MXPA00002082A - Electrochemical deposition of a composite polymer-metal oxide - Google Patents

Abstract

A process for forming polymer films through electrochemical techniques utilizing electrolytes with include conductive polymer. The resulting polymer films are electrically conductive and corrosion and wear resistant. Polyamino-benzene (polyaniline), for example, undergoes an insulator-to-metal transition upon doping with protonic acids in an acid/base-type reaction. Composite polymer-aluminum oxide films may be formed by modifying the anodizing electrolyte, resulting in the codeposition of polyaniline during aluminum anodization. A nonprotonated, ring-sulfonated aluminun salt of polyaniline was determined to be the reaction product within the aluminum oxide phase of the codeposited films. A second process, which incorporates electrochemical sealing of the anodic layer with polyaniline, was also developed. The formation of these composite films is documented through experimental processing, and characterized through scientific analysis and engineering tests. Scientific characterization determined the codeposition process yields chemically and metallurgically bound composite films. Engineering testing determined the films, obtained through a single step, exhibit superior wear and comparable corrosion resistance to conventionally anodized and sealed films processed through two steps, demonstrating the increased manufacturing efficiency that can be realized using the processes of the present invention.

Description

ELECTROCHEMICAL DEPOSITION OF A COMPOUND METAL POLYMER-OXIDE This invention relates to the use and formation of composite films through electrodeposition and anodization techniques. More specifically, the invention relates to the electrochemical formation of composite polymer-metal oxide films using an electrolyte which incorporates a conductive polymer. A common anodization process uses aluminum as a substrate. The anodizing process of aluminum is the most frequent: it is used to produce decorative finishes, to increase the corrosion or wear resistance of the aluminum substrate, or to provide an adherent interface for subsequent coatings. In some cases, the anodic film requires additional processing after film formation to achieve these characteristics.The supplemental coating is carried out through various sealing processes and conversion coatings, which seal the porous structure of the film as Anodized to offer resistance to corrosion, pigmentation, and / or to provide lubricity to increase wear resistance.

When the anodic film is used as an adherent interface for subsequent coatings, its purpose is usually to join different metals. For a long time there has been a need for reliable means to chemically bond different materials whose atomic structures and compositions make them chemically immiscible, such as metals, ceramics and polymers. The coatings used to allow joining a ceramic to a metal typically have constituents which are miscible with their deponent substrates. For ceramic-to-metal bonding, these constituents are metal oxides and glass formers that get wet and bond to the ceramic surface. These coatings also include additional immiscible constituents which, by virtue of their immiscibility, create a new surface upon which the bonding process can be effected. Known methods for providing such coatings, such as thick and thin film metallization techniques, form a composite interface between the bonding surfaces, which makes it possible to complete the chemical bonding of different metals and materials. However, these methods have not allowed joining polymer to metal using a chemical bond.

Some of the most common polymer-metal bonds use adhesives. These unions do not require or miscibility in the formation of intermediate phases. The »strength of the resulting polymer-metal bond The use of an adhesive normally has an impact on the quality of the preparation of the substrate surface.

This is because the adhesive, while not cured, will flow to fill the features of the surface morphology. In this way, a union has been formed mechanics between the adhesive and the surface of the substrate.

Although some of the strength of the joint is derived from the polar forces between the adhesive and the surface, these forces are relatively minor and do not contribute in any meaningful way to the overall integrity of the union. Polymer-metal bonds "without adhesive" have also been developed in the electronics industry. These unions provide the advantage of downsizing, as well as the fact that they allow for greater flexibility of connectors and electrical circuits. Bonding without adhesive can be obtained by "seeding" a chemically prepared polymer surface. The nature of the bonding without adhesive involves the binding of a noble metal salt to a functional ligand on the surface of the polymer, followed by the reduction of the noble metal to a state of zero valence. The surface becomes slightly conductive, which allows the non-electrolytic deposition of the metal. The resulting metal surface can then be • 5 coated by means of electrodeposition. However, the seeded film is insufficiently conductive for direct use for electrosurgery. In this way, without the preparation of the improved surface necessary to allow electrodeposition, the forces bond without weak adhesives and low adhesions.

• The typical failure mode of both polymer-metal bonds with adhesive and without adhesive is the delamination or "peeling" of the adhesive or one of the interface surfaces of the coupled interface. The failures occur due to inadequate or inadequate surface preparation, surface contamination, or the use of a badly applied, erroneous, outdated or otherwise deficient adhesive. The preparation of the surface for the polymer-metal bond goes from the Simple cleaning of the surface to the development of a supplementary conversion coating on the metal surface. For steel bases, phosphate type conversion coatings are commonly used. For aluminum bases, the surface with frequency is anodized. If properly deposited, the nature of the conversion coating or anodic film is that of a metal phosphate layer or a metal oxide layer chemically bonded to the metal substrate. However, such coatings act only as a surface improver to promote adhesion for polymer binding. In other words, the conversion coating / anodic film acts as a primer or primer, and although it chemically bonds to the metal surface, it does not chemically bond to the subsequent polymer coating. Anodic coatings used as "stand-alone" films, deposited for corrosion and wear resistance or for decorative purposes, but not to provide bonding of different materials, have been created using a two-step process in which a polymer or Another material is applied to the surface of the anodic film after the anodization has occurred. With the polymer-based supplemental coatings, the polymer is not chemically bonded to the oxide film and is of a thickness limited by the following factors: the properties of effective mechanical adhesion of the film to the oxide; the diameter of the pores in the oxide film; the wetting characteristics of the oxide surface; and the viscosity of the polymer coating. Because the supplemental coating is of a finite thickness that does not fully introduce the porous structure, it can be peeled off and removed from the surface of the substrate during service and, therefore, has a limited lifetime of use. In another process, known as the "Metalast" process and described in U.S. Patent No. 5,132,003 to Mitani, a polymer and acrylate are electropolymerized followed by a hard coating anodization. However, in this process, the acrylate polymer does not actively participate in the anodization reaction, and requires a subsequent treatment of a second electrolytic bath which incorporates a metal salt, which forms a composite coating finished in three steps. Other supplemental coatings, placed to confer resistance to impact corrosion, involve the conversion of the oxide into a metal complex, the most common being the chromate conversion coating. When deposited, these coatings are gelatinous and therefore fragile. With dehydration, the supplemental coating becomes more durable but the life of the coating is limited by the thickness of the coating and by the amount of abrasion experienced by the components during service.

In two publications, Huang, W.S. et al., Polyaniline, A Novel Conductive Polymer -Morphology and Chemistry of its Oxidation and Reduction in Aqueous Electrolytes, Journal of the Chemical Society, Faraday Transactions 1, 92: 2385-2400 (1986), and Chiang J.C. et al., "Polyaniline": Proton Acid Pollution of the Emeraldine Form to the Regimen. Metallic, Synthetic Metals, 13: 193-205 (1986), describes how polyaniline can be transformed from the insulating regime to the conductor by adulterating the polymer with protonic acids. In this way, an already polymerized polyaniline film can be electrochemically or chemically adulterated to produce a conductive surface for subsequent processing. The reaction is reversible; therefore, by changing the external exposure parameters, it can be adulterated to make the conductive polyaniline and "desadulterate" it to make it insulator. The adulteration process involves an oxidative polymerization reaction where the protonic acid is bound to the polymer skeleton through ring sulfonation, the "de-adulteration" is a reduction reaction, as shown in Figure 1. The use of electropolymerized polyaniline as a surface conductive layer has been studied. Electropolymerization has been shown to occur on already formed polyaniline films as well as in an electrodeposition reaction of electrolytes containing aniline monomers in solution with protonic acids. Or V.P. Parkhutik et al., "Deposition of Polyaniline Films 5 on Porous Silicone Layers", Journal of the Electrochemical Society; Vol. 140, No. 6 (June, 1993), describes a process whereby thin layers of conductive polyaniline are electrodeposited from sulfuric acid solutions on 10 layers of anodized porous silicon, developed to »2. or A / dm2 with pore diameters of approximately 4 nm. This publication indicates that films developed on anodized silicon cathodes exhibit good adhesion, resistance to acids and typical infrared structures for the oxidation state of emeraldine conductive of polyaniline. A polymerization potential of +0.6 to +1.0 v is also described. SCE. However, the actual silicon-polyaniline linkage is not documented. Also, the study by Parkhutik et 20 al., As well as U.S. Patent No. 4,943,892 of Tsuchiya, for example, describes a process (anodization, followed by electropolymerization) of two steps. In those references, the electropolymerization is carried out by immersing the already anodized workpiece in an aniline monomer solution in the appropriate concentration of protonic acid and initiating the polymerization reaction on the work surface by applying the characteristic voltage for the state of desired oxidation of the polyaniline, or cyclizing the work piece, as prepared for the electropolymerization, through a series of characteristic voltages for the different phases of the polyaniline. In those studies, the resulting polymeric film, thus deposited, exhibited the characteristics of the conductive emeraldine phase of polyaniline. Additional US patents describing this or similar processes with various applications are: 4,769,115 (Masaharu); 5,422,194 (Masaharu); 5,556,518 (Xkinlen); and 5,567,209 (Kobayashi). Researchers would have been dissuaded by the use of an aluminum-polyaniline reaction to form an anodized coating because the anodization potentials of standard aluminum exceed the published polymerization potentials for polyaniline. This raises the concern that the polyaniline molecule will be degraded during anodization. The degradation is thought to occur by cleavage of the carbon-hydrogen or carbon-hydrogen bonds of the monomer within the electrolyte during anodization. More specifically, there is concern that polyaniline may degrade to hydroquinone at potentials greater than 0.8 volts and, therefore, may not have significant impact or interaction with the anodic film. In this way, the electropolymerization and use of the polymer film as a surface conductive layer have been studied. Other publications describe the use of the conductive layer as a precursor for subsequent metal electrodeposition. See, for example, Angelopoulos et al., Conducting Polyanilines: Applications in Computer Manufacturing, Procedures of the 49th Conference and Annual Technical Exhibition of the SPE, 765-769 (1991), incorporated by reference. However, none describes the formation of a composite metal-oxide oxide film from the anodization of the metal with the polymer deposited simultaneously from a monomer solution within the electrolyte. Therefore, it would be advantageous to provide an anodized coating that essentially eliminates the use of an adhesive bond for subsequent polymer coatings. It would also be desirable to provide a self-sealing, self-sealing, chemically bonded polymer-to-metal coating in a single step, which would result in substantial time and material savings and would at the same time provide an industrially viable process. Particularly it would be useful to also find in the use of a II Composite coating of polymer-autonomous metal oxide chemically bound to a metallic substrate achieved through a standard anodizing process, since the polymer phase would be completely and homogeneously integrated within the metal oxide, such coating would provide superior wear and corrosion resistance.

• BRIEF DESCRIPTION OF THE DRAWINGS The novel features of the invention are set forth in the appended claims. However, preferred embodiments of the invention, together with their additional intended objects and advantages, will be better understood with reference to the following description taken in conjunction with the accompanying drawings in which: Figure 1 shows the reactions of basic adulteration and desadulteration of polyaniline; Figure 2 is a representative Tafel plot for polyaniline; Figure 3 shows the names, chemical compositions, approximate structures and characteristic voltages for the different oxidation states (phases) of the polyaniline; Figure 4a shows the half cell reaction for polyaniline; Figure 4b shows the oxidation and reduction reaction for polyaniline; Figure 5a shows the structure of the adulterated polyaniline with substituted sulfonic acids in the ring; Figure 5 shows the structure of the sodium salt of the ring-substituted, non-protonated polyaniline; Figure 6 is a schematic view of the columnar structure of the anodized polyaniline film on the aluminum substrate; Figure 7 is a schematic view of a cross section through a single pore of an anode film; Figure 8 is a representative micrograph photo (amplification: 400X; attack reagent: Keller reactivated) to an anodized and conventionally sealed coating; Figure 9 is a microprobe image and fluorine dot map of a cross section prepared through an anodized film with hard coating "impregnated" with PTFE, with the lower right side plate showing a fluorine scan of the location and relative amount of PTFE and indicating that the polymer coating is limited to the surface of the oxide layer; Figure 10 is a schematic view of the proposed structure on an anodic film electrochemically sealed with polyaniline; Figure 11 shows the results of the FT-IR analysis of the finished codeposited films, which indicate that a polyaniline polymer phase was included within the aluminum oxide film; Figure 12 shows the results of the CV analysis, which indicate the presence of polyaniline, degraded by a high voltage exposure; Figure 13 shows the results of the FT-IR analysis, which confirm the reaction of the polyaniline with the (anodized) film of aluminum oxide during co-deposition; Figure 14 is a SEM image of the surface of a conventionally anodized film, illustrating the structure of the porous surface of the aluminum oxide (Boehmite) film; Figure 15 is an SEM image of the cross section of a film as anodized; Figure 16 is an SEM image of the surface of an anodized film with a codeposited finish, illustrating the dilation of the portion. Figure 17 is a SEM image of the cross section of a double film; Figure 18 shows the results of the EPMA analysis for the codeposited film; Figure 19 is an SEM image of the surface of the codeposited film, showing that the Boehmitic surface is no longer discernible; Figure 20 is a SEM image of a cross section of a codeposited film; Figure 21 shows the results of the EPMA analysis, which indicate that the codeposited film is completely impregnated with nitrogen and therefore showing the total integration that appears to be a polymer phase with an anodized aluminum oxide film; and Figure 22 shows data. EELS indicating that the deposition of the polymer proceeds as the aluminum oxide film grows.

BRIEF DESCRIPTION OF THE INVENTION In the present invention it preserves the advantages of known coatings and processes to form coatings that provide resistance to wear and corrosion, as well as a primer finish for polymer-metal bonding, and sealed finishes. It also provides new advantages and overcomes the disadvantages associated with such coatings. An anodic coating process for aluminum and aluminum alloy substrates has been devised and tested experimentally, which allows the formation of films composed of aluminum oxide-pyrimer. An important step in this process of modifying the sulfuric acid electrolyte to include aniline monomer. The polymeric additive can be made electroactive (ie, conductive) through the substitution of the ring on the aminobenzene structure in a protonic acid. The protonic acid in this process is the electrolyte of sulfuric acid. Since anodization and polymerization are more oxidative, experiments were performed to verify that they will occur simultaneously. This process was called "codeposition" here. Successful experiments resulted in uniform and continuous films which were formed consistently as described below. The scientific characterization determined that the polyaniline was deposited as the formed aluminum oxide film and grew from the surface of the substrate. It was determined that an aluminum salt of sulfonated polyaniline in the ring, not protonated, was the product of the reaction through the anodic film. Additional polyaniline was also identified as a polymer as if it were deposited on the surface of the films. These results determined the co-deposition process that produces fully integrated composite films, completely linked chemically and metallurgically, in one step. The design characterization determined that codeposited films exhibited comparable corrosion resistance and greater wear resistance than anodized films conventionally processed through two steps. In addition to the use of the composite anodic film as a transition layer to facilitate the joining of different materials, the film produced through the co-deposition process of the present invention can also serve as an "autonomous" finish which exhibits resistance to the comparable corrosion and superior wear resistance of the sealed metal oxide layers produced by conventional anodizing and electrocoating techniques. The resulting coatings can also function as a primer primer for the polymer-metal bond. In a preferred embodiment of the present invention, an anodization process for forming a composite film on a metal substrate is provided. The metallic substrate is anodized simultaneously with the deposition of a polymer or polymeric phase of an electrolyte. The electrolyte is incorporated as a conductive polymer into a solution of protonic acid. In another preferred embodiment of the present invention, an anodizing process is provided to form a co-deposited composite film of metal-polymer oxide on a metal substrate. A polymer or conductive polymer phase is incorporated into a protonic acid solution within an electrolyte. The metal substrate is anodized simultaneously with the co-deposition of the polymer or conductive polymer phase within the metal oxide during the formation of the metal oxide film on the surface of the substrate. A discrete polymer film can be electropolymerized onto the surface of the composite film to produce a fully sealed conductive polymeric film on the surface of the co-deposited composite film. In a preferred embodiment, the electropolymerized polymer is one of two conductive oxide states of polyaniline, such as emeraldine, and the monomer added to the electrolyte is aniline. In another preferred embodiment, the electrolyte is based on or includes a mixture of one or more of the following protonic acids: sulfuric acid; Methylsulfonic acid; chromic acid; oxalic acid; or phosphoric acid. In still other embodiments, the metal substrate is selected from one or more of the following metals: aluminum; silicon; zinc; magnesium; or titanium. The resultant codeposited composite film can be used for a variety of applications of wear resistance or corrosion resistance, it can be formed on a standard anodic film, or it can be formed with an electropolymerized film. In a preferred embodiment, the process of the present invention results in the formation of an aluminum salt of sulfonated polyaniline in the ring, not protonated, as a reaction product within the pores of the composite film. Preferably, the aluminum oxide has a columnar Boehmitic structure.

DETAILED DESCRIPTION OF THE PREFERRED MODALITIES The present invention relates to compositions and processes employing the co-deposition of a conductive polymer, such as polyaniline during an anodization or electropolymerization process to provide a direct polymer-to-metal chemical bond. The term "codeposited" as used herein means the growth of a metal oxide film, such as that obtained on aluminum through anodization, while simultaneously depositing a conductive polymer within the structure of the film. The composite film can function as a transition layer to facilitate the joining of different materials, as well as to serve as an "autonomous" finish which exhibits comparable corrosion resistance and superior wear resistance than the sealed metal oxide layers produced by the conventional anodization and electro-coating techniques. Thus, the present invention overcomes the limitations of polymer-to-metal bonding by creating a chemically bonded interfacial layer. This interfacial layer has two phases: a metal oxide phase, and a polymer phase. The biphasic interfacial layer provides a chemical bond between the metal substrate and subsequent polymer coatings. There is a true metallurgical bond between the substrate and the metal oxide, while there is a chemical bond within a composite film between the oxide and the polymer. The presence of chemically bound polyaniline within the film allows interdiffusion between the film and subsequent polymer coatings, creating a fully bonded composite structure. This structure also offers better design properties (resistance to corrosion and wear) as a standalone film. In a preferred embodiment, it has been determined that a film composed of aluminum oxide-polyaniline offers a reactive surface that allows chemical interaction with subsequent polymer bonds. Polymer-composite film bonding offers the advantage of chemical rather than mechanical bonding for subsequent polymer coatings. This chemical bond will exhibit superior bond strengths to the currently available adhesive bonds. When used with a standalone film, the electrochemical nature of the aniline monomer within the electrolyte produces a dense, completely sealed anodic film structure. The feasibility of the process is based on the electrical conductivity of polyaniline in solution after substitution with protonic acids. Polyaniline films can also be adulterated by exposing them to protonic acid solutions. Polyaniline can be oxidized to a metallic state through adulteration. The resulting acid-base chemistry within the polymer system can be changed externally by an electrochemical or chemical method. Clearly, because the mechanism of adulteration involves protonic acids (loss of a proton, specifically H +), the reaction depends on the pH. Johnson, BJ, Park, SM, Conductor XIX Polymer Electrochemistry, Oxidation of Nail Aniline and Polyaniline - Modified Platinum Electrodes Studied by Electrochemical Impedance Spectroscopy, Journal of the Electrochemical Society, 143, No. 4, 1269-1276 ( 1996), incorporated herein by reference, used impedance measurements to construct a linear Tafel representation for polymerization by oxidation of the aniline on a logarithmic scale (see FIGURE 2). These characteristics of the reaction are necessary for the electrodeposition reactions. Therefore, it was hypothesized that the coating formulations can be developed with an aniline monomer in solution, based on conventional anodization chemistry, which can produce unique films which incorporate polyaniline in the metal oxide film.

Conductive polyaniline Conductive polymers are highly conjugated systems which can be converted from atak insulating or semiconductor regime to the metallic regime to through chemical or electrochemical adulteration. Polyaniline (polyaminobenzene) refers to a class of conductive polymers with different oxidation states and, therefore, p-type conduction. This material undergoes a transition from insulator to metal after being adulterated with protonic acids in an acid / base type reaction. The conductivity of the polyaniline materials is a function of both the degree of oxidation and the degree of protonation. Conductive polymers exhibit a window of potential within which they are drivers. In this way, the polymer will be non-conductive (completely reduced) when the potential is too low, and will decompose when the potential is too high. Studies have shown that conductivity is not limited to a certain range of potential, but at a certain pH range. The lower the pH, the greater the adulteration and / or substitution of the ring. A linear representation was shown on a logarithmic scale between the applied potential and the response to the current during the polymerization of the aniline. These characteristics indicate that the material exhibits Tafel behavior, an electrochemical feature necessary for electrodeposition. For polyaniline, there are three main forms that correspond to the different oxidation states that occur within this driving window. The approximate chemical compositions with their corresponding names and structures are shown in FIGURE 3. Some or all of the groups -N = can be protonated by aqueous acids to produce a range of corresponding salts, some of which are highly conductive. The most highly conductive form of polyaniline is the salt of emeraldine. The balance of the acid-oxidation state of the different states of the polyaniline can be changed externally by an electrochemical or chemical method. The oxidation-reduction reaction for polyaniline and the half-cell potential corresponding to the oxidation-reduction reaction for polyaniline are shown in FIGURE 4. For this reaction, the half-cell potential is the average of the anodic and cathodic peak potentials obtained from cyclic voltammetric studies reported (see, for example, .S. Huang, B.D. Humphrey and A.G.

MacDiarmid, "Polyaniline, A Novel Conductive Polymer - Morphology and Chemistry of its Oxidation and Reduction in Aqueous Electrolytes", Journal of the Chemical Society, Faraday Transactions 1, vol. 82, pp. 2385-2400 (1986), incorporated herein by reference). Therefore, predictions of the electrocoating capacity of an electrolyte solution containing polyaniline are possible. The formulation of an electrolyte with aniline monomer soluble in acid is based on the fact that the oxidation state of the emeraldine base can be converted from an insulator to a conductor by external proton adulteration. J. Yue et al., "Effect of the Sulfonic Acid Group on the Polyaniline Skeleton", Journal of the American Chemical Society, Vol. 113 (1991), incorporated herein by reference, discusses a method of adulteration which involves the introduction of an acidic group on the polymer chain to convert the polymer into a self-entrapped conducting polymer. The study of Yue, perhaps familiar to polymer chemists but probably not to those informed only electrodeposition. The anodization techniques specifically direct the effect of the sulfonic acid groups on the polyaniline chain and note the compatibility and stability of the adulterated polyaniline with sulphonated sulfonic acid in the ring. Sodium and potassium non-protonated salts, sulfonated in the ring, were also synthesized by the processes according to the present invention (see FIGS. 5a and 5b). F Maeda et al., Electrochemical and Thermal Behavior of Polyaniline in Ion-Containing Solutions S042 ~, Journal of the Electrochemical Society, 142, No. 7, 2261-2265 (1995), incorporated herein by reference, evaluates electrochemical behavior and thermal of polyaniline in aqueous solutions that contain S042 ~ ions to clarify the process of adulteration that makes the polyaniline electrochemically functional. The review of these studies suggests to the inventor that oxidative reactions that normally require an electrolyte based on sulfuric acid can be modified to reflect the inclusion of the polymer in the reaction product, i.e., the coating. Since the aluminum anodization reaction can be carried out in sulfuric acid and put - that the reaction of Polymerization for polyaniline is an oxidative polymerization, it was hypothesized that polyaniline can react with the aluminum substrate or within the aluminum oxide coating during anodization to form a chemically bound complex. Because Since aluminum is an active metal, similar to sodium and potassium, the inventor also hypothesized that the complex would be an aluminum salt of sulfonated polyaniline in the ring, not protonated. Experiments were carried out to verify this conclusion, as explained below.

Aluminum Anodization Anodization is the designation of the electrochemistry of certain metals to form stable oxide films on their surfaces. Films of various hardnesses and thicknesses can be produced that serve various purposes by adjusting the parameters of the process. Although there are a number of metals that can be anodized (specifically, functional metals, which include titanium, tantalum, magnesium, beryllium and zinc), aluminum has been of greater commercial significance to date due to the unique nature of its anodic film. Most commonly, the aluminum anodization process is used to produce decorative finishes, to produce corrosion or abrasion resistance of the aluminum substrate, or to provide an adherent interface for subsequent coatings. Here, the documented parameters were considered to produce corrosion and wear resistant films, as well as films that provide an adherent interface for subsequent polymer coatings. The nature of the anodization process is based on the electrochemical principle that when a current is passed through an electrolyte in which an aluminum anode is used, the anion migrates to the anode. The anion is then discharged with a loss of one or more electrons. In an aqueous solution, the anion consists in part of oxygen, which is adsorbed by the aluminum surface. As the chemisorption proceeds, the surface is reconstituted, forming a contiguous film of aluminum oxide as A1203. The resulting oxide film is slightly soluble in the electrolyte. The slightly soluble characteristic of the film causes localized dissolution. In this way pores are formed in the coating which are sufficiently wide to allow continuous access of current via the electrolyte to the metal. The growth of the anodic film continues and is gradually retarded as the film becomes thicker and the electrical resistance increases. When the growth rate of the film has decreased until it is equal to the dissolution speed of the film in the electrolyte, the thickness of the film remains constant.

The resulting film is therefore of two-phase aluminum oxide. The dual structure consists of a thin, non-porous inner oxide layer adjacent to the substrate metal (also called the "barrier layer") and a porous, thick external oxide layer. The continuous anodization reaction takes place from the surface of the aluminum substrate, that is, from the interface of the aluminum barrier layer. The film grows effectively from within; therefore, surface adsorption / reconstitution reactions occur continuously through the process, consuming the aluminum substrate. Nevertheless, the external part of the film is in contact with the electrolyte during the entire anodization time, and this interface is developed in the second external phase. If the conditions of anodization favor the dissolution of the film, this phase is porous A1203. The external porous oxide has a columnar cellular structure, as shown in FIGURE 6. Since the aluminum is being consumed to form the anodic film, the thickness of the substrate will decrease accordingly. The oxide produced, however, is less dense and of greater volume than the aluminum consumed. Therefore, the dimensions of the component usually increase.

The microstructure, hardness and thickness of the layers depend on the parameters of the anodization process. These parameters include time, temperature, bath composition and formation voltage. The anodizing electrolytes can be solutions of chromic acid, sulfuric acid, oxalic acid, phosphoric acid, boric acid or mixtures thereof. Although the approach of the described experiments that was on the anodization of electrolytic formulations based on sulfuric acid, it will be appreciated by those skilled in the art that other electrolytic anodization solutions can be used (and are indeed used in real industrial applications). The sulfuric acid solutions, at 5-25% by volume, are the most widely used anodization electrolytes. Anodic films used for subsequent coating applications are usually produced from a 10-15% sulfuric acid electrolyte. The bath is usually operated at temperatures of 20-25 ° C, a current density of 1.5 amps / dm2, and a bath voltage of 10-25V. The films produced fluctuate in thickness of 16-30 microns. The thicker, harder and more porous coatings are produced by increasing the bath voltage and current density and decreasing the operating temperature; This is known as "hard coating anodization". The chemical reaction that takes place on the surface of the aluminum anode can be written as follows: 4A1 + 6 (H2S04) - > 2 (A1203) + 6 (S03) + 3H2 (g) + 6H + (g) + 6e " S. Wernick, et al., The Treatment and Surface Finish of Aluminum and its Alloys, Vol. 1, ASM International, Metals Park, Ohio (5th Electrodeposition .. 1987), incorporated herein by reference, reports the composition of the resulting film as: 72% of A1203; 15% H20; and 13% of S03. "The sulfate content of the normal sulfuric acid coating is between 13% and 17% but is higher at lower operating temperatures and increases with the current density. in the form of a film they can be considered as follows: the external porous film is composed of partially hydrated alumina (l2? 3H20), and sulfate ion (S03 ~), which is discharged at the base of the pores of the columnar structure of the outer film (see FIGURES 7 and 8) The inherent porous nature of the outer layer of the anodic film requires that the film be sealed to provide a protective coating.The sealing mechanism is not completely understood but is part that involves the conversion from amorphous oxide of the pores to alpha alumina monohydrate This conversion is accompanied by a change in volume.It is thought that the change in volume seals the oxide film "clogging", the pores, so that the anodic film becomes impermeable and increases its protective capacity for the substrate metal. Various types of sealants have been developed to increase corrosion resistance, allow pigmentation and / or make good lubrication of worn surfaces last. A variety of polymeric sealants based on polytetrafluoroethylene (PTFE) and their capabilities to enter the pores of the anodic film structure have been developed. However, the large size of the PTFE polymer molecules relative to the pores of the anodic film • (a minimum of 50nm for the colloidal PTFE particles against pore diameters of '4-20 nm for anodized films), and entropic effects of the particles in solution (ie, that the larger particles tend to attract each other), prohibit the current incorporation of polymeric PTFE sealants into the microstructure of the unsealed anodized film, as shown in FIGURE 9 .

DEVELOPMENT OF THE ELECTROCHEMICAL PROCESS FROM POLYMER TO METAL JOINT Deposition of Polyaniline Films on Anodized Aluminum It is the acid nature, porous, of the film anodized with sulfuric acid which makes the development of an interfacial polyaniline-metal bond particularly attractive. Because the same carrier (sulfuric acid) could be used with both anodization and electropolymerization processes, experiments were performed to verify if the reactions could occur simultaneously. The polyaniline was deposited on an anodized aluminum sheet using an anodized aluminum substrate as a working electrode in an aniline-electrolyte monomer solution of sulfuric acid. The polymerization reaction was initiated on its surface by applying a characteristic voltage for the polymerization of the emeraldine salt phase of the polyaniline. Bonding was facilitated not only by crystallization and volume change of the anodized film sealing process, but also by the bonding of the polymer to acid and sulfide ligands at the base of the pores of the outer layer of the anodized film . The resulting sealant is a sulphonated polyaniline film in the sulfonic acid ring chemically bound to the pores of the anodized structure. This reaction is more of electropolymerization than of real electrodeposition. However, their function as an anodic film sealer can prove to be significant. Anodization proceeds at voltages that exceed the polymerization potentials for polyaniline. Therefore, to incorporate an ideal polymeric phase, which retains the characteristics of the pure polymer, within or attached to the surface of the anodized film, the anodization reaction must be stopped and the parameters adjusted to those appropriate for the electropolymerization of the target polymer, similar to the method used by Parkhutik on silicon. Su had the hypothesis (and it was verified experimentally as shown below) that electropolymerization could be achieved with a sulfuric acid electrolyte formulation that incorporates aniline monomer by stopping the aluminum anodization reaction after reaching the desired film thickness and procedure. in a potentiostatic mode at characteristic voltages for the desired phase of polyaniline. This allows the direct deposition of a polymer film on the anodized aluminum film. Alternatively, direct deposition on the surface of the codeposited film may occur. The proposed electropolymerization reaction is different from co-deposition since it is a two-step process which produces thin coatings of "ideal" polyaniline on an anodized or pre-existing co-deposited film. However, its function as a sealing process for anodic films can be commercially significant. It was hypothesized that the binding of the polyaniline to the anodic film would be facilitated not only by the crystallization and change in volume of the sealing process of the anodized film, but also by the binding of the polymer to functional sulfuric acid ligands in the base of the pores of the outer layer of the anodized film, forming non-protonated polyaniline aluminum salts, sulfonates in the ring, within the structure. The inventor also had the theory that an additional oxidative polymerization can proceed during the sealing reaction to produce a protonated polymer layer whose phase would be identified through cyclic voltammetry.

FIGURE 10 illustrates the proposed structure for an anodic film sealed with polyaniline.

? Aluminum Anodization and Electrodeposition Simultaneous Polyaniline The similarities between the actual anodization process and the electrodeposition of polyaniline on various substrates suggest to the inventor the possibility of carrying out the reactions simultaneously, producing a • 10 film composed of metal-polymer oxide. As the reaction proceeds for the electrochemical sealing with polyaniline, it was hypothesized that the polyaniline will be deposited and reacted with the aluminum oxide film. However, this reaction occurs at measure that the aluminum oxide film and will continue to deposit and react as the oxide film grows. It is believed that some of the polyaniline in the electrolyte reacts during anodization to form sulfonated polyaniline in the acid ring Sulphonic, and some of the polyaniline reagents during anodization to form an aluminum salt of unprotonated polyaniline, sulfonated in the ring. The two separate hypothetical reactions are presented below: 25 3 [-C6H4) -N (H) -] + 2A1 + 3 (H2S04) - > 3 [-C6H4] -N (H) -S03] + A1203 + 6H + + 6e ~ (2) 3 [-C6H4] -N (H) -] + 5A1 + 3 (H2SO4) - • 3 [-C6H4] -N (H) -S03Al] + A1203 + 9H + + e "(3) Considering the values of half-cell reactions: 3 [-C6H4] -N (H) -] x - »[-C6H4) -N (H) +] X + qxe" E0 = 0.11 volts vs. SCE Al3 + + 3"e" - At E0 = -1,662 volts vs. SHE (a) [16] Converting the value of the half cell reaction from FIGURE 4 to SHE, E0 = 0.131 volts. The driving force for the electropolymerization / oxidation reaction of aluminum can be considered the difference between the half-cell reactions, or the equation of FIGURE 4 as the cathode.

V = E ° cathode - E ° anode (5) V = 0.131 volts - (-1,662 volts; V = 1,793 volts The positive value for the driving force of the reaction proposed as equation (2), above, indicates that the reaction will proceed as written and that the polyaniline will react with the (oxide of) aluminum and sulfuric acid to form a metal oxide composition -sulfonated polyaniline. A reaction between the base polymer and the aniline polymer is ensured by the Tafel behavior. Further investigation and experimentation is required to determine the actual kinetic parameters of the electrode for polyaniline in sulfuric acid with an aluminum anode. The positive value for the driving force indicates the possibility of a speed limiting step. The polymerization potential is hypothetical in that step. The maximum potential for polyaniline is its pernigraniline oxide state, which is 0.8 volt, and which can be controlled during a secondary sealing operation. Even if this completely oxidized state of the polymer is from the electrodeposited phase, it is well documented that a phase shift through cyclic voltammetry can be obtained back to the conductive emeraldine oxidation state. The reversible polymerization characteristic is really favorable, since it can be applied to the composite film which may or may not require conductivity of the film.

Theoretical results, although they suggest that an aluminum-polyaniline reaction could occur, raising concerns that the polyaniline molecule will be degraded during anodization. It is thought that the degradation occurs by means of the oxidation of the carbon-hydrogen bonds cleaved and the formation of double bonds with an oxygen ion characteristic of the carbonyl groups present in hydroquinone. Therefore, if degradation occurs within the electrolyte, the inclusion of the monomer in the electrolyte may not have significant impact or interaction as an ideal polymer with the anodic film. Experiments were conducted to determine what types of films could be formed through the proposed reactions to determine the impact that the inclusion of a possibly degraded polymer on the microstructure of the anodic film could have. The polymer-composite film bond would also offer better design and adhesion properties, and resistance to corrosion and wear as a standalone film. This is due to the electroactive nature of the aniline monomer within the electrolyte, which allows the complete integration of the polymer into the metal oxide film during the anodization reaction, producing a dense, completely sealed, anodic film structure. It is also believed that polyaniline complexes with sulfonic acid and aluminum ligands within the porous structure of aluminum oxide during anodization, which forms chemical bonds within the composite film.

Experimental Procedure for Developing Real Composite Films / Scientific Characterization Small-scale Laboratory Experimentation Experimentation focused on the development of composite films by actually anodizing aluminum anodes in sulfuric acid / aniline electrolyte. The sealing studies were conducted to the polymerization potentials suitable for the different oxidation states of the polyaniline on the anodized aluminum substrate surface. The analysis was carried out to characterize the resulting films and to determine their quality. In the small-scale laboratory experiments, standard 2M H2SO4 solutions were prepared to be used as the anodizing electrolyte in a 600 ml beaker. The standard anodization experiments were carried out galvanostatically at DC current values of 20 milliamps and 300 milliamperes. The choice of current densities was based on the original silicon anodization study carried out by Parkhutik and the "Rule of 720". This simple formula is: current (amperes) * exposure time (minute) = coating thickness (surface area to be coated) (feet) * (0.092m'i) * 720 (Thickness of coating in thousands of inches (2.54 cm).) The Rule of 720 can be used to determine the exposure of the anodization reaction, given the desired film thickness and the current density appropriate for an anodization reaction. This formula is commonly used throughout the anodization industry and seems to be based on the Ilkovic equation that uses the half cell potential for aluminum.The working and reference electrodes for the analysis were 1 cm x 3 cm coupons cut from aluminum foil 5657. The reference electrode was a calomel electrode with a crushed glass bead joint obtained from Fisher Scientific Electrochemical measurements were made with an EG &G Princeton Applied Research Model 273 power supply with both working capacities potentiostatic and electroplating All the anodization and codeposition experiments were carried out in the electroplating mode The electropolymerization was carried out in the potentiostatic mode. The initial processing involved the electroplating anodization of a 5657 aluminum alloy sheet. This aluminum sheet exhibited a somewhat reflective finish with 2 molar H2SO4 at 20 milliamps for 1 hour (current density = 0.66 amps / dm2). The visual appearance of the anodized films was that of a satin finish. The experiments proceeded with the addition of 0.5M aniline monomer to the 2M sulfuric acid solution, after the first anodization with the sulfuric acid electrolyte alone for one (1) hour at a current density of 0.66 amps / dm2. The resulting H2S04 aniline solution was then used to simultaneously anodize the aluminum and, theoretically, deposit polyaniline in the Bohemite structure, consequently referred to as co-deposition. The final examination of the finished films determined that they exhibited a similar appearance to a satin finish with reflectivity comparable to those of the anodized films, without the addition of aniline monomer to the electrolyte. The final set of small-scale experiments proceeded with an electrolyte of 2M sulfuric acid / 0.5 M aniline. Co-deposition was carried out for 1 hour at 20 milliamperes (current density 0.66 amperes / dm2). The final evaluation of the finished films determined a matte satin finish with reflectivity similar to that of the anodized films, without the addition of aniline monomer to the electrolyte. Polymerization of the polyaniline was potentiometrically attempted on conventionally prepared anodized films by adding 0.05M aniline monomer to the 2M sulfuric acid after the anodization reaction had stopped. After the added aniline was solubilized in the electrolyte, a polymerization potential of 0.6 volts, corresponding to the published polymerization potential of the emeraldine salt of the polyaniline, was applied to the anodized electrode. The reaction was allowed to proceed for five (5) minutes. The final evaluation of the resulting film determined that it exhibited a milky white appearance. The experiments were repeated at the polymerization potentials for leucoemeraldine and pernigraniline, 0.4 volts and 0.8 volts respectively. The films formed at both voltages did not exhibit the same appearance as the anodized electrode and sealed with the aniline monomer in 0.6 volt solution. They exhibited the same appearance as those anodized without the monomer in solution.G.

? Larger Experiments 5 The experimentation was continued by escalating the equipment used for the anodization process. A 20-liter polypropylene tank was built. 6061 aluminum alloy cathodes and copper conductive bars were used. Small 6061 aluminum alloy supports were also constructed. A calibrated rectifier was used to maintain the current / power density, manufactured by Rapid Electric Company, Inc., Brookfield, CT, reference no. 97133A, which was able to provide a range of DC potential from 1 to 15 volts and a CD current range from 0 to 15 amps. Electrolyte solutions of identical composition to those of the small scale experiments were used, using sulfuric acid and aniline monomer from sources identical. Four inch by four inch (10.16 cm x 10.16 cm) square anodes of 5657 Aluminum alloy as well as 6061 Aluminum alloy were constructed. Calculations of the thickness and exposure time were made following the "Rule of 720".

The parameters were varied to reduce / increase the exposure time to produce different thicknesses of composite film. With the increase in the size of the electrolytic bath, it was not practical to make a new solution 5 with each anodization reaction. Therefore, experiments were carried out to determine the consumption rate of the aniline monomer with each of the anodization reactions lasting one hour. High Pressure Liquid Chromatography (CLAP) 10 was performed on electrolytic solution samples after one (1), two 82) and three (3) sequential anodization experiments. The samples were analyzed by CLAP under the following conditions: Column: C-18, 250 x 4.6mm, particles of 5 15 microns Mobile phase: KH2P04 0.05M, pH3.2: Acetonitrile (60:40) Flow rate: l. Oml / min Detector: Photodiode Array @ 254 nm 20 Due to the acidity of the samples, small injection volumes are used to allow the buffer in the mobile phase to maintain the correct pH. The injection volume for all samples was 1 microliter. Using the standard that was prepared in the laboratory and the 0.05M aniline sample, the aniline concentrations were calculated for the three samples that had been used in the anodization experiments. The concentrations of aniline in the samples are summarized in Table I, below. The concentrations followed a downward trend as an additional anodization test was carried out. An average consumption rate of 13% of the total monomer in solution was determined with each anodization test of one (1) hour.

TABLE 1 SPEED OF CONSUMPTION OF THE ANILINE MONOMER OF THE ANODIZATION ELECTROLYTE Peak sample at 2.33 min peak at 3.93 min Control 0.05 M 1 Test 0.044 M 0.048 M 2 Tests 0.038 M 0.043 M 2 Tests 0.034 M 0.041 M The results of the CLAP study determined that a monomer addition corresponding to 13% of the initial monomer addition equal to 0.05 M in volume is required to maintain the monomer concentration so that the coating is formed consistently. Co-deposition at higher monomer concentrations produced more polymer in the finished films. Additional studies are required to determine the advantages of having more codeposited polymer in the anodic film. In addition to the required addition of the aniline monomer to maintain the 0.05 M concentration, the maintenance of the solution was carried out as it would be for a standard anodization bath. Total free acid levels were checked routinely as well as the aluminum content within the bath. Additions of deionized water were made to maintain the acid concentration of 2 M. To achieve a minimum concentration of aluminum of 3 grams per liter, one (1) liter of pre-existing anodizing electrolyte was introduced from an anodization line maintained from 8 to 12 grams per liter to the anodizing electrolyte each time a fresh solution was made. A black-looking particulate film was observed on the surface of the cathodes with the subsequent sequential anodization experiments. The infrared analysis by Fourier Transformation (FT-IR) of the film was carried out to establish its nature. The FT-IR allows the identification of organic compounds through the obtaining of the characteristic infrared absorbances, presenting them as spectra and comparing them with a library of standards. Film samples were collected and prepared for analysis by rinsing with deionized water to remove any aluminum complexes that have formed on the surface of the cathodes during anodization. The FT-IR of the particles comprising the films determined that two phases of polyaniline were present. A particulate phase exhibited a color different green and spectrum for polyaniline. It was concluded that, based on color, the phase was emeraldine, the highly conductive phase of polyaniline. The particles exhibited a degraded spectrum; however, benzene ring structures were presented within of the spectrum obtained for the samples collected, which suggested that they were comprised of polyaniline phase (aniline). It was noted that the presence of the formation of the polymer film on the surfaces of the cathode The efficiency of the anodization reaction decreased because the volume of the formed film was insulating and increased the resistance of the reaction in the electrolyte. Therefore, the cathodes were cleaned of film between the anodization tests by rubbing them down and rinsing them in water.

A similar voltage-current response was noted for large-scale experiments as in small-scale laboratory experiments. The coatings that were developed exhibited the same visual appearance. These results determine the stability of the reaction with an increase in size and indicate that the process has industrial application.

Scientific Characterization of Composite Films The nature and quality of the films were established through scientific and design or engineering characterization studies. The scientific characterization proceeded by means of the following methods: visual and macroscopic examination, metallographic analysis (microstructural), Exploration Electron Microscopy with Dispersive Energy X-ray Analysis (SEM / EDS), Transmission Electron Microscopy with Energy Loss Spectroscopy Electronics (TEM / EELS), Fourier Transform Infrared Spectroscopy (FT-IR), Cyclic Voltammetry (CV) and Electronic Microsonde Analysis (EPMA) with Dispersive Wavelength (DS) Analysis. These methods were used to characterize the chemical and metallurgical nature of the films, as described here.

As discussed above, the finished composite films exhibited a satin finish with reflectivity comparable to that of the anodized films, without the addition of monomer to the electrolyte. The discernment between the anodized films with the addition of monomer and those without was made visually observing the drying patterns of the film after the removal of the anodes of the electrolyte and of rinsing them in running, clean water. The coatings that had been formed in the electrolyte containing the monomer also exhibited a white halo in the wetting meniscus as the drying proceeded. The white halo also disappeared when the drying was completed. Conventionally anodized films do not exhibit the white halo. The presence of the halo was attributed to the inclusion of the polymer phase within the metal oxide film. The FT-IR analysis of the finished codeposited films determined that a polyaniline polymer phase was actually included within the aluminum oxide film, as shown in FIGURE '11. Further experimentation proceeded by means of cyclic voltammetry (CV) to identify the exact deposited phase. The anodization was carried out with platinum electrodes following the same procedures documented in the previous chapter. Because platinum is a noble metal and is not subject to the oxidation reactions presented by aluminum and other functional metals, the CV could proceed on depositing the surface of the platinum anode without interference from the metal oxide on the polymer. This allowed the identification of the deposited polymer phase using the reaction parameters of the codeposition. A green, black, coherent, tenacious film was obtained on the anode surface through the anodization parameters used for the co-deposition reaction. This was surprising, since the polymer phase obtained during the co-deposition with the aluminum anode appears to be translucent on both finished diodes and at the same time that the anodes were wetted. This indicated that a reaction between aluminum and polyaniline actually occurred. After the anodization experiment on the platinum electrode, the EG &amp energy supply; G Princeton Applied Research Model 273 described above was placed at a scanning speed of 50 mV per second over the characteristic voltages for the different phases (oxide states) for polyaniline (0 volts to 1 volt). As the exploration proceeded from 0.4 volts to 0.8 volts, changes in the appearance of the film were noted, indicating that due to the reversibility of the well-documented phase of polyaniline, the polyaniline oxide phase deposited during the anodization to the Selected parameters is emeraldina. The results determined a typical voltammetric behavior for polyaniline with open circuit potentials within the emeraldine regime (value = +0.5 volts). In effect, an additional peak was noted on the voltammogram, from approximately 0.77 volts to 1.0 volts, which is characteristic for polyaniline degraded by exposure to a high voltage. As shown in FIGURE 12. The FT-IR determined that the green-black phase was actually polyaniline. After comparison of the spectrum obtained from the codeposited film (FIGURE 11), a good fit was determined, confirming that the polyaniline reacted with the aluminum oxide film (anodized) when deposited, as shown in FIGURE 13. The test of the surface of the anodized films formed by the experimental parameters described within the SEM described the typical surface structure of an aluminum oxide film (Bohemite) porous. The preparation and metallographic examination with a calibrated metallurgical microscope with 2000X amplification capabilities determined that the developed films were uniform and continuous, and measured approximately 0.2 thousandths of an inch (50.8 μm) of thickness, which corresponded to the calculation of thickness? by the "Rule of 720". The microstructure was typical for a conventional anodized film: a thin barrier layer with a columnar Bohemite aluminum oxide structure. This was revealed through the metallographic examination and through SEM / EDS. See FIGURES 14 and 15. 10 Experiments then proceeded with the addition of 0.05 M aniline monomer to 2 M sulfuric acid solution, after the first anodization with sulfuric acid electrolyte alone for one (1) hour (current density = 0.66 amps / dm2). The evaluation The usual one determined that the films exhibited a similar satin finish with reflectivity comparable to that of the anodized films, without the addition of aniline monomer to the electrolyte. The SEM analysis of the films developed in this way exhibited different formations of surface phase. It was evident that the porous structure of Boehmite had dilated with the introduction of the aniline monomer into the electrolyte. Dilation of the pore (see FIGURE 16) is strongly supported by the theoretical results that the aniline monomer would react with the aluminum during the anodization reaction.

The preparation and metallographic analysis of these films determined that they were uniform and continuous and had a thickness that averaged slightly more than 0.2 thousandths of an inch (millimeters). They also exhibited a different duplex phase formation. The transition in the microstructure of the film from a conventional columnar anodic film (AI2O3) to a seemingly denser microstructure with an amorphous white polymer phase was noted through metallographic examination and SEM examination. As shown in FIGURE 17, those results indicated that the reaction changed immediately with the addition of aniline monomer to the electrolyte. More importantly, the results indicated that the polyaniline was deposited in the pre-existing anodized layer as the additional aluminum oxidation (anodization) reaction proceeded. The electronic probe microanalysis (EPMA) noted a different elemental segregation that corresponded to the phase transition. Only the typical elements under a standard anodized film directly adjacent to the aluminum substrate (aluminum, sulfur and oxygen) were observed. The upper portion of the film exhibited pore dilation, denser microstructure with the inclusion of the amorphous phase; it also exhibited the inclusion of nitrogen with the standard elements of the nodule film, indicating that the polymeric appearance phase introduced the columnar structure of A1203 (see FIGURE 18). The SEM examination of the surface of codeposited films completely revealed that the addition of aniline which apparently dilated the columns of the Bohemite structure of the double film grew on top of the oxide structure, forming a contiguous surface coating. The preparation and metallographic analysis determined the anodization process produced uniform and continuous films that measured 0.4 thousandths of an inch (millimeters) in thickness. SEM determined that the films had retained the Bohemite columnar structure but exhibited a dense, fine microstructure similar to that of the portion of the double film. The upper surface of the film exhibited on apparent flow of the polymer phase forming a polymeric surface film. The EMA determined that the films were completely impregnated with nitrogen, indicating the total integration of what appears to be a polymer phase with the anodized aluminum oxide film, as shown in FIGS. 18 and 21.

The comparative examination of metallographic cross sections of fully codeposited films and doubles to films conventionally anodized to the same electrochemical parameters revealed a different increase in thickness with the addition of the aniline monomer to the sulfuric acid electrolyte. The greater thickness of the deposited coatings of the electrolytes with the addition of aniline, together with the information derived from the CV that the anodization parameters do not degrade the polyaniline (in fact, when deposited on platinum, it is obtained in the oxidation state of emeraldine), as well as the knowledge that polyaniline reacts with aluminum to form a white reaction product which dilates the pores of the bohemite structure, strongly suggests that the reaction product simply occupies more space within the film of oxide. In other words, although the oxide film itself may be less dense (the larger pores), the space is occupied by the aluminum salt of polyaniline and possibly by the electropolymerized polyaniline. Another possible contributing factor to the increase in thickness is that due to the high concentration of sulfuric acid within the electrolyte, the level of substitution of sulfonic acid on the benzene ring of the aniline monomer in solution is also very high. Although this can break the conjugate structure of polyaniline, reducing the lengths of the polymer chain in solution will not change the conductivity of the solution. Even with the change in structural conformation, the Sulfonated molecules in the individual Ring will retain the electronic movement isolated, and will not move in the direction of the imposed potential. Therefore, it may be that the formation of the oxide film with finer microstructure proceeds with the deposition of the degraded polymer apparently not only because the smaller polymer chains offer more individual binding sites for the sulfonated polyaniline linkage in the ring -Al, also because of the stability of the polymer in the electrolyte and the fact that the conductivity and retroactivity of the solution is maintained through the coating process. This last theory is supported by the CV results, which determined characteristic peak for degraded polyaniline due to high voltage exposure. The polyaniline-aluminum compound formed within the composite layer during co-deposition exhibited a white color when wet and appeared translucent when dried. White translucent phase was not developed in reverse of the co-deposition of the platinum electrodes. However, following the experimental procedure described above, in a 2M sulfuric acid with 0.05 M aniline electrolyte saturated with aluminum sulfate, a film was produced which exhibited a spectrum of FT-IR very similar to that of the codeposited films. The spectrum exhibited a downward shift with absorbance bands encompassing the area of the characteristic spectrum for Aluminum Sulphate. These results indicate, together with the supporting data, that the compound formed is a non-protonated aluminum polyaniline polymer salt, sulfonated in the ring. The degradation of the polyaniline in solution was also revealed during the CLAP analysis carried out to determine the speed of monomer consumption during co-deposition. It was observed that a different broadening or ridge formation had formed over the 2.33 minute peak, suggesting that one occurred. monomeric reaction within the electrolyte as the anodization proceeded. It is hypothesized that the reaction is that of a spontaneous oxidative polymerization. In other words, the polymer chains are formed in solution. Based on the previous theory, they should be agglomerated or short networks of small polyaniline chains, and possibly charged. Gel Permeation Chromatography (GPC) studies have shown that this phenomenon occurs in polyaniline solutions. The term "degradation" is therefore relative, since the polymer characteristics derived from the decoding process appear to be favorable and have substantial design or engineering applications. Finally, the metallographic analysis and SEM of the films formed by means of electropolymerization to the characteristic potentials for the emeraldine phrase of the polyaniline, after the electrodes were oxidized following the standard anodization procedures, it was determined that the oxide film it had degraded significantly during the electropolymerization reaction. Although the columnar Bohemian character of the films was retained, the columnar separation increased in a damaging manner, evidently through chemical attack. However, it was noted that the polymer film coated coated the columns as well as the surface, where it remained consistent. Although these experimental results did not produce quality films, they show that with further experimentation with the process parameters (i.e., reduced exposure time and / or reduced acid concentration of the electrolyte for electropolymerization), an ideal, successful polymeric seal can be developed. . The development of successful electropolymerization on codeposited films will prove important in the formation of surface conductive metal oxide-polymer composite films.

Engineering Caractrization After composite films were formed on aluminum anodes, as described above, they were subjected to various forms of testing to determine both their quality and the possibility of their practical application. The tests were performed to determine adhesion and flexibility, wear resistance and corrosion resistance. In addition, measures were taken to determine the surface insulation resistance and surface reflectivity tests were carried out. The surface reflectivity test was carried out on coated 5657 anodes through the co-deposition process at various thicknesses, specifically to evaluate the viability of the coating in the aluminum roll anodization industry (where the finished product is used as reflectors in application of ceiling lamps) . The results of these tests, discussed below, were used to indicate the feasibility of several applications of the composite film. The surface conductivity (leaf resistance) of the anodized codeposited films was determined with a four-point probe and a Simpson micro-ohmmeter with a sensitivity range of 40 milliohms at 20 ohms. It was determined that all films formed by the co-deposition process were non-conductive. This supports the theory that sulfonated polymer networks, whose conjugation is interrupted by a change in conformation due to the level of substitution within the electrolyte, are deposited as aluminum oxide film forms on the substrate. They also indicate that the formation of a non-protonated Ring Sulfonated Polyaniline aluminum salt is the reaction product formed between aluminum oxide and polyaniline. The adhesion of the coating was evaluated by ASTM B571"Test Methods to Determine the Adhesion of Metallic Coatings". (See, specifically, paragraphs 8 and 13, which refer to the tests of "rectification / sawing" and "rectification by stroke", respectively). None of the samples exhibited peeling, delamination or delamination, demonstrating the excellent adhesion of the composite films deposited. The corrosion resistance of the coatings was evaluated by ASTM B117"Practice to Operate Saline Spray (Haze) Apparatus". The samples were exposed for 24, 48 and 96 hours to a saline spray. The samples were compared with standard anodic films, which had been sealed with nickel acetate. The samples exhibited comparable corrosion resistance, in their condition as deposited, to those of anodized and conventionally sealed samples which had been processed through two steps. Possibly the most significant characteristic established for the films was wear resistance. A modified Taber abrasion test was developed based on the Specification Military MIL-A1-8625F; "Anodic Coatings for Aluminum and Aluminum Alloys "for the lighting industry to determine the wear resistance of conventionally anodized, unsealed, thin films For the modified test, the tests were prepared to test the wear as they are for the typical Taber test and the resistance to infinite contact of the films was established with ohmmeter.The tests proceeded with abrasive wheels CS-17 and a load of 1000 grains, and were interrupted at intervals of 400 cycles to verify the electrical continuity.The test was developed when measured a measurable drop in strength, meaning that the anodic coating had worn out completely, exposing the electrically conductive aluminum base metal.The modified Taber abrasion test above on conventionally unsealed, anodized films, at a thickness of 0.00011 inches ( 0.00028 μm), exhibited wear resistance at 1600 continuous cycles. The modified Taber abrasion test on a codeposited anodized panel (with 0.05M aniline monomer in the 2M sulfuric acid electrolyte) at a thickness of 0.00015 inches (0.00381 μm) exhibited wear resistance at 4000 continuous cycles. An anodized panel codeposited to a thickness of .00051 inches (0.01295 μm) was tested following the modified Taber abrasion test procedure. A test exceeded the 4000 cycles demonstrated by the thinnest sample and also allowed to proceed up to 10, 000 cycles (the standard number of cycles for anodized samples with hard coating) without total wear of the coating.

Metallographic examination determined that wear of approximately 0.0002 inches had occurred (0.005 μm) of the coating through the test. The comparative SEM examination in the wear area with an unproven area on the same panel determined the apparent uniform wear of the surface without evidence of peeling, peeling, delamination or fracture. This was one more proof of the excellent adhesion of the film. The apparently smooth surface suggests that the polymer phase imparts lubricity to the surface, allowing wear resistance. The finer microstructure presented by the co-deposited films together with the excellent adhesion contributes to the wear resistance due to the seemingly better characteristics of internal toughness of the finished films. Panels of 5657 aluminum alloy codeposited (0.05M aniline in 2M sulfuric acid) at thicknesses of 0.00015, 0.0003, and 0.0005 inches (0.00381, 0. 00762, and 0.0127 μm) were subjected to reflectivity test. Although an initial decrease in the reflectivity of the uncoated panels to the coated ones was noted, the readings were stabilized with increasing thickness. It was also determined that the image distinction was consistently 99%. This discovery was surprising since the standard anodic films exhibit a continuous decrease in reflectivity as the thickness increases. The stability in the reflectivity data for the codeposited films was attributed to the fine-grained microstructure of the codeposited films. The dye stain resistance test by ASTM B136 was performed on co-deposited samples at thicknesses of 0.00015, 0.0003, and 0.0005 inches (0.00381, 0.00762, and 0.0127 μm). After a 5 minute exposure to a drop of nitric acid, by the specification, the films quickly accepted the dye. This is not considered a favorable response for sealed anodic films. However, it is hypothesized that the polyaniline phase co-deposited within the coating may be soluble in nitric acid, and that the test may be inappropriate to assess the serviceability and application of the finished codeposited films. An interesting feature established by this test is the way in which the films readily accepted the dye after acid exposure. The corresponding areas on the same panels that were not exposed to the acid drop were tested to determine the staining ability by directly placing a drop of dye on the surface of the films. After allowing the dye to remain on the surface for 5 minutes, it was gently cleaned. The films readily accepted the dye without the acid treatment. This indicated that the phase of the polyaniline within the bohemite structure absorbs the dye, which suggests that the coating can be used for decorative applications. The results indicate favorable engineering or design characteristics, especially in adhesion and wear resistance for the film co-deposited. Additional research and development is necessary to determine the characteristics of the polymerized seal.

Discussion of Characterization Results Previous analyzes determined that the co-deposition process produces uniform and continuous two-phase films. The images -of the document -SEM and TEM oxidation reaction of aluminum iterfacial (anodization) proceed when the (poly) aniline reacts with and deposits out to become part of the anodic film. The CV of the polyaniline and platinum electrodes determined that the polymer is not significantly degraded by the parameters of the co-deposition process. All the polyaniline phases were produced by cycling "codeposited" films through their characteristic voltage ranges. further, the FT-IR conclusively determined that a polyaniline phase, with absorbance bands characteristic of the emeraldine phase (oxidation state) were formed consistently on both platinum electrodes and within the codeposited films. The EELS data (FIGURE 22) also support the results of the microscopic images that polymer deposition proceeds as the aluminum oxide film grows. A significant decrease in oxygen was also determined in the double-phase region of the composite film. This strongly suggests that the reductive dissolution of the oxygen film proceeds during the anodization, offering binding sites to adulterate and oxidize (polymerize) the aniline monomer in the electrolyte. It is well documented that the success of the aluminum anodization process depends on the solubility of the oxide film that forms inside the electrolyte, so that the electrolyte can continuously react with the substrate through the pores that are formed, through of the solution, in the resulting oxide film. It is also documented that the aluminum sulphite ion is discharged at the base of the pores that form in the film. With the addition of sulfonated aniline in the electrolyte ring, we have the theory and it has been analytically proven that the reaction between the sulfonated aniline in the ring and the aluminum sulfite ion proceeds following a mechanism in which the organic monomer is it oxidizes (polymerizes) while the metal oxide is being dissolved. See Lagdlund, M. et. Al., Electronic Structure and Chemistry of Polymers Conjugated to Interfaces Studied by Photoelectronic Spectroscopy, Preprint of the Handbook of Conducting Polymers (2nd ed.1996), Stone, A.T. et. al., Reductive Dissolution of Metal Oxides in the Chemistry of Aquatic Surfaces et al., Pp 221-254, John Wiley & Sons, N.Y. 1987); Huang, C.L. et. al., Coating of Inorganic Particles et. al., Journal of Colloid and Interface Science, 170, pp 275-283 (1995), the descriptions of each of which are incorporated here for reference. It was proposed that the electroactive sulfite ions attached to the backbone of the polyaniline chain react with the dissolution products of the oxide film (and / or the aluminum sulfite ions) discharged at the base of the pores in the Bohemite structure react with the aniline monomer) to form an aluminum salt of unprotonated polyaniline which therefore chemically binds to the pores of the Bohemite structure. Due to the functionality of three more of the aluminum, this resulting salt is a large molecule, which by virtue of its binding to the oxide structure, dilates the pores of the anodic film, resulting in correspondingly thicker films due to its inclusion . The resulting composite films are therefore metallurgically bonded to the aluminum substrate (aluminum to aluminum oxide) and chemically internally bound (aluminum oxide-to-aluminum salt of non-protonated polyaniline). As the films become thicker, and the reaction product of the polymer dominates the structure of the composition, there will be correspondingly more polymer and less protonated salt on the surface of the film. The films produced by anodization and simultaneous aluminum deposition of the sulfonated polyaniline in the ring (an electroactive polymer) exhibit uniform and continuous structures which are of thicknesses which significantly exceed the calculated thickness of conventionally anodized film processes for flows and similar current densities. This is due to the deposition of the electroactive polymer within the bohemite structure as aluminum anodization proceeds. This shows that polyaniline reacts with aluminum oxide, 5 forming a fully integrated two-phase film with a fine microstructure. The thickness of the composite film varies with the amount of aniline monomer available in the electrolyte; the films were correspondingly more delegated with less monomer available in solution. In practice, Therefore, consideration can be given to increasing the speed of growth of the film with the addition of the aniline to the electrolyte. The meaning from the point of view of the engineering or the design of the microstructure of the film is the formation of an adherent film, resistant to corrosion and wear in one step. The resistance to adhesion and corrosion is comparable to that of anodized and sealed films conventionally processed through two steps. The adhesion is the same because the substrate-film bond does not change essentially by the co-deposition process. Corrosion resistance is achieved in one step because the non-protonated aluminum salt of the polyaniline "covers and seals" the pores of the bohemite structure. The wear resistance of codeposited films is superior to that of conventionally anodized films. This is due to the synergistic effect of the composite structure of multiple phases. 5 The polymer-rich surface is softer than the underlying composition and self-lubricating. The hardest underlying composition is tenacious and durable.

Summary and Discussion 10 An anodic coating process has been developed in theory and has been experimentally tested, which allows the formation of composite aluminum oxide-polymer films on the aluminum substrate. The key to the process is the modification of the electrolyte of anodization to include the aniline monomer. The structure of the amino-benzene (polyaniline) can become electroactive, that is, conductive, through the substitution of the ring in a protonic acid. The protonic acid in this process is sulfuric acid. 20 The polymerization process for polyaniline is oxidative. Electrochemical studies have shown that the polymer exhibits linear relationships between voltage and current (Tafel behavior), a necessary feature for the electro-coating. These characteristics indicate that the electrodeposition / polymerization reaction for polyaniline was anodic in nature. Aluminum metal is commonly anodized in sulfuric acid electrolytes to form stable oxide films on the surface for a variety of industrial applications. It has been determined that the two reactions of anodization and deposition of aluminum on the polyaniline of the electrolyte would occur simultaneously for the following reasons. • Solubility of the (poly) aniline within the sulfuric acid • Replacement reaction of the ring of the sulfonates of the polyaniline molecule in an electroactive state • The electropolymerization of the polyaniline occurs anodically • The same electrolyte can be used both with the anodization of the aluminum as with the electrodeposition of the sulfonated polyaniline in the ring. Consistent, uniform and continuous films were formed through the co-deposition process. Through manipulation of the process parameters it was shown that the electroactive polymer actually deposited on the aluminum oxide structure as it formed on the surface of the aluminum substrate. The resulting composite films exhibited a double-phase structure; aluminum oxide with a non-crystalline translucent polymeric phase. The analysis determined that the polymer phase was a reaction product of aluminum-polyaniline, most likely an aluminum salt of polyaniline, sulfonated in the ring, not protonated. Those results determined the Modification of the anodizing electrolyte to include aniline monomer, and the co-deposition process, forming a completely chemically bonded structure: the aluminum oxide constituent is metallurgically bound to the substrate and a polyaniline salt of Aluminum, sulfonated in the ring, not protonated, is chemically bound to the structure of the aluminum oxide. The engineering characterization of the codeposited films determined that the coatings are adherent and exhibit resistance to corrosion comparable and wear resistance superior to those of conventionally anodized, sealed layers. In addition, initial experimentation with the electropolymerization of polyaniline on anodized or co-deposited films to produce an ideal bonded polymer bond chemically to metal shows merits.

Process Considerations The method for the development of the process was with the intention of providing an electrolyte formulation and a procedure that was practical and easy to implement in the industry. The solubility of the aniline in sulfuric acid at the experimental concentrations produced a formulation that was initially stable and easy to use. With time and with the use, it was found that the polymer polymerizes spontaneously, although it remains in solution reducing its efficiency. It was determined that the rate of electroactive polymer consumption determined by CLAP was approximately 13% with each one (1) hour codeposition test. Therefore, it was found that it was necessary to maintain the corresponding additions of aniline to the determined amount of monomer consumed per test to maintain not only the codeposited polymer level but to maintain the efficiency of the electrochemical reaction. After consideration of the possible toxicity of the aniline monomer and the handling of the residues, a search was made in the literature to investigate other uses for (poly) aniline. It was found that polyaniline had been in use for more than 100 years as dyes for a variety of fabrics, including leather. In addition, sulfonated polyaniline (especially, sulfanilic acid amide) has medical importance Considerable F as a class of antibiotics known as sulfa drugs. Morrison, R.T. et. Al., Organic Chemistry, Allyn, and Bacon, Boston (1973). With the long-term history of the successful use of polyaniline, as well as the knowledge that aniline spontaneously polymerizes oxidatively, It is believed that a significant level of toxicity can not be associated with the use of polyaniline. However, care must be taken in the handling of the aniline monomer to avoid direct contact, due to its level of reactivity (oxidation). 15 The consistency of the coatings obtained through the co-deposition process, the identification of the lateral reactions that occur during the processing, as well as the method to overcome their effects, determined that the reaction is repeatable and controllable. Recognizing the reactivity of the aniline monomer (and the sulfuric acid) and handling the formulation with care, especially when monomer additions are made, the formulation should be safe to use. The treatment of residues should not be difficult since the aniline polymerizes spontaneously, and once bound, is extremely stable. To compare the co-deposition process with coexisting processes, the aspects of corrosion resistance, wear resistance and the number of process steps were considered. Depending on the application, corrosion resistance of conventionally anodized films is achieved through sealing, at least, through exposure to steam (boiling water). The wear resistance of conventionally anodized films is improved by various surface treatments after fluoropolymer anodization. The co-deposition process produces fully bonded composite films that are fully integrated in one step. It is believed that no other known existing anodic process used to coat aluminum does this. The reduction in the amount of the processing steps by co-deposition can therefore potentially reduce time and costs, while providing a film exhibiting comparable corrosion resistance and superior wear resistance. By fully developing the electrochemical seal, it is possible that an additional step will allow the chemical bonding of a polymer to a metal to be completed. In addition, since the seal would retain the characteristics of the deposited polyaniline, the chemically bonded surface could possibly be electrically conductive, adding to potential applications.

Alternatives and Other Potential Applications It has been developed in theory and experimentally tested an anodic coating process the which produces composite films of polymer-metal oxide on an aluminum substrate. Importantly, the process is the modification of the anodizing electrolyte to include aniline monomer. The structure of amino-benzene can be made electroactive, that is, conductive, through the substitution of the ring in a protonic acid. The protonic acid in this process is sulfuric acid. The nature of the composition of the film has been scientifically characterized and indicates the following Structure: the aluminum oxide constituent is metallurgically bonded to the substrate and a non-protonated aluminum polyaniline salt sulfonated in the ring is chemically bound to the bohemite structure of the aluminum oxide. The resulting coating is adheres and exhibits comparable corrosion resistance and wear resistance superior to that of conventionally sealed, anodized layers. The finished film can be coated via electropolymerization techniques with electroactive polyaniline to produce a film composed of a chemically bonded conductive surface. Although the focus of this application has been on the development of composite films of polymer-metal oxide on aluminum, it will be appreciated that the solubility of aniline in protonic acids other than sulfuric acid indicates the possibility of using other electrolytes so that similar composite films can be developed, using the one-step process of the present invention, on other metal substrates ( example, copper, steel, silicon, zinc, magnesium or titanium). For example, with silicon, a film composed of silicon dioxide could be formed. This increases the potential uses of the process. It is believed that the applications of such composite interface are currently far from being achieved. Like a standalone film, the coatings exhibit excellent clarity and reflectivity as well as aluminum windings used in the lighting industry. The coatings also easily accept dye, making them desirable for architectural and decorative applications. More significantly, for aluminum products that are normally anodized with a f hard coating, the homogeneous, fully integrated 5 end, formed with the polyaniline exhibits remarkable wear resistance in a one-step process. Any product that is on a laminated polymer-metal structure, such as gaskets, capacitors, pipes and piston and bearing components, fuel pumps, circuit boards or various types of sensors, more cheaply, and result in a more reliable product, using the one-step co-deposition coating process of the present invention . As In yet another example, the products, conductors or otherwise, may benefit from the use of the process of the present invention. Also, the modification of the microstructure of the conventional anodic film, which uses the present invention, to produce a film resistant to wear and corrosion, dense, without requiring a secondary sealing operation could illuminate the need for additional sealing baths, reducing time and cost. Wear resistance and corrosion can exhibit the most impact Significant since the conductive nature of the monomer within the electrolyte produces a completely integrated film structure, with the codeposited polymer in the anodic film (see FIGS. 17, 18, 20 and 21). As an interfacial composition, placed to facilitate polymer-to-metal bonding, direct bonding of other active site polymers on the polyaniline backbone provides adhesion of laminated structures, such as gaskets, capacitors, circuit boards, and laminates decorative Further research and development is necessary to develop these characteristics through the polymerization of polyaniline on the codeposited coating. The description of the preferred embodiments of the invention has focused on the co-deposition of the conductive polyaniline during the aluminum anodization process, and the use of the sulfuric acid as the electrolyte. This is partly due to the well-known structure of the anodized films on aluminum, and the well-documented solubility of the aniline monomer in sulfuric acid. Once the principles of the present invention are understood, however, those skilled in the art will appreciate that it may be possible to employ conductive polymers other than polyaniline in the anodizing electrolyte, ie, other polypyrrole polymers that can be adulterated to bring them to a driver state. Also, since aniline exhibits good solubility in other acidic solutions as well as those incorporated during anodization, it may be possible to develop films for the purpose of forming polymer-oxide-metal composite films. Three basic processes have been described: (1) standard anodization and hard coating; (2) electropolymerization of polyaniline from an acid electrolyte onto a metal electrode; and (3) co-deposition of a polyaniline phase or oxide state during aluminum anodization. Of these basic processes the third is the focus of the present invention. Consistent with the principles of the co-deposition process described here, the co-deposition process can be modified to produce at least five types of double films: 1) Standard anodic film + codeposited film 2) Hard coated anodic film + codeposited film 3) Co-deposited film + electropolymerized film 4) Standard anodic film + electropolymerized film 5) Anodic film with hard coating + electropolymerized film In all cases, the purpose of the process is to produce adherent, wear-resistant and corrosion-resistant films. Applications that use those characteristics, especially wear resistance, it is believed that the applications that use these characteristics, especially that of resistance to wear, are treated by the prior art, even with the electropolymerization process. Consideration should also be given to the fact that favorable properties can be obtained with the electropolymerization of the polyaniline on the surface of double film types 1) and 2), above, by forming a discrete third layer of polymer. Of course, it should be understood that the various changes and modifications to the embodiments described herein will be apparent to those skilled in the art. Examples of such modifications are provided in the preceding section. Such modifications and changes may be made to illustrate the embodiments without departing from the spirit and scope of the present invention, and without diminishing the claimed advantages. Therefore, it is intended that such changes and modifications be covered by the following claims. It is noted that in relation to this date, the best method known to the applicant to carry out the aforementioned invention, is that which is clear from the present description of the invention.

Claims (25)

CLAIMS Having described the invention as above, the content of the following claims is claimed as property:

1. An anodizing process for forming a composite film on a metallic substrate, characterized in that it comprises the steps of anodizing the metallic substrate simultaneously with the deposition of a polymer or polymeric phase of an electrolyte, the electrolyte incorporating the conductive polymer into an acid solution protonic.

2. An anodizing process for forming a composite film of metal-oxide oxide on a metal substrate, characterized in that it comprises the steps of < : provide an electrolyte; incorporating a conductive polymer or polymer phase into a protonic acid solution within the electrolyte; and anodizing the metal substrate while simultaneously depositing the polymer or conductive polymer phase within the metal oxide during the formation of the metal oxide film on the surface of the substrate.

3. The anodization process according to claim 2, characterized in that it also comprises the step of electropolymerizing a discrete polymer film on the surface of the film F composite to produce a conductive polymer film, completely sealed, on the surface of the composite film deposited.

4. The anodization process according to claim 3, characterized in that the polymer 10 electropolymerized is an emeraldine phase of F polyaniline.

5. The anodization process according to claim 2, characterized in that the addition of monomer to the electrolyte is aniline.

6. The anodization process according to claim 2, characterized in that the conductive polymer consists of one of the conductive oxide states of the polyaniline. The anodization process according to claim 2, characterized in that the electrolyte is based on or includes a mixture of one or more of the following protonic acids: sulfuric acid; methyl sulfonic acid, chromic acid, oxalic acid; or phosphoric acid. The anodization process according to claim 2, characterized in that the metallic substrate is selected from one or more of the following metals: aniline; silicon; zinc; magnesium; or titanium. 9. The anodization process according to claim 2, characterized in that the codeposited composite film is used for an application of wear resistance. 10. The anodizing process according to claim 2, characterized in that the codeposited composite film is used for a corrosion-resistant application. The anodization process according to claim 2, characterized in that the codeposited composite film is formed on a standard anodic film. 12. The anodization process according to claim 2, characterized in that the composite film deposited is formed on an anodic hard coating film. The anodization process according to claim 2, characterized in that the codeposited composite film is formed with an electropolymerized film. The anodization process according to claim 2, characterized in that an aluminum salt of substituted polyaniline in the ring is formed, not protonated. 15. The anodization process according to claim 15, characterized in that the salt of F 5 Sulfonated polyaniline aluminum in the non-protonated ring is formed in the pores of the composite film. 16. The anodization process according to claim 15, characterized in that the aluminum oxide has a columnar Bohemite structure. 10 1

7. An anodization process where they form F an aluminum salt of sulfonated polyaniline in the ring, not protonated. 1

8. A two step coating process to provide a metal substrate with a film, Characterized in that it comprises the steps of: performing an anodization process to form a metal oxide film; and therefore carry out an electrolytic finishing process, where a conductive polymer in a solution of The protonic acid within the electrolyte forms a double structure, which is completely metallurgically bound to the metal substrate and chemically bound within the film. 1

9. A two step coating process to provide an aluminum substrate with a film, Characterized in that it comprises the steps of: a. perform a hard coating anodization to form a hard metal oxide coating; b. subsequently perform an electrolytic termination process using an electrolyte that incorporates a polymer or conductive polymer phase into a protonic acid solution within the electrolyte; c. continue the anodization process while simultaneously depositing the polymer (phase) conductive of the electrolyte, inside the metal oxide, as the anodization process continues. 20. A process of coating in two steps to form a composite film on a metal substrate, characterized in that it comprises the steps of: a. perform the simultaneous anodization with the deposition of a polymer or polymer phase of an electrolyte, the electrolyte incorporates conductive polymer into a solution of protonic acid; and b. subsequently carry out a finishing process by electropolymerization in which the conductive polymer is deposited from the electrolyte, imposing a characteristic potential for the desired polymer phase. 21. A two-step coating process for forming a composite film on a metallic substrate, characterized in that it comprises the steps of: a. perform the simultaneous anodization with the deposition of a polymer or polymer phase of an electrolyte, the electrolyte incorporates conductive polymer into a solution of protonic acid; and 5 b. subsequently carry out a finishing process by electropolymerization in which the conductive film is deposited from the electrolyte by cycling the metal substrate in the electrolyte through a range of characteristic potentials for the deposit of the polymer. 22. A process of coating in two steps to form a film on a metal substrate, characterized in that it comprises the steps of: a. performing a conventional anodization process on the metal substrate to form a metal oxide layer on the substrate; b. provide an electrolyte which incorporates a conductive polymer in a solution of protonic acid with the electrolyte; and 20 c. perform a finishing process by electropolymerization in which the polymer of the electrolyte is deposited. 23. The two step coating process according to claim 22, characterized 25 because the conductive polymer of the electrolyte is deposited either by imposing a characteristic potential for the desired polymer phase, or by cycling the substrate in the electrolyte through a range of characteristic potentials for polymer deposition. F 5 24. A two-step coating process for forming a film on a metallic substrate, characterized in that it comprises the steps of: a. perform a hard coating anodization to form a hard metal oxide coating 10 on the metal substrate; F b. provide an electrolyte; c. incorporating a conductive polymer into a protonic acid solution within the electrolyte; and d. subsequently perform a process of 15 terminated by electropolymerization in which the conductive polymer is deposited from the electrolyte. 25. The two step coating process according to claim 24, characterized in that the electrolyte conducting polymer is deposited either by imposing a characteristic potential for the desired polymer phase, or by cycling the substrate in the electrolyte through a range of characteristic potentials for polymer deposition. SUMMARY OF THE INVENTION A process for forming polymefilms to a cf through electrochemical techniques that utilize electrolytes which include a conductive polymer. 5 The resulting polymefilms are electlly conductive and resistant to wear and tear. Polyamino-benzene (polyaniline), for example, undergoes an insulator to metal transition after being adulterated with protonic acids in a reaction of the type F 10 acid / base. The composite polymer-aluminum oxide films can be formed by modifying the anodizing electrolyte, resulting in the co-deposition of the polyaniline during aluminum anodization. It was determined that an aluminum salt of polyaniline 15 sulfonated in the ring, not protonated, is the product of the reaction within the aluminum oxide phase of the codeposited films. A second process was also developed, which incorporates the electrochemical sealing of the anodic layer with polyaniline. 20 The formation of these composite films was documented through experimental processing, and was characterized through scientific analysis and engineering tests. The scientific characterization determined the co-deposition process that produces bonded films 25 chemically and metallurgically. Engineering tests determined the films, obtained through a single step, exhibiting superior wear and corrosion resistance comparable to those of anodized and conventionally sealed films through two steps, demonstrating that greater efficiency can be obtained in the manufacture using the process of the present invention.