    [0179] A solution of chitosan in water is prepared as indicated in Example 1. The surface of the wooden object to be coated is mechanically cleaned, then the object is painted with the chitosan gel. Painting can be manual or by aerosol spraying or other automatic procedure. The wooden object with the coating is allowed to dry at a temperature of 50 ° C for 1 h. The transformation of the precursor layer into the carbonaceous protective coating is carried out by irradiation with a CO2 laser operating at 20% of its maximum power. The system allows the object to be arranged on a motorized support so that it moves in the 3 dimensions of space and can be exposed to the laser beam over its entire surface.
    [0181] Example 11. Preparation of a carbonaceous vitreous coating on a wooden object from chitosan films containing silicon carbide nanoparticles as susceptor and transformation by means of microwaves.
    [0183] An aqueous chitosan suspension is prepared as indicated in Example 2, but substituting the zinc nanoparticles in the same proportion for others of 20 nm average size silicon carbide. Alternatively, nanoparticles of other susceptor materials can be used. The dispersion is homogenized by mechanical means and ultrasound. The homogeneous dispersion is used to coat the surface of the wooden object. The transformation of the precursor chitosan into the carbonaceous protective coating is carried out by placing the object in an oven microwaves that produce localized heating around silicon carbide nanoparticles. The power of the microwave oven is 500 W and the treatment time is two periods of 30 seconds each with an interval between the two treatments of 5 minutes.
    [0185] Example 12. Preparation of a carbonaceous vitreous coating on a wooden object from chitosan films containing iron carbide nanoparticles as inducer and transformation by magnetic induction.
    [0186] The procedure is as in Example 11, but replacing the silicon carbide with iron carbide with a particle size of less than 40 nm. Alternatively, nanoparticles of other inducer materials can be used. After coating the surface of the wooden object, the transformation of the chitosan into the carbonaceous protective coating can be carried out by magnetic induction by controlling the temperature of the layer at values around 550 ° C for a period of time of 5 minutes. Induction treatment can be repeated for other periods after an interval of 10 minutes between them.
    [0188] Example 13. Preparation of a carbonaceous glass coating on a plastic object from polystyrene films by transformation with an infrared laser.
    [0189] A solution of polystyrene in dichloromethane is prepared as indicated in Example 6 and the object consisting of resin, fiber or plastic is coated by spraying with an aerosol in a chamber at 50 ° C. After drying the object, the carbonaceous protective film is formed by irradiating the surface with a CO2 laser operating at a power lower than 20%.
    [0191] Example 14. Preparation of a carbonaceous glassy coating on a resin object, polymeric fiber or plastic material from polyacrylonitrile films containing silicon carbide nanoparticles as inducer and transformation by microwave.
    [0192] 200 mg of low molecular weight polyacrylonitrile are dissolved in 100 mL of methylpyrrolidone by stirring for 24 h. After this time, 25 mg of silicon carbide nanoparticles are added and the suspension is dispersed homogeneously by means of mechanical stirring or ultrasound. This suspension is used to coat the object with resin, polymeric fiber or plastic material. The transformation of the precursor film into the carbonaceous protective coating is carried out by microwave irradiation at a power of 500 W for a 30 second period. This microwave treatment can be repeated 10 minutes after the first application.
    [0194] Example 15. Preparation of a carbonaceous vitreous coating on a resin object, polymeric fiber or plastic material from polystyrene films containing iron carbide nanoparticles as inducer and transformation by magnetic induction.
    [0195] 200 mg of polystyrene with an average molecular weight of 150,000 daltons are dissolved in 100 mL of dichloromethane by stirring for 2 h at room temperature. After this time, iron carbide nanoparticles with an average size of 25 nm are suspended and the suspension is shaken or sonicated. This dispersion is used to form the precursor films that are transformed into the carbonaceous protective coating on the resin, polymeric fiber or plastic object when subjected to heating by magnetic induction at temperatures of 550 ° C for 1 minute in a chamber in the absence of oxygen. The magnetic induction cycle can be repeated a second time 10 minutes after the first treatment.
    [0197] Example 16. Preparation of a carbonaceous vitreous coating layer on the facade of a building already constructed from a chitosan solution containing silicon carbide nanoparticles as susceptor and transformation by microwaves.
    [0198] We proceed to clean the facade of the building to be coated with detergents and subsequent rinsing. The facade is then sprayed or painted with a chitosan suspension containing silicon carbide prepared as indicated in examples 1 and 11. This film is transformed into the corresponding vitreous enamel by treatment with cycles of 30 seconds at a power of 700 W with a portable microwave emitter. The treatment cycle can be repeated two or more times.
    [0200] Example 17. Preparation of a carbonaceous vitreous coating layer on exterior or interior constructive elements from a chitosan solution containing silicon carbide nanoparticles as susceptor and transformation by microwaves.
    [0201] Following the procedure described in Example 16, other types of construction elements, both exterior and interior, can be protected with the anticorrosive carbonaceous enamel.
    [0202] Example 18. Preparation of a carbonaceous vitreous coating layer on an aircraft fuselage component from a chitosan solution containing silicon carbide nanoparticles as susceptor and microwave transformation. Proceed as in Example 11 but using a clean part of the fuselage of an aircraft.
    权利要求:
    Claims (16)
    [1]
    1. An anticorrosive coating to cover a substrate characterized in that:
    to. It comprises a carbonaceous vitreous enamel with an amorphous structure, with a carbon atom content greater than 40% with respect to the total number of atoms and where said carbon atoms present sp2 and sp3 hybridization; b. It has a uniform thickness on the surface of the substrate that varies between 1nm and 100nm;
    [2]
    2. An anticorrosive coating according to claim 1, wherein the carbonaceous vitreous enamel has a Raman spectrum with three vibrations in the regions between 3000-2700, 1650-1550 and 1400-1300 cm "1.
    [3]
    3. An anticorrosive coating according to claim 1 or 2, comprising heteroatoms between 0 to 10% by weight with respect to the total of atoms that are selected from the group consisting of N, P, Si, B or a combination thereof .
    [4]
    4. Method for obtaining an anticorrosive coating described in claim 1, characterized in that it comprises:
    to. depositing by dipping, painting or spraying a precursor polymer of natural or synthetic origin with a thickness between 1nm and 100nm on the surface of a substrate, and
    b. transform the precursor polymer into carbonaceous vitreous enamel by: - term treatment by electric or gas furnace at a temperature between 350 ° C and 900 ° C for a period of 45 to 90 minutes; or
    - microwave irradiation at a power between 400W to 800W for a period between 30 to 90 seconds, followed by a period of rest of 3 to 6 minutes, repeating the interval of treatment and rest between 2 to 6 times; or - magnetic induction at a temperature between 400 ° C to 750 ° C for a period of between 1 to 8 minutes, followed by a rest period of between 8 to 11 minutes, in the absence of oxygen, repeating the treatment interval and rest 4 to 10 times; or
    - continuous laser irradiation for 30 seconds or pulsed laser irradiation by means of 10 pulses per second for 30 seconds at a wavelength comprised between 255 to 1200 nm, the irradiation being repeated up to a maximum of 10 times with rest intervals of one minute; or
    - by exposure to plasma gases at atmospheric pressure for an interval of between 12 to 18 minutes followed by periods of rest of the same interval of time.
    [5]
    5. Method for obtaining an anticorrosive coating according to claim 4, wherein said method comprises an additional stage prior to stage (a) which consists of pretreating the surface of the substrate by means of the technique selected from the group consisting of treatments corrosive chemicals with acids, bases, oxidizing or reducing agents, chemical cleaning, or physical processes that are selected between mechanical blows and shot blasting as well as any one of their combinations.
    [6]
    6. Method of obtaining an anticorrosive coating according to claim 4 or 5, where the substrate is selected from the group consisting of a metallic material, ceramic, wood, glass, resin, fiber, a polymeric material and a building element already built that is selected between facades and sculptures.
    [7]
    7. Method of obtaining an anticorrosive coating according to claim 6, where when the substrate is a metallic material it is selected from the group consisting of iron, aluminum, titanium, copper and silver as well as any one of its alloys.
    [8]
    8. Method for obtaining an anticorrosive coating according to any one of claims 4 to 7, wherein the precursor polymer is a natural or synthetic polymer.
    [9]
    9. Method of obtaining an anticorrosive coating according to claim 6, where when the substrate is a polymeric material it is selected from the group consisting of resins, fiber and plastic material, as well as any one of their combinations.
    [10]
    10. Method of obtaining an anticorrosive coating according to claim 8, where when the precursor polymer is a natural polymer, this is a polysaccharide or natural protein that is selected from the group consisting of alginates, chitosan, carrageenans and gelatins, as well as any one of its combinations.
    [11]
    11. Method of obtaining an anticorrosive coating according to claim 8, wherein when the precursor polymer is a synthetic polymer selected from the group consisting of polystyrene, soluble substituted polystyrene and polyacrylonitrile as well as any one of their combinations.
    [12]
    12. Method for obtaining an anticorrosive coating according to any one of claims 4 to 11, wherein the precursor polymer comprises in its composition from 0.1 to 10% by weight with respect to the total weight of at least one additive having sacrificial agent function, pigmenting function or transformation promoting function of the precursor polymer.
    [13]
    13. Method for obtaining an anticorrosive coating according to claim 12, wherein when the additive has a sacrificial agent function, it is selected from the group consisting of zinc, nickel and aluminum nanoparticles or a combination of the foregoing.
    [14]
    14. Method of obtaining an anticorrosive coating according to claim 12, where when the additive has a pigmenting function they are aluminum nanoparticles or metal oxides that are selected from the group consisting of titanium oxides, iron oxides and metal oxides transition, as well as any one of its combinations.
    [15]
    15. Method for obtaining an anticorrosive coating according to claim 12, wherein when the additive has a promoting function of the transformation of the precursor polymer, it is selected from the group consisting of silicon carbide and iron carbide nanoparticles.
    [16]
    16. Use of an anti-corrosion coating of claim 1 to form a continuous layer resistant to corrosion, chemical and environmental oxidation on the surface of a substrate.

    Roman sh lft fcm "
    Figure 2
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    同族专利:
    公开号 | 公开日
    ES2843743B2|2022-02-15|
    WO2021148695A1|2021-07-29|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    EP1055649A2|1999-05-24|2000-11-29|MRCC, Inc.|Vitreous carbon composite and method of making and using same|
    WO2002095083A1|2001-05-22|2002-11-28|International Business Machines Corporation|Composite glassy carbon disk substrate|
    EP2813469A1|2012-02-06|2014-12-17|Abengoa Solar New Technologies, S.A.|Method for preparing films of graphene or graphene materials on non-metallic substrates|
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