Nanoceramic treatment for multiple surfaces

Abstract

The invention relates to a single-component coating solution, applied prior to painting, that improves the adhesion and corrosion resistance of metal surfaces when they are subsequently painted. It is primarily a stable solution that replaces the hexavalent-chromium-based products available on the market, which are expensive, highly hazardous to workers and harmful to the environment, as they require the mixing of highly dangerous products. The invention relates to a product based on zirconium fluorotitanate nanoparticles, the nanoparticle, the uses and the method of application, for the pre-treatment of surfaces prior to painting.

Description

[0001] Nanoceramic treatment for multiple surfaces.

[0002] DESCRIPTIVE MEMORANDUM

[0003] TECHNICAL FIELD OF THE INVENTION

[0004] The present invention focuses on the field of surface treatment formulations, specifically on pre-painting surface treatments for various metals in the following industries: automobiles, metal furniture, electrical transformers, architectural cladding, metal blinds, metal ceilings, and others. Specifically, it relates to zirconium fluorotitanate nanoparticles as a preventative surface treatment that improves adhesion and corrosion resistance.

[0005] BACKGROUND OF THE INVENTION

[0006] This technology focuses on surface treatment prior to painting, on various metals in the following industries: automobiles, metal furniture, electrical transformers, architectural cladding, metal blinds, metal ceilings, etc.

[0007] In general, the paint industry seeks to achieve the best durability, the best weather resistance, anti-corrosive and anti-fungal properties, and resistance to humidity, among many other qualities.

[0008] However, to achieve these effects of extending the lifespan of paints, there are a series of pre-painting steps in which the metal surfaces are treated, coated, or chemically modified before being painted, in order to achieve these characteristics and prolong the paint's lifespan. Nanoceramic treatment for multiple surfaces.

[0009] Today, it is widely used in pre-painting solutions, such as chromium-based solutions, for example, immersion baths (specifically hexavalent chromium). This is environmentally unfriendly, toxic to users or workers who handle it, and difficult to dispose of in the environment.

[0010] Therefore, the invention is based on solving the problem of eliminating the use of chromium-based solutions (and specifically hexavalent chromium) as a pretreatment for painting. While solutions currently exist, they are operationally very dangerous and costly, as they require wastewater treatment plants compared to other products used in Chile (with nanotechnology). These products are premixed and must be finished by the user, which contains harmful products and poses a risk to workers. Furthermore, they are unstable with pH variations, requiring preparation and subsequent rinsing with distilled water, making them impractical.

[0011] There are different types of solutions available on the market, ranging from pre-treatments to dual-purpose paints, which have the function of being "anti-corrosive." However, an "anti-corrosive" paint does not fulfill the same functions as a pre-treatment, especially at an industrial level, where legislation requires that any element or surface (including metals) that is painted industrially must undergo a pre-treatment to improve its adhesion, durability, and corrosion resistance, among other characteristics, which are not achieved with dual-purpose anti-corrosive paints.

[0012] This is why there are different options on the market, which are listed below and which differ from the present invention:

[0013] The website (Interempresas)

[0014]

[0015]

[0016] It reveals that nanotechnology applied to paints and coatings seeks to improve the nanoceramic treatment for multiple surfaces.

[0017] Quality and product design are enhanced by titanium nanoparticles, as they provide thermal stability and resistance to mechanical damage and corrosion. Depending on the type of nanomaterial used, the properties of the paints vary. Titanium dioxide (TiO2) nanoparticles reduce allergies and the environmental impact of paints. They also have an anti-odor and anti-graffiti formulation and exhibit high resistance to dust and dirt. Silver or copper nanoparticles with TiO2 can generate electricity. Iron oxide and indium facilitate radiation absorption and fluorescence emission. Zinc oxide improves anti-corrosive properties. Zinc sulfide oxide and copper oxide exhibit high resistance to wear and abrasion and are ideal for developing fire-retardant paints (introduction). Therefore, this document describes the use of titanium nanoparticles in paints as an anti-corrosive coating.However, it does not indicate chromium, nor replacing treatments based on chromium solutions, nor zirconium fluorotitanate nanoparticles.

[0018] The website (SpecialChem:

[0019]

[0020] https: / / coatings.specialchem.com / news / industry-news / researchers-titanium-oxide-nanoparticles-self-cleaning-wall-paints-000233582), di vu I ga that a research team is developing special titanium oxide nanoparticles that can be added to common, commercially available wall paint to establish a self-cleaning power. The nanoparticles are photocatalytically active; they can use sunlight not only to bind substances from the air but also to subsequently break them down. The wall makes the air cleaner and cleans itself at the same time (introduction). Therefore, this document indicates the use of titanium nanoparticles in paints. However, it does not mention chromium, nor does it mention replacing treatments based on chromium solutions, nor zirconium fluorotitanate nanoparticles.

[0021] The scientific publication (Pazokifard et al.) reports the effect of adding silane-treated TiO2 nanoparticles on the self-cleaning properties of an acrylic facade coating. Tetraethoxyorthosilicate (TEOS) was used for the surface treatment of the TiO2 nanoparticles. The effect of the surface treatment and nanoparticle content on the photocatalytic activity of the acrylic coating and its self-cleaning properties was studied. Nanoceramic treatment for multiple surfaces.

[0022] To this end, the photodegradation of the dye Rhodamine B (Rh. B), as a model dye, was investigated using colorimetric techniques while coating samples were exposed to UVA irradiation. The performance of the acrylic coating films was evaluated by measuring the change in gloss under accelerated weathering conditions. The results showed that the addition of treated and untreated TiO2 nanoparticles provides self-cleaning properties to the acrylic coatings. However, treating the silica surface of the TiO2 nanoparticles reduces the coating degradation caused by TiO2. This is more evident when using higher concentrations of the treated TiO2 nanoparticles (abstract). Therefore, this paper indicates the use of titanium nanoparticles for the chemical surface treatment and coating of acrylics.However, it does not indicate its use on metals, nor prior to painting, and does not mention chromium, nor replacing treatments based on chromium solutions, nor zirconium fluorotitanate nanoparticles.

[0023] The scientific publication (Solano et al.) reports an increase in the production of smart nanomaterials for solid surface coatings. These nanomaterials offer a wide range of functionalities, including anticorrosive, antibacterial, and self-cleaning properties. Titanium dioxide (TiO2) and zinc oxide (ZnO) nanoparticles were synthesized using a green chemistry approach. These nanoparticles were fully characterized, and a commercial enamel-type paint was modified using different concentrations (2, 3.5, and 5% w / v) of nanoparticles. These nanocharged paints were then brushed onto the surfaces of various materials, such as carbon steel sheets, wood sheets, and aluminum discs. The anticorrosive, self-cleaning, and antibacterial properties of the nanocharged paints were evaluated to determine their suitability for this application.According to the characterization results, the TiO2 and ZnO nanoparticles exhibited similar physicochemical properties compared to those synthesized using traditional methods. The anti-corrosion results revealed that the nanofilled paints provide a barrier using low concentrations of nanoparticles, due to the reduction of surface agglomeration and the resulting high porosity. Regarding self-cleaning, a nanoceramic treatment mechanism for multiple surfaces was used.

[0024] The proposed degradation assay demonstrated that the presence of both nanoparticles in the paint resulted in high degradation of methylene blue due to the high surface area provided by the nanoparticles. On the other hand, antibacterial activity under UV light was observed only for the ZnO nanoparticles, which may be related to the diffusion of nanoparticles into the bacterial cell membrane, affecting normal function. These results showed promise for the modification of paints with TiO2 and ZnO nanoparticles and their application to solid surfaces in construction, and even in the textile industry (abstract). Therefore, this paper indicates the use of titanium nanoparticles in paints for the chemical treatment of metallic surfaces, providing anticorrosive and self-cleaning properties.However, it does not mention chromium, nor replacing treatments based on chromium solutions, nor zirconium fluorotitanate nanoparticles.

[0025] The scientific publication (Maqbool et al.) reports that adding photocatalytically active TiO2 nanoparticles (NPs) to polymer paints is a viable path toward self-cleaning coatings. While modifying the paint with TiO2 nanoparticles can enhance photoactivity, it can also cause polymer degradation and the release of toxic volatile organic compounds. To counteract these adverse effects, a synthesis method for non-metal (P, N, and C) doped TiO2 nanoparticles is presented, based purely on waste valorization. Characterization of PNC-doped TiO2 nanoparticles by vibrational and photoelectronic spectroscopy, electron microscopy, diffraction, and thermal analysis suggests that the TiO2 nanoparticles were modified with phosphate (P=O), imine species (R=NR), and carbon, which also hindered the anatase / rutile phase transformation, even after calcination at 700°C.When added to water-based paints, PNC-doped TiO2 nanoparticles achieved 96% removal of surface-adsorbed contaminants under natural sunlight or UV light, while maintaining the paint formulation's stability, as confirmed by Fourier transform infrared (FTIR) surface analysis. The origin of the photo-induced self-cleaning properties was elucidated using synchronous, three-dimensional (3D) photoluminescence spectroscopy, indicating that the dopants resulted in 7.3-fold greater inhibition of multi-surface nanoceramic treatments.

[0026] The strength of photoinduced e⁻ / h⁺ recombination compared to a reference P25 photocatalyst (abstract). Therefore, this document indicates the use of titanium nanoparticles in paints for the chemical treatment of surfaces, providing self-cleaning properties. However, it does not mention chromium, nor replacing treatments based on chromium solutions, nor zirconium fluorotitanate nanoparticles.

[0027] The scientific publication (Chen et al.) reports that nanomaterials such as titanium dioxide and zinc oxide are established photocatalysts with well-known applications in a variety of fields. They can be used in paints and coatings as pigments while also providing functionalities such as antimicrobial properties. Antimicrobial properties have become increasingly important due to various diseases transmitted by microorganisms that cause both short- and long-term effects in humans. However, the photodegradation of organic components within the paint reduces its durability and lifespan due to changes in appearance. Inorganic binders such as potassium silicate, sodium silicate, lithium silicate, and phosphate offer an opportunity to replace organic binders, ensuring a balance between functionality and durability.This study critically reviewed a variety of antimicrobial additives, including TiO2, Ag, and ZnO nanomaterials and quaternary ammonium salts, used in functional paints and coatings, as well as the mechanisms of antimicrobial activity of TiO2-based materials (abstract). In general, Ag, ZnO, and TiO2 nanomaterials have been shown to perform well as antimicrobial additives in paints and coatings. These nanomaterials are photocatalysts, and some of them can work well with certain inorganic binders for coating formulations in various applications. The advantages of TiO2, such as its chemical inertness, non-toxicity, and environmental friendliness, make it more advantageous compared to other nanomaterials like nanoAg and nanoZnO. As demonstrated, titanium dioxide nanomaterials are also important pigments and self-cleaning agents in paint design (conclusions).Therefore, this document indicates the use of titanium nanoparticles in paints, for the chemical treatment of metallic surfaces providing nanoceramic treatment properties for multiple surfaces.

[0028] antimicrobial and self-cleaning. However, it does not mention chromium, nor replacing treatments based on chromium solutions, nor zirconium fluorotitanate nanoparticles.

[0029] The scientific publication (Binte et al.) reports the use of nanometer-sized titanium dioxide (TiO2) nanoparticles for the photocatalytic reduction of hexavalent chromium in the presence of formic acid. Photoreduction of Cr(VI) in the absence of formic acid was quite slow. When formic acid was added to the chromium solution as a void eliminator, a rapid photocatalytic reduction of Cr(VI) was observed, due to void consumption and the acceleration of the oxidation reaction. Furthermore, three commercial TiO2 nanoparticles were evaluated to determine their photoactivity in Cr(VI) reduction (abstract). Therefore, this document describes the use of titanium nanoparticles for chromium reduction in solution. However, it does not refer to paints, the treatment of metal surfaces with titanium NP-based paints, or zirconium fluorotitanate nanoparticles.

[0030] The scientific publication (All Ahmed et al.) reports the development of simple and cost-effective methods for reducing Cr(VI) in water to the less toxic and easily separable Cr(III) using titanium dioxide (TiO2). The TiO2 nanoparticles were prepared using a sol-gel method with titania tetrachloride and characterized using X-ray diffraction (XRD), scanning electron microscopy (SEM), energy-dispersive X-ray fluorescence (EDX), and UV-visible spectroscopy. UV-visible spectroscopy indicated that the TiO2 nanoparticles played a significant role in reducing the concentration of Cr(VI) in water samples across a pH range of 1 to 4. The reduction in Cr(VI) concentration after treatment is attributed to the photocatalytic effect of the TiO2 nanoparticles in water samples exposed to direct sunlight (abstract).Therefore, this document indicates the use of titania nanoparticles for chromium reduction in water, given their photocatalytic effect. However, it makes no mention of paints, nor the treatment of metallic surfaces with paints based on titanium nanoparticles, nor zirconium fluorotitanate nanoparticles. Nanoceramic treatment for multiple surfaces.

[0031] The scientific publication (Malakootian et al.) reports the removal of Cr(VI) by photocatalytic reduction of titanium dioxide (TiO2) (in nanoparticle form) and the effect of phenol and humic acid (HA) on its removal efficiency. Experiments were conducted in both simulated synthetic wastewater and real wastewater. Several parameters were considered, including pH, contact time, Cr(VI) and TiO2 concentrations, and a constant concentration of phenol and HA. The Cr(VI) removal efficiency was 81% with TiO2 alone, and 89.7% and 96.2% with HA and phenol, respectively. Cr(VI) removal efficiency improved with decreasing pH and contact time. With increasing TiO2 dosage, Cr(VI) removal increased to 0.5 g / L and then decreased to 1 g / L. The efficiency of Cr (VI) removal decreases with increasing initial Cr (VI) concentration.The removal efficiency, at an initial phenol and HA concentration of 10 mg / L, improved with increasing contact time. Heavy metal ions and organic pollutants are commonly present in real wastewater. This research suggests that the TiO2 photocatalytic reaction could be applied to more effectively treat wastewater containing Cr(VI) and organic compounds (abstract). This research is a laboratory experimental study conducted over six months (October 2017–March 2012). Experiments were performed on both simulated synthetic wastewater and wastewater from the paint industry (materials and methods). Therefore, this paper indicates the use of titanium nanoparticles for chromium reduction in water (and in wastewater from the paint industry), given their photocatalytic effect.However, it does not refer to the use of nanoparticles in paints, nor the treatment of metallic surfaces with paints based on titanium NPs, nor zirconium fluorotitanate nanoparticles.

[0032] The granted patent (US 8632843 B2) discloses methods and systems that control the application of a material to micro-rough implant surfaces. Therefore, the present invention provides a method for applying crystalline nanoparticles to the surface of an implant to produce an implant with a layer of crystalline nanoparticles on its surface. This method of nanoparticle application is designed to promote nanoceramic treatment for multiple surfaces.

[0033] Integration of implants, such as dental and orthopedic screws, into living tissue, and offers the ability to control the thickness and uniformity of the nanoparticle layer, in one or more layers, while simultaneously retaining the microroughness of the implant (abstract). As used, the phrase "liquid deposition technique" refers to any method of applying a liquid nanoparticle solution to an implant surface. Examples of liquid solution application methods include, but are not limited to, immersing the implant in a microemulsion containing crystalline nanoparticles, brushing, and painting (column 6). Whereas, the procedure of the invention focuses on the implant comprising at least one of the following metals: (a) titanium; (b) tantalum; (c) stainless steel; (d) chromium; (e) cobalt; (f) alloys thereof; or combinations thereof (claim 17).Therefore, this document indicates the use of titanium nanoparticles for surface coating (specifically for dental implants). However, it refers interchangeably to the use of titanium or chromium, and in no case does it suggest replacing treatments based on chromium solutions with titanium nanoparticles or zirconia fluorotitanate nanoparticles.

[0034] The patent application (CN 106967985 A) discloses anti-corrosion coatings for metallic surfaces. It provides a type of chromium-free aqueous anti-corrosion paint and a method for preparing the same (abstract). A type of chromium-free aqueous anti-corrosive paint is claimed, characterized in that its raw materials, by weight, include: aluminum-zinc-magnesium silicon polynary alloy, 150-300 parts bronze, 5-20 parts modified nano powder, 50-100 parts epoxy silane coupling, 5-15 parts chelating agent of titanium phosphate coupling, 60-120 parts ethylene glycol, 25-200 parts silane hydrolysate auxiliary agent, 4-6.5 parts thickener, 0.5-1 parts defoamer, 18-36 parts tween, 9-18 parts phosphomolybdate, and 10-30 parts quaternary ammonium salt titanate esters, wherein the aluminum-zinc-magnesium silicon multicomponent alloy powder bag includes aluminum.magnesium, silicon, zinc, and auxiliary element, the mass ratio of aluminum, magnesium, silicon, zinc, and auxiliary element being 55.5-75: 3, 2-9, 6: 0.35-5.7: 18.22-40.87: 0.08-5.5, the auxiliary element being Ni, Mn, Ti, Ag, Zr, La, Ce, Pr, Nd, Se, Er, and Y, at least one (claim 1). Therefore, given the Multi-Surface Nanoceramic Treatment,

[0035] The powder size can be considered in terms of nanoparticle size; consequently, this document indicates the use of titanium nanoparticles for coating metallic surfaces as a replacement for chromium. However, it does not refer solely to titanium nanoparticles, but to a complete mixture of elements and compounds to achieve this type of paint, which differs from the product of the present invention, which is "single-component" and does not consist of zirconium fluorotitanate nanoparticles.

[0036] The patent application (US 5026440 A) discloses a process for treating a degreased, etched, and pickled metal surface to improve the adhesion and corrosion protection of organic surface coatings applied to the metal surface after treatment, comprising the steps of: (a) contacting the degreased, etched, and pickled surface with a treatment liquid that is an aqueous solution, emulsion, or dispersion of aluminum-zirconium complexes obtained as a reaction product of a chelated aluminum component, an organofunctional ligand component, and a zirconium oxyhalide component, the organofunctional ligand being chemically bonded in the reaction product to the chelated aluminum unit and the zirconium unit; (b) rinsing the surface contacted in step (a) with water;and (c) contacting the rinsed surface from step (b) with a solution, emulsion, or aqueous dispersion of one or more inorganic and / or organic film-forming materials, the concentration of all film-forming materials and other solids in said solution, emulsion, or aqueous dispersion being no greater than approximately 2 g / L (claim 1). And a process wherein the metal oxides are selected from silicon oxide, titanium dioxide, and / or aluminum oxide (claims 15-16). Therefore, this document indicates the use of titanium for coating metallic surfaces. However, it does not indicate nanoparticles, chromium, or replacing chromium solution-based treatments, nor zirconium fluorotitanate nanoparticles.

[0037] The granted patent (ES 2730005 T3) discloses a chromium-free, acidic aqueous solution of a fluorocomplex of at least one element M selected from group B, Si, Ti, Zr, and Hf, with a pH value in the range of 2 to 5.5, for the treatment of metallic surfaces. Nanoceramic treatment for multiple surfaces.

[0038] characterized in that it additionally contains a) both zinc ions and magnesium ions, b) one or more components selected from: tin ions, bismuth ions, buffer systems for the pH range of 2.5 to 5.5, c) copper ions and / or silver ions (claim 1). Preferably, the aqueous solution contains an amount of fluorocomplex such that the concentration of metal M is in the range of 1 to 5,000 mg / L, preferably in the range of 5 to 1,000 mg / L, and in particular in the range of 10 to 500 mg / L. Zirconium and / or titanium are especially preferred as metal M. Furthermore, it is preferred that in the fluorocomplex, element M be selected from the group Si, Ti, Zr, and Hf, and that the aqueous solution contain on average at least 1, preferably at least 3, and in particular at least 5 fluorine ions per ion of element M (page 4). 11.A method for the corrosion protection treatment of exposed metal surfaces, characterized in that the metal surfaces, after contact with an aqueous solution of a fluorocomplex, are subsequently washed with an aqueous solution containing one or more components selected from compounds or salts of the elements cobalt, nickel, tin, copper, titanium, and zirconium and / or water-soluble or water-dispersible organic polymers (claim 12). Therefore, this document indicates the use of titanium for coating metal surfaces in a chromium-free solution. However, it does not indicate the use of nanoparticles, paints, or its replacement for treatments based on chromium solutions. Furthermore, this product is a complete mixture of elements and compounds to achieve this metal treatment solution, which differs from the product of the present invention, which is a single-component product and contains neither zirconium fluorotitanate nanoparticles.

[0039] The patent application (ES 2372248 T3) discloses a procedure for coating a metal strip, in which the strip, or the strip segments produced from it in the following process, are first coated with at least one protective layer against corrosion and then with at least one layer containing polymers, similar to a varnish, it being realized that the strip, after having been coated with at least one protective layer against corrosion or after having been coated with at least one layer of a varnish-like coating, is divided to give strip segments, it being realized that the strip segments are then shaped, assembled and / or coated with at least a multi-surface nanoceramic treatment.

[0040] a varnish-like coating and / or with a varnish layer, wherein the varnish-like coating is formed by coating the surface with an aqueous dispersion, which together with water contains a) an organic film-forming material, comprising at least one water-soluble or water-dispersed polymer with an acid number in the range of 5 to 200, constituted on the basis of mixtures of man-made resins and / or mixed polymers based on a man-made resin constituted on the basis of an acrylate, ethylene, urea and formaldehyde, a polyester, a polyurethane, styrene, styrene and butadiene and / or a mixed polymer of an acrylic compound, a polyester and a polyurethane, a polyester containing carboxyl groups, a mixed polymer of ethylene and an acrylic compound, melamine and formaldehyde and / or styrene and an acrylate, b) at least one inorganic compound in the form of particles with an average particle diameter,measured in a scanning electron microscope, which is located in the diameter range of 0.005 to 0.3 pm and c) at least one slip agent, wherein the metallic surface, coated with at least one corrosion-protective layer, is brought into contact with the aqueous composition, and a film containing particles is formed on the metallic surface, which is then dried or dried and further hardened, no actinic radiation being used for hardening, the dried or dried and also hardened film having a layer thickness located in the range of 0.01 to 10 pm (abstract). The process is characterized in that the aqueous composition is broadly or totally free of chromium (VI) compounds (claim 3). Said process considers that the liquid, solution, or suspension for at least one of the corrosion-protective layers and / or the polymer-containing layers,Similar to varnishes, they contain, along with water, at least one inorganic compound in the form of particles with an average particle diameter, measured using a scanning electron microscope, in the diameter range of 0.003 to 1 pm (i.e., nanoparticles), consisting of AlZOs, BaSC, oxide(s) of rare earth elements, at least one other rare earth element compound, SiO2, a silicate, T1O2, Y2O3, Zn, ZnO and / or ZrCh (claim 57). Therefore, this document also focuses on solving the same problem of coating a metallic surface with a chromium-free coating or varnish given its toxic effects; thus, it indicates the use of titanium nanoparticles for coating metallic surfaces in a multi-surface nanoceramic treatment solution.

[0041] Chromium-free, including as a pre-treatment to the coating. However, it does not refer solely to titanium nanoparticles, but to a complete mixture of elements and compounds to achieve this type of varnish or coating, which differs from the product of the present invention, which is "single-component", nor zirconium fluorotitanate nanoparticle.

[0042] The scientific publication (López et al.) reports that zirconium titanate is a widely used compound in electroceramic applications, although applications in catalysis and sensors have also been described. Given the anisotropy in the crystallographic thermal expansion of this compound, it could be considered as a constituent of structural components. In general, to ensure the structural integrity and microstructural homogeneity of a ceramic part, relatively low cooling rates from the fabrication temperature are necessary. This requirement is of fundamental importance for zirconium titanate, since small variations in composition and cooling rate produce significant variations in both phase distribution and thermal expansion. This work reviews existing studies on the stability of zirconium titanate within the ZrO₂-TiO₂ and ZrO₂-TiO₂-Y₂O₃ systems.The main discrepancies regarding compatible phases in the current literature are described, and their possible origins are discussed. Existing data on the crystallographic thermal expansion of this compound are also reviewed (abstract). However, this document does not address pretreatment of paints, a single-component product, or zirconium fluorotitanate nanoparticles.

[0043] The scientific publication (Winiarski et al.) reports that chromium-free conversion coatings were deposited from a bath containing potassium hexafluorotitanate(IV). The substrate was electrogalvanized carbon steel. The resulting coatings had a microspheroidal structure and were homogeneous. XPS analysis showed that the coatings were composed of oxides, hydroxides, phosphates, carbonates, and fluorinated compounds. As part of this study, the influence of coating deposition time on surface morphology, chemical composition, and physicomechanical properties was examined for the application of nanoceramic treatments to multiple surfaces.

[0044] Samples. DC polarization measurements, electrochemical impedance spectroscopy, and neutral salt spray tests showed that the investigated chromium-free coatings significantly increase the corrosion resistance of electrogalvanized steel in a chloride environment. However, this document does not refer to a pretreatment of paints, a "single-component" coating, or zirconium fluorotitanate nanoparticles.

[0045] The scientific publication (Vidya et al.) reports that in the field of nanotechnology, the development of new approaches for the synthesis of zirconium titanate (ZTO) ceramic material is receiving considerable attention. ZTO is a well-known ceramic material with high mechanical strength, high chemical stability, high melting and refractive indices, and a high surface-to-volume ratio. All these positive characteristics have led to its potential use in optical devices, wastewater treatment as a photocatalyst, ceramic pigment, humidity sensors, dielectric material, ceramic capacitors, and more. Gaining knowledge about the synthesis of nanolattices and their properties benefits the environment, society, and the economy. Choosing a sustainable synthesis method will help save energy, time, and money, as well as increase efficiency. Adopting environmentally friendly precursors minimizes waste production.This review, the first of its kind, highlighted different types of synthesis methods adopted by various researchers for the synthesis of zirconium fluorotitanate (ZTO) nanoparticles and analyzed the importance or effect of the metal precursor ratio, as well as the calcination temperature and crystallite size on a single platform, along with the challenges and future prospects (abstract). However, this document does not address a pretreatment for paints, a single-component product, or zirconium fluorotitanate nanoparticles.

[0046] The scientific publication (Sekuiarac et al.) reports that zirconium conversion coatings (ZrCC) were prepared on an aluminum alloy AlSi·Mg 0.3 by immersing the latter in baths of 100–500 ppm of HzZrFs. Electrochemical characterization was performed while the alloy was immersed in 0.5 M NaCl for up to 10 days. Immersion tests were conducted for up to 28 days. Microstructural characterization was performed. Nanoceramic treatment for multiple surfaces.

[0047] Detailed analysis of the coatings before and after immersion. The ZrCC-200 coating had a bilayer structure that was thicker around the intermetallic particles (130–150 nm) than in the matrix (50–60 nm). The corrosion resistance of the ZrCC-200 coating improved during immersion, which was attributed to the transformation of ZrF₂ (ZrOₓF₂) to ZrC₂' (ZrCₓFₓFₓ) and the formation of Al(OH)₃ in the outermost part of the coating (abstract). Pretreating a metal surface during its preparation for industrial applications is a very important step. It should improve the adhesion of topcoats and enhance the corrosion resistance of the substrate. Chemical conversion coatings have been used for such purposes for many years in the appliance, automotive, architectural, defense, and aerospace industries.Chemical conversion coatings are the preferred option in industry for surface pretreatment due to their ease of preparation. The most well-known conversion coatings are chromate and phosphate coatings. However, the latter have already been banned in the EU and the US due to health and environmental concerns, while phosphate coatings are being phased out for environmental and economic reasons. Therefore, there is an ongoing search within the industry, which presents an opportunity for scientific research, to find environmentally friendly alternatives to these coatings. The most viable substitutes, already introduced into the industry, are zirconium conversion coatings (ZrCC) and trivalent chromium processing (TCP). Suitable zirconium conversion coating baths are typically composed of H2ZrF6 and various organic / inorganic additives (introduction).Although this document discusses a chemical conversion coating pretreatment for surfaces, it does not refer to a "single component" or zirconium fluorotitanate nanoparticle.

[0048] The scientific publication (Gao et al.) – a scientific article – reports that the construction of flexible perovskite-structured ceramic fibrous materials could potentially facilitate applications in photocatalysis, wearable devices, and energy storage. However, current perovskite-structured ceramic fibrous materials are brittle and exhibit low resistance to deformation, which has limited their widespread applications. In this work, nanofiber membranes were fabricated using nanoceramic treatment for multiple surfaces.

[0049] Flexible zirconium-doped strontium titanate (ZSTO) nanofibers were produced using a combination of sol-gel and electrospinning methods. The microstructures (pore and crystal) of the ZSTO nanofibers were affected by the zirconium doping content and were closely related to the flexibility of the resulting membranes. The likely mechanism of flexibility of the ZSTO nanofiber membranes is presented. Furthermore, silver phosphate-modified ZSTO (AZSTO) exhibited superior photocatalytic performance towards tetracycline hydrochloride (TCHC) and antibacterial performance against Gram-negative and Gram-positive bacteria under visible light irradiation, including 85% degradation to TCHC within 60 min, a >99.99% inhibition rate, and a >3 mm inhibition zone against Gram-positive bacteria.Furthermore, the superoxide free radical (O₂⁻) and holes played significant roles in the degradation of TCHC, as verified by a radical scavenging experiment. Additionally, the membranes exhibited good reusability over five cycles without the tedious recycling operations required for micro / nanoparticle-based catalysts. The successful fabrication of ZSTO nanofiber membranes would provide a new perspective on photocatalysts, antibacterial materials, and wearable devices (abstract). However, this paper does not address a pretreatment for paints, a single-component product, or zirconium fluorotitanate nanoparticles.

[0050] The patent application (ES 2499515 T3) discloses a process for preparing potassium fluorotitanate comprising the following steps: A) placing ilmenite powder in a reactor and adding a refined solution of HF and peroxide for complete immersion, so that they can react sufficiently as follows to produce fluorotitanic acid; B) filtering the solution resulting from step A and placing the filtrate in another reactor, then after cooling the fluorotitanic acid, adding a KCl solution, so that they can react sufficiently as follows to produce the potassium fluorotitanate precipitate: HzTiFe + KCl -> KzTiF 5+ HCI and then filter the resulting solution using centrifugal dripping; C) add a solution of K2CO3 to the new reaction system formed by the filtrate from step B, and control the pH value of the reaction system, so that the following chemical reaction occurs: HsFeFg + K2CO3 + HCI + HjO -> Fe(OH) 3 + Nanoceramic treatment for multiple surfaces.

[0051] KCl + KF + H₂O then extract the iron elements as flocculent precipitates of Fe(OH)₂ and recycle the KCl and KF solution (abstract). However, it does not refer to a pretreatment of paints, nor to a "single component", nor to zirconium fluorotitanate nanoparticle.

[0052] In conclusion, while titanium nanoparticles are widely used, a single-component solution that does not use chromium or other hazardous substances applied pre-painting is lacking. Therefore, there is a need to develop new formulations that are environmentally friendly, non-toxic for workers to handle, and that improve the characteristics of paints (such as adhesion and corrosion resistance) applied after pre-painting.

[0053] SUMMARY OF THE INVENTION

[0054] Considering that pre-treatment solutions prior to painting are chromium-based products, which are operationally high cost and very dangerous for workers, since they must mix very dangerous products.

[0055] The present invention solves this problem by means of a pre-paint coating composition comprising zirconium fluorotitanate nanoparticles. The composition or nanoparticles are used as a pre-paint coating to improve paint adhesion and corrosion resistance. A pre-paint coating method is also described, comprising adding a zirconium fluorotitanate nanoparticle-based pre-coating formulation to the paint, with the following steps: a) Preparation; b) Dilution / Mixing; c) Adjusting the Mixing Temperature; d) Stirring; e) Surface Coating; f) Exposure Time; and g) Drying.

[0056] EXAMPLES OF USE Nanoceramic treatment for multiple surfaces.

[0057] To further illustrate the invention, we have included a series of concrete examples of its use. These all correspond to real-world situations in which the previously described nanoparticles have been used. These examples serve only as representative supporting elements for a better understanding of the invention and its components, parts, and dimensions.

[0058] Three specific applications of the present invention will be presented as examples. These examples of use will then be listed.

[0059] Example 1: Application of Alkaline Degreaser. Applied by immersion or spraying, in a tank or tunnel with sprayers at a temperature between 40 and 50°C.

[0060] Example 2: Rinse with deionized or soft water. Applied by immersion or spraying, in a tub or tunnel with sprinklers, at room temperature.

[0061] Example 3: Application of NANOCERAMIC. Applied by immersion, spraying, in a vat or tunnel with sprinklers, or through a roller line, at room temperature.

[0062] FIGURE DESCRIPTION

[0063] Figure 1: Application of the nanoparticle under real-world conditions. The application of the nanoceramic material is shown in a test at the ALUZINC plant, in corrosion and blistering tests.

[0064] DETAILED DESCRIPTION OF THE INVENTION

[0065] For a better understanding of the present invention, the following definitions are necessary, which should only be understood as elements that aid in understanding the particular technical characteristics in this technical field. Nanoceramic treatment for multiple surfaces.

[0066] As used in the present invention, the term “Single-component” refers to the present invention, which is a ready-to-use formulation that the customer does not need to mix with other toxic components (such as commercially available solutions that contain hexavalent chromium, lead, and other substances). Therefore, the present invention, being a single-component coating, is safe for the worker and is ready to use (it only needs to be diluted with water, not with other toxic components).

[0067] As used in the present invention, the terms "pre-treatment" and "pre-paint" refer to coating or treatment compositions applied before painting the surface. This is a critical step in industry, as all industrially painted surfaces must undergo a pre-treatment step to comply with regulations. This is not achieved with dual-purpose anti-corrosive paints, since these paints contain other components and are not as efficient as processes that employ a pre-coating or pre-treatment (therefore, pre-treatment compositions are not comparable to, nor similar to, anti-corrosive paints).

[0068] As used in the present invention, the term “Premix” refers to a composition that must be mixed after application. These are considered “multicomponent” and are the current compositions on the market (which use nanotechnology) and are applied as a pretreatment to paint (and are products currently sold in Chile). The customer must complete the mixing of these “premixes,” which poses a risk to workers, especially since they contain toxic elements such as chromium. Furthermore, they are unstable when exposed to pH variations, so they must be prepared and subsequently rinsed with deionized or soft water, making them environmentally unviable and more expensive. This differs from the present invention, which is a single-component product.

[0069] As used in the present invention, the term “Ncmoparticles 11This refers to a particle with all three dimensions smaller than 100 nm. Nanoparticles have physical and chemical properties that can be very different from those of larger materials. Nanoceramic treatment for multiple surfaces.

[0070] size. They are an area of ​​scientific research with many potential applications in fields such as biomedicine, optics, electronics, nanochemistry, agriculture and, in this invention, surface coatings.

[0071] As used in the present invention, the term "Zirconium Fluorotitanate," "Zirconium Fluorotitanate," "Zirconium Fluoro-titanate," "Zirconium Fluorothiotanate," and their variants are used interchangeably and refer to the nanoparticle generated by the present invention, which is used as a pre-treatment to paint, which is environmentally friendly (unlike current solutions that use chromium), since the present invention is a "fluora" which is biodegradable and makes it disposable.

[0072] As used in the present invention, the term "nanoceramic" refers to ceramic nanoparticles that are generally classified as inorganic, heat-resistant, non-metallic solids composed of metallic and non-metallic compounds. A nanoceramic treatment refers to treating materials at the molecular level by rearranging the atoms.

[0073] In a first aspect of the invention, a new type of nanoparticle is presented, which corresponds to zirconium fluorotitanate nanoparticles, which had not been previously developed or described, to generate a composition or coating prior to painting.

[0074] In a second aspect of the invention, it is used as a pre-treatment to paint, to improve paint adhesion and corrosion resistance, which is not a paint as such and is not comparable or equivalent to anti-corrosive paints or "dual" paints.

[0075] Another advantage is that the present invention is a single-component solution, unlike prior art solutions which are multi-component. Specifically, this invention solves the problem of using toxic compounds such as hexavalent chromium, a typical component used in pre-paint solutions currently on the market. Nanoceramic treatment for multiple surfaces.

[0076] This is relevant because the chromium-derived compounds used in all products on the market are toxic, making them environmentally unfriendly and requiring costly wastewater treatment processes. Since they are developed as "multi-component" solutions, it is the worker who must mix them and is exposed to the harmful effects of these prior art solutions.

[0077] Based on the above, the solutions on the market that are "multi-component" are unstable to pH variations, whereas the present invention allows maintaining the pH in the process (between 3.0 - 5.0 pH), therefore, the present invention remains stable to pH variations, which is an advantage.

[0078] Furthermore, paint baths are used in industry for coating surfaces (such as metals, among others). In this regard, current pre-treatment baths saturate rapidly due to pH changes, whereas the solution of the present invention is more stable with respect to pH changes, thus allowing for longer use of the pre-treatment baths and reducing costs. This differs from current chrome plating baths or baths with other types of nanoparticles available on the market.

[0079] Another advantage of the present invention is that, due to its components, it can be diluted in deionized or soft water, whereas solutions of the prior art have to be diluted in other components and always with distilled water, which increases costs.

[0080] Furthermore, with this invention, different metals can be treated interchangeably, thus avoiding costs associated with changing baths with solutions for the different types of metals to be treated, as happens with current methods available on the market.

[0081] So with our invention, another advantage is achieved, in the sense that the pre-treatment with zirconium fluorotitanate nanoparticles generates a chemical reaction on the surface of the metal or the treated surface, whereas the enamels, or dual paints of the previous art only nanoceramic treatment for multiple surfaces.

[0082] They coat the surface (and do not generate a chemical reaction), so this coating can be easily removed physically (by scraping or peeling the surface).

[0083] Thus, the aim is to explain the technical advantages of the invention through the accompanying description, examples, and figures. Therefore, the present invention is intended to be protected in the various non-limiting embodiments indicated below:

[0084] 1. A pre-paint treatment composition comprising zirconium fluorotitanate nanoparticles.

[0085] 2. The pre-treatment composition prior to painting, of embodiment 1, which corresponds to a single component of zirconium fluorotitanate nanoparticles.

[0086] 3. The pre-treatment composition prior to painting, of embodiment 1, wherein said zirconium fluorotitanate nanoparticles comprise: Titanium Dioxide; Zirconium Carbonate 40%; Hydrofluoric Acid 70%; Sodium Molybdate; Soft Water q.s.

[0087] 4. The pre-painting pre-treatment composition of embodiment 3, wherein each 100 grams of said zirconium fluorotitanate nanoparticles comprises:

[0088] • 0.2 g of Titanium Dioxide;

[0089] • 10 g of Zirconium Carbonate 40%;

[0090] • 5.0 g of Hydrofluoric Acid 70%;

[0091] • 0.3 g of Sodium Molybdate;

[0092] • 84.5 grams of Soft Water QSP.

[0093] 5. The pre-treatment composition prior to painting, of embodiment 3, wherein said Titanium Dioxide and Sodium Molybdate are additives.

[0094] 6. The composition of the pre-treatment prior to painting, of embodiment 3, where said Zirconium Carbonate 40% and Hydrofluoric Acid 70% are active ingredients.

[0095] 7. The pre-treatment composition prior to painting of embodiment 3, where said Soft Water CSP is a complementary component. Nanoceramic treatment for multiple surfaces.

[0096] 8. The pre-treatment composition prior to painting of any of embodiments 1-7, wherein said composition is a nanoceramic pre-treatment, which treats the materials at the molecular level.

[0097] 9. The pre-treatment composition prior to painting of any of embodiments 1-7, wherein said composition is stable to pH variations.

[0098] 10. The pre-treatment composition prior to painting of embodiment 9, where said composition allows maintaining the pH in the process between pH 3.0 - 5.0.

[0099] 11. A pre-paint treatment nanoparticle comprising zirconium fluorotitanate nanoparticles.

[0100] 12. The nanoparticle of embodiment 11, wherein the nanoparticle is formulated by the addition of Titanium Dioxide; Zirconium Carbonate 40%; Hydrofluoric Acid 70%; Sodium Molybdate; Soft Water q.s.

[0101] 13. Use of the composition of embodiments 1-10, or of the nanoparticle of embodiments 11-12, because it serves to be applied as a pre-treatment coating prior to painting and comprises zirconium fluorotitanate nanoparticles.

[0102] 14. Use according to embodiment 13, because it serves to improve paint adhesion and corrosion resistance.

[0103] 15. A pre-treatment method prior to painting, comprising adding a pre-coating formulation based on zirconium fluorotitanate nanoparticles to the painting with the steps of:

[0104] a) Preparation;

[0105] b) Dilution Mixture;

[0106] c) Adjust the Mixture temperature;

[0107] d) Agitation;

[0108] e) Surface coating;

[0109] f) Exposure Time; and

[0110] g) Drying. Nanoceramic treatment for multiple surfaces.

[0111] 16. The method according to embodiment 15, wherein in step a), the mixture is prepared directly in the tub or in an auxiliary tank, adding the Nanoparticle product to the de-ionized water (or soft water),

[0112] 17. The method according to embodiment 15, where in step b), it is diluted between 3 - 5% v / v, depending on the temperature and type of metal.

[0113] 18. The method according to embodiment 15, wherein in step c) is adjusted to room temperature (20 - 25°C).

[0114] 19. The method according to embodiment 15, wherein in step d), once the solution is prepared, it is stirred for 10 minutes (with moderate stirring).

[0115] 20. The method according to embodiment 15, wherein in step e) it is coated by immersion in a tub, or by spraying in a tunnel with sprinklers and wetting by rollers.

[0116] 21. The method according to realization 15, where in step f) a minimum of 30 seconds is used, up to 90 seconds, depending on the speed of the line.

[0117] 22. The method according to embodiment 15, wherein in step g), after the nanoceramic process, the treated parts can be air dried, with compressed air, in a drying oven, or fans.

[0118] 23. The method according to embodiment 15, wherein additionally, when an Alkaline Degreaser is applied, it is applied by immersion or spraying, in a tub or tunnel with sprayers at a temperature between 40 and 50°C.

[0119] 24. The method according to realization 15, where additionally a rinse can be made with Deionized or Soft Water, applied by immersion or spraying, in a tub or tunnel with sprinklers, at room temperature.

[0120] EXAMPLES

[0121] The description of the rigorous tests for the functioning of the invention, as well as the different configurations and specific formulation applications for pre-painting treatment, can be seen in the following application examples. Nanoceramic treatment for multiple surfaces.

[0122] Example 1: Formulation of nanoparticles.

[0123] The pre-paint coating comprising zirconium fluorotitanate nanoparticles is prepared by adding the following components, indicated in Table 1 below:

[0124] Table 1: Content per 100 grams of Nanoparticles.

[0125] Quantity Type

[0126] Component Description CAS No. Component (g)

[0127] Additive Titanium Dioxide 0.2 13463-67-7 Active Ingredient Zirconium Carbonate 40% 10.0 36577-48-7 Active Ingredient Hydrofluoric Acid 70% 5.0 7664-39-3 Additive Sodium Molybdate 0.3 10102-40-6 Component

[0128] Soft Water CSP 84.5 7732-18-5

[0129] complementary

[0130]

[0131] Example 2: Method of applying the nanoparticle formulation.

[0132] The protocol or method for adding the zirconium fluorotitanate nanoparticle-based pre-coating formulation is applied in the following step-by-step manner:

[0133] • Preparation: The mixture is prepared directly in the vat or an auxiliary tank by adding the nanoparticle product to deionized water (or soft water). • Mixture Dilution: 3-5% v / v, depending on the temperature and type of metal. • Mixing Temperature: Room temperature (20-25°C). • Stirring: Once the solution is prepared, stir for 10 minutes (with moderate agitation). • Surface Coating Protocol: By immersion in a vat, by spraying in a tunnel with sprinklers, and by wetting with rollers. • Exposure Times: Minimum 30 seconds up to 90 seconds, depending on the line speed. Nanoceramic treatment for multiple surfaces.

[0134] • Drying: After the Nanoceramic process, the treated pieces must be dried in the open air, with compressed air, in a drying oven or fans.

[0135] Example 3: Corrosion and blistering tests at the ALUZINC production plant.

[0136] The corrosion or oxidation assessment is based on the reference standard, according to ASTM D610 / 01. The sample is rated Grade 10 (Scale 0-10), where 10-9 represents the absence or slight blistering. Letter ratings: S (In one place), G (General), P (Dispersed and Precise), 0 (No corrosion).

[0137] Furthermore, blistering is evaluated based on the reference standard, according to ASTM D714-02. Samples are rated according to the following blistering grades, with 10 being the most favorable value in the tests. (Scale of 0-10). Letter ratings: F (slight), M (medium), MD (medium-dense), D (dense).

[0138] Corrosion and blistering tests were performed under real-world conditions near the ALUZINC company (Figure 1). The sample evaluated showed no blistering at the center of the Evans cross according to ASTM 714-02, nor any corrosion according to ASTM 610 / 01 after 1337 hours of exposure. The test will continue until 1500 hours have been completed. The blistering at the corners is due to the adhesive paper seal (Figure 1).

[0139] The measured values ​​of both tests are shown from 0 to 1337 hours of testing in Table 2, according to the values ​​measured by each standard.

[0140] Table 2: Evaluation of samples exposed to blistering and corrosion.

[0141] Blistering Corrosion Degree

[0142] Sample Type

[0143] ASTM 714-02 ASTM 610 / 01

[0144] Sample 280 hours 10 F 10

[0145] Sample 545 hours 10 F 10

[0146]

[0147] Nanoceramic treatment for multiple surfaces.

[0148] Sample 701 hours 10 F 10

[0149] Sample 918 hours 10 F 10

[0150] Sample 1337 hours 10 F 10

[0151]

[0152] REFERENCES

[0153] * Interempresas (Mariana Morcillo). Nanotechnology: the revolution in the paint industry. URL:

[0154] https: / / www.interempresas.net / Industria-Pintura / Articulos / 488130-Nanotecnologia-la-Revolucion-en-la-industria-de-la-Pintura.html

[0155]

[0156] . (2023). ® SpecialChem. Researchers Create Titanium Oxide Nanoparticles for Self-cleaning Wall Paints. URL:

[0157]

[0158] (2024). ® Pazokifard et al. Investigating the role of surface treated titanium dioxide nanoparticles on self-cleaning behavior of an acrylic facade coating. (2023).

[0159] ® Solano et al. Preparation of modified paints with nano-structured additives and its potential applications.

[0160] (2020).

[0161] • Maqbool et al. Highly Stable Self-Cleaning Paints Based on Waste-Valorized PNC-Doped TiO2Nanoparticles.

[0162] (2024).

[0163] * Chen et al. Titanium dioxide and other nanomaterials based antimicrobial additives in functional paints and coatings: Review. (2022).

[0164] « Binte et al. Photocatalytic Reduction of Hexavalent Chromium with Nanosized TiO2in Presence of Formic Acid.

[0165] (2019).

[0166] ® Ali Ahmed et al. Photo-reduction of Chromium from water by TiO2nanoparticles. (2018).

[0167] * Malakootian et al. Hexavalent chromium removal by titanium dioxide photocatalytic reduction and the effect of phenol and humic acid on its removal efficiency. (2016).

[0168] * US 8,632,843, B2. Promimic AB. Methods and systems of controlled coating of nanoparticles onto micro-rough implant surfaces and associated implants. (2014).

[0169] *CN 106967985 A, Yangcheng Institute of Technology. A kind of aqueous chromium-free anticorrosive paint and preparation method thereof. (2017).

[0170] ® US 5,026,440, Gerhard Collardin GmbH. Chromium free treatment before coating metal surfaces. (1991). Nanoceramic treatment for multiple surfaces.

[0171] * ES 2730005 T3. Henke AG and Co KGaA. Wet process and chromium-free acid solution for the corrosion protection treatment of steel surfaces. (2019).

[0172] * ES 2372248 T3. Chemetall GmbH. Process for pre-treating and / or coating metal surfaces prior to forming with a varnish-like coating, and use of the substrates thus coated. (2012).

[0173] ® López. Zirconium thiana: thermodynamic stability and thermal expansion. (2011).

[0174] • Winiarski et al. Corrosion resistance of chromium-free conversion coatings deposited on electrogalvanized steel from potassium hexafluorotitanate (IV) containing bath, (2013),

[0175] *Vidya et al. Zirconium titanate nanoparticles: Brief review on the synthesis. (2023).

[0176] • Šekularac et al. Prolonged protection, by zirconium conversion coatings, of AISi7Mg0.3 aluminum alloy in chloride solution. (2020).

[0177] ® Gao et al. Flexible zirconium doped strontium titanate nanofibrous membranes with enhanced visible-light photocatalytic performance and antibacterial activities. (2021).

[0178] ® ES 2499515 T3. Sun Xing Chemical and Metallurgical Materials (Shenzhen) Co Ltd. Proceso para la producción de fluorotitanato de potasio. (2014).

Claims

CLAIMS 1. A pre-painting pre-treatment composition, CHARACTERIZED in that it comprises zirconium fluorotitanate nanoparticles.

2. The pre-treatment composition prior to painting, of claim 1, CHARACTERIZED in that it corresponds to a single component of zirconium fluorotitanate nanoparticles.

3. The pre-treatment composition prior to painting, of claim 1, CHARACTERIZED in that said zirconium fluorotitanate nanoparticles comprise: Titanium Dioxide; Zirconium Carbonate 40%; Hydrofluoric Acid 70%; Sodium Molybdate; Soft Water q.s.

4. The pre-painting pre-treatment composition of claim 3, CHARACTERIZED in that each 100 grams of said zirconium fluorotitanate nanoparticles comprises: ® 0.2 g of Titanium Dioxide; ® 10 g of Zirconium Carbonate 40%; ® 5.0 g of Hydrofluoric Acid 70%; ® 0.3 g of Sodium Molybdate; ® 84.5 grams of Soft Water QSP.

5. The pre-treatment composition prior to painting, of claim 3, CHARACTERIZED in that said Titanium Dioxide and Sodium Molybdate are additives.

6. The pre-treatment composition prior to painting, of claim 3, CHARACTERIZED in that said Zirconium Carbonate 40% and Hydrofluoric Acid 70%, are active ingredients.

7. The pre-treatment composition prior to painting of claim 3, CHARACTERIZED in that said Soft Water QSP, is a complementary component, 8. The pre-treatment composition prior to painting of any of claims 1-7, CHARACTERIZED in that said composition is a nanoceramic pre-treatment, which treats the materials at the molecular level.

9. The pre-treatment composition prior to painting of any of claims 1-7, CHARACTERIZED in that said composition is stable to pH variations.

10. The pre-treatment composition prior to painting of claim 9, CHARACTERIZED in that said composition allows maintaining the pH in the process between pH 3.0 - 5.

0.

11. A pre-paint treatment nanoparticle, CHARACTERIZED in that it comprises zirconium fluorotitanate nanoparticles.

12. The nanoparticle of claim 11, CHARACTERIZED in that the nanoparticle is formulated by the addition of Titanium Dioxide; Zirconium Carbonate 40%; Hydrofluoric Acid 70%; Sodium Molybdate; Soft Water q.s.

13. Use of the composition of claims 1-10, or of the nanoparticle of claims 11-12, CHARACTERIZED in that it serves to be applied as a pre-treatment coating prior to painting and comprises zirconium fluorotitanate nanoparticles.

14. The use according to claim 13, CHARACTERIZED in that it serves to improve paint adhesion and corrosion resistance.

15. A pre-painting pre-treatment method, CHARACTERIZED in that it comprises adding a pre-painting coating formulation based on zirconium fluorotitanate nanoparticles with the steps of a) Preparation; b) Dilution Mixture; c) Adjust the Mixture temperature; d) Agitation; e) Surface coating; f) Exposure Time; and g) Drying.

16. The method according to claim 15, CHARACTERIZED in that in step a), the mixture is prepared directly in the tub or in an auxiliary tank, adding the Nanoparticle product to the de-ionized water (or soft water).

17. The method according to claim 15, CHARACTERIZED in that the [material] in step b) is diluted between 3 - 5% v / v, depending on the temperature and type of metal.

18. The method according to claim 15, CHARACTERIZED in that the step c) is adjusted to room temperature (20 - 25°C).

19. The method according to claim 15, CHARACTERIZED in that in step d), once the solution is prepared, it is stirred for 10 minutes (with moderate stirring).

20. The method according to claim 15, CHARACTERIZED in that in step e) it is coated by immersion in a tub, or by spraying in a tunnel with sprinklers and wetting by rollers.

21. The method according to claim 15, CHARACTERIZED in that in step f) a minimum of 30 seconds, up to 90 seconds, is used, depending on the speed of the line.

22. The method according to claim 15, CHARACTERIZED in that in step g), after the nanoceramic process, the treated parts can be dried in the open air, with compressed air, in a drying oven, or fans.

23. The method according to claim 15, CHARACTERIZED in that, additionally, when an Alkaline Degreaser is applied, it is applied by immersion or spraying, in a tub or tunnel with sprayers at a temperature between 40 and 50°C.

24. The method according to claim 15, CHARACTERIZED in that an additional rinse can be made with Deionized or Soft Water, applied by immersion or spraying, in a tub or tunnel with sprinklers, at room temperature.

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