WO2015001461A1 - Hybrid sol-gel compositions and corrosion-resistant coatings based upon same - Google Patents

Hybrid sol-gel compositions and corrosion-resistant coatings based upon same

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Publication number
WO2015001461A1
WO2015001461A1 PCT/IB2014/062687 IB2014062687W WO2015001461A1 WO 2015001461 A1 WO2015001461 A1 WO 2015001461A1 IB 2014062687 W IB2014062687 W IB 2014062687W WO 2015001461 A1 WO2015001461 A1 WO 2015001461A1
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Prior art keywords
sol
substrate
gel
composition
metal
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PCT/IB2014/062687
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French (fr)
Inventor
Peter RODIC
Ingrid MILOSEV
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Jozef Stefan Institute
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/48Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
    • C08G77/56Boron-containing linkages
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/48Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
    • C08G77/58Metal-containing linkages
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; MISCELLANEOUS COMPOSITIONS; MISCELLANEOUS APPLICATIONS OF MATERIALS
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/14Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; MISCELLANEOUS COMPOSITIONS; MISCELLANEOUS APPLICATIONS OF MATERIALS
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08Anti-corrosive paints

Abstract

A curable hybrid sol-gel composition includes the combination of: (a) a first sol comprising the combination of (i) a hydrolysable silicon alkoxide and (ii) a silicon alkoxide having a least one non-hydrolysable substituent bonded to the silicon atom; and (b) a second sol comprising the combination of (i) a hydrolysable metal oxide in which the central metal atom is selected from the group consisting of Ti, Zr, Al, B, Sn, and V, and (ii) a (meth)acrylic acid-functional component. The cured composition is useful in a variety of compositions, e.g., as an anti-corrosion coating for metal substrates.

Description

HYBRID SOL-GEL COMPOSITIONS AND CORROSION-

RESISTANT COATINGS BASED UPON SAME

TECHNICAL FIELD

This invention relates to hybrid sol-gel compositions and the use of such compositions as corrosion-resistant coatings.

BACKGROUND

Corrosion of metals represents a significant problem for many metals used in a number of industries. A prominent example relates to aluminum and aluminum alloys used in the aerospace industry. Corrosion over time compromises the integrity of the metal and structures based upon the metal. Various approaches have been proposed for improving corrosion resistance of metals. Examples include passivation, application of various organic and inorganic protective coatings, cathodic and anodic protection, incorporation of corrosion inhibitors, and the like. However, a number of these approaches require the use of environmentally hazardous materials (e.g., chromates) and/or generate significant amounts of volatile organic compounds (VOC's), neither of which is desirable. SUMMARY

In one aspect, a curable hybrid sol-gel composition is described that includes the combination of: (a) a first sol comprising the combination of (i) a hydrolysable silicon alkoxide and (ii) a silicon alkoxide having at least one non-hydrolysable substituent bonded to the silicon atom; and (b) a second sol comprising the combination of (i) a hydrolysable metal oxide in which the central metal atom is selected from the group consisting of Ti, Zr, Al, B, Sn, and V, and (ii) a (meth)acrylic acid-functional component.

In some embodiments, the hydrolysable silicon alkoxide has the formula: SiCOR^OR^OR^OR4) wherein each R1, R2, R3, and R4, independently, is a substituted or unsubstituted C1-C14 alkyl, aryl, alkenyl, or alkynyl group. For example, each R1, R2, R3, and R4, independently, may be a substituted or

unsubstituted C1-C14 alkyl group, e.g., an unsubstituted C1-C6 alkyl group. An example of a suitable hydrolysable silicon alkoxide is tetraethyl orthosilicate. As used herein, the terms "alkyl," "alkenyl," and "alkynyl" refer to both straight chain, branched, and cyclic groups.

In some embodiments, the silicon alkoxide having at least one non- hydrolysable substituent bonded to the silicon atom has the formula: R8-(CH2)m- Si(OR5)(OR6)(OR7) where each R5, R6, and R7, independently, is a substituted or unsubstituted C1-C14 alkyl, aryl, alkenyl, or alkynyl group; m is 0-20; and R8 is a (meth)acrylate, amino, glycidyl, or isocyanato group. For example, each R5, R6, and R7, independently, may be an unsubstituted C1-C6 alkyl group. The subscript "m" may be a value from 1-6. R8 may be a (meth)acrylate group. An example of a suitable silicon alkoxide having a least one non-hydrolysable substituent bonded to the silicon atom is 3-methacryloxypropyltrimethoxy silane.

In some embodiments, the second sol includes the combination of (i) a hydrolysable metal oxide in which the central metal atom is Zr. The metal oxide may have the formula: Zr(OR9)(OR10)(ORn)(OR12) wherein each R9, R10, R11, and R12, independently, is a substituted or unsubstituted C1-C14 alkyl, aryl, alkenyl, or alkynyl group. For example, each R9, R10, R11, and R12, independently, may be a substituted or unsubstituted C1-C14 alkyl group, e.g., an unsubstituted C1-C6 alkyl group. An example of a metal oxide useful for inclusion in the second sol is zirconium tetrapropoxide.

The (meth)acrylic acid-functional component may be (meth)acrylic acid. It can also be an oligomer or polymer containing (meth)acrylic acid groups, e.g., polyacrylic acid.

In some embodiments, the curable sol-gel includes the combination of: (a) a first sol comprising the combination of tetraethyl orthosilicate (TEOS) and 3- methacryloxypropyltrimethoxysilane (MAPTMS); and (b) a second sol comprising the combination of zirconium tetrapropoxide (ZTP) and (meth)acrylic acid (MAA).

The curable hybrid sol-gel compositions may be prepared by combining the first and second sols, and then ageing the combination for a period of at least 1 minute. In some embodiments, ageing may occur for a period ranging from about 30 minutes to about 5 days. In other embodiments, the combination is aged for at least 30 days.

The curable hybrid sol-gel compositions may be used as anti-corrosion coatings when applied to the surface of a substrate (e.g., a metal or metal alloy substrate such as an aluminum or aluminum alloy substrate) and then cured. The coating may be cured by exposing it to ultraviolet radiation, e.g., daylight in the presence of oxygen (air) or in an inert atmosphere.

In some embodiments, a corrosion inhibitor such as a cerium(III) salt (e.g., cerium(III) nitrate or cerium(III) acetate), a cerium(IV) salt, or cerium oxide may be added to the hybrid sol-gel composition. Such additives may offer additional corrosion protection.

As used herein, the term "hydrolysable silicon alkoxide" means a Si-O-R structure, where R represents any of the R groups described above. Similarly, the term "hydrolysable metal oxide" means a M-O-R structure, where M is a metal and R represents any of the R groups described above. The bonds of such structures, when contacted with water or a water-miscible solvent such as an alcohol, readily break.

As used herein, a silicon alkoxide having a "non-hydrolysable substituent bonded to the silicon atom" means a Si-R structure, where R represents any of the R groups described above. The bonds of such structures, when contacted with water or a water-miscible solvent such as an alcohol, do not readily break.

As used herein, the terms "(meth)acrylic" and "(meth)acrylate" refer to both acrylic and methacrylic groups, and both acrylate and methacrylate groups, respectively.

The curable hybrid sol-gel compositions can be used to form corrosion and crack-resistant coatings that are stable over extended periods of time. The compositions can be easily manufactured and cured under mild conditions, e.g., exposure to daylight, rather than requiring exposure to high temperatures. In addition, the compositions and cured coatings can be prepared without the use of

environmentally hazardous reagents.

The details of one or more embodiments of the invention are set forth in the accompanying drawings and the description below. Other features, objects, and advantages of the invention will be apparent from the description and drawings, and from the claims. DESCRIPTION OF DRAWINGS

FIG. 1 presents electrochemical potentiodynamic polarization curves for (a) an uncoated aluminum alloy substrate and (b) the same substrate provided with the hybrid sol-gel composition described in Example 2 measured in 0.1M NaOH.

FIG. 2 presents electrochemical potentiodynamic polarization curves for (a) an uncoated magnesium alloy substrate and (b) the same substrate provided with the hybrid sol-gel composition described in Example 4 measured in simulated Hanks (physiological) solution.

FIGS. 3(a), (b), (c), and (d) are photographs comparing untreated aluminum alloy substrates and aluminum alloy substrates provided with the hybrid sol-gel composition described in Example 5 after exposure to salt spray for various periods of time.

Like reference symbols in the various drawings indicate like elements.

DETAILED DESCRIPTION

A curable hybrid sol-gel composition includes the combination of: (a) a first sol comprising the combination of (i) a hydrolysable silicon alkoxide and (ii) a silicon alkoxide having at least one non-hydrolysable substituent bonded to the silicon atom; and (b) a second sol comprising the combination of (i) a hydrolysable metal oxide in which the central metal atom is selected from the group consisting of Ti, Zr, Al, B, Sn, and V, and (ii) a (meth)acrylic acid-functional component. Specific classes of reactants, and the relative amounts of such reactants, are selected based upon the desired properties of the final coating. Exemplary hydrolysable silicon alkoxides, silicon alkoxides having at least one non-hydrolysable substituent bonded to the silicon atom, hydrolysable metal oxide having a central atom selected from Ti, Zr, Al, B, Sn, and V, and (meth)acrylic acid-functional components are set forth in the Summary of the Invention, above.

Including organic groups in the individual reactants results in the formation of dense coatings upon curing. Such coatings are more flexible and crack-resistant than all-inorganic coatings. This, in turn, enables the coatings to provide long-term corrosion resistance for the underlying substrate.

The hybrid sol-gel composition is prepared by forming the first and second sols, and then combining them. Once combined, the reactants undergo a series of hydrolysis and condensation reactions. The reactions may be conducted in aqueous solution, or in a mixture of aqueous and organic solvents (e.g., a mixture of water and a water-miscible alcohol such as methanol, ethanol, or propanol). The reactions may, if desired, be a catalyzed by addition of an acid or base catalyst. The catalyst, in turn, may be inorganic or organic. Representative examples of suitable acids include acetic acid, (meth)acrylic acid, hydrogen chloride, hydrogen bromide, hydrogen iodide, nitric acid, sulfuric acid, phosphoric acid, formic acid, propionic acid, butanoic acid, and salicyclic acid. Representative examples of suitable bases include ammonia, and alkali and alkaline earth bases, e.g., KOH, NaOH, Ca(OH)2, and the like. In general, the catalyst concentration ranges from about 0.01 μΜ to about 1M. In some embodiments, the concentration ranges from about 0.01 μΜ to about 1 mM.

The (meth)acrylic acid-functional component forms a chelate with the hydrolysable metal oxide in the second sol to inhibit reactivity of the hydrolysable metal oxide and thereby prevent premature reaction. After combining the second sol with the first sol, the (meth)acrylic acid-functional component is liberated and free to react further. For example, upon exposure to heat, ultraviolet radiation, or e-beam radiation, it can polymerize and/or crosslink, thereby improving the density of the final product.

A crosslinking agent may be included in the composition to facilitate cure and formation of a dense coating. The crosslinking agents may be thermally activated, photo-activated, or e-beam activated. Examples include Bisphenol A, bismaleimide, diethylene triamine, urea-functional compounds, and (meth)acrylate-functional agents.

After the two sols have been combined, the resulting composition is aged, preferably at room temperature. Ageing contributes to the formation of a dense coating. The specific ageing period is selected based upon the individual reactants and relative amounts thereof. In general, the ageing period is at least 1 minute. In some embodiments it ranges from 0.5 hours and 5 days. In other embodiments, it may be at least 30 days.

After ageing is complete, the resulting hybrid sol-gel composition may be coated on a substrate. A variety of substrates that are prone to corrosion are suitable, including ceramic and metal substrates. Representative metal substrates include aluminum, magnesium, and alloys thereof. Other suitable substrates include polymeric substrates (e.g., polyesters and polycarbonates), glass, and ceramic substrates (e.g., metal oxide substrates). The composition may be deposited by a variety of methods, including dipping, brushing, knife coating, rolling, spraying, spin coating, laminar-flow or meniscus coating, tape coating, screen printing, and curtain coating. Spin-coating is the preferred method.

Following deposition, the coating is dried and cured. The coating may be cured thermally, photochemically, e.g., by exposure to ultraviolet radiation, or by exposure to e-beam. For example, the coating may be cured by simple exposure to daylight, either in the presence of oxygen (air) or under an inert atmosphere. Curing may occur at ambient temperatures or at temperatures up to about 300°C.

The cured coatings are useful in a number of applications. For example, they could be used as anti-corrosion coatings for metal substrates in construction and aerospace applications, as well as electronic components and devices. In addition, the coatings could be useful as adhesion promoters for improving the adhesion of a topcoat to a substrate. The coatings also could be useful in optical applications, including microlens arrays, Fresnels lenses, and the like, because they can form thin (e.g., 5-10 μιη) layers and do not absorb ultraviolet radiation. In addition, various therapeutic agents (e.g., drugs, anti-viral agents, anti -bacterial agents,

microorganisms, and the like) could be incorporated in the coatings and then released over time, making the coatings useful in applications such as implantable medical devices.

Example 1

A first sol (sol A) was prepared by combining 0.66 g TEOS and 5.10 g MAPTMS in a beaker. As the contents of the beaker were stirred vigorously, 0.75 g water and 2.0 mg HCl were added dropwise to initiate a hydrolysis reaction. Initially, phase separation was observed between insoluble silica precursors and water.

A second sol (sol B) was prepared separately. A mixture of 4.50 g ZTP in 1- propanol and 0.21 g MAA was prepared in a beaker. The molar ratio of ZTP to MAA was 4: 1. The MAA forms a chelate with the ZTP. After the second sol is combined with the first sol, the MAA is free and available to react with MAPTMS.

Both sols were stirred for half an hour, after which sol B was added slowly to sol A with vigorous stirring. The molar ratio of MAPTMS to ZTP was 1 :0.48. After mixing, the solution was stirred for about 48 hours to age the solution. Ageing the solution creates a dense network.

An aluminum alloy substrate (AA 2024-T3) was ground with 800- and 1200- grit SiC emery papers, rinsed under tap water followed by distilled water, and dried in air. The substrate was further cleaned ultrasonically for 10 minutes in an organic solvent such as ethanol. The aged sol composition was applied to the substrate using a spin-coater. An excess amount of the sol was applied on the surface by injecting the fluid through a 0.2 μιη syringe. The substrate was then rotated at a speed of 4000 rpm for 30 seconds to produce a transparent sol-gel coating film. The coated substrate was then dried first at room temperature to evaporate the solvent slowly, and then on a pre-heated hotplate at 100°C under daylight for 1 hour to form the final cured coating.

Example 2

Sol A was prepared as described in Example 1. A second sol (sol C) was prepared separately as follows. A mixture of 4.50 g ZTP in 1-propanol and 1.67 g MAA was prepared in a beaker. The molar ratio of ZTP to MAA was 1:2. As in Example 1, the MAA forms a chelate with the ZTP and is freed after the first and second sols are combined, making it available to react with MAPTMS and/or itself. Both sols were stirred for half an hour, after which sol C was added slowly to sol A with vigorous stirring. The molar ratio of MAPTMS to ZTP was 1 :0.48. After mixing, the solution was stirred for about 48 hours to age the solution. Ageing the solution creates a dense network.

A coated substrate was prepared as described in Example 1. The coated substrate was dried at room temperature under sunlight for 1 hour to form the final cured coating.

The electrochemical corrosion properties of the coated substrate were determined using potentiodynamic polarization measurements for an uncoated and coated sample during immersion in 0.1 M NaOH. Electrochemical measurements were formed in a three-electrode standard corrosion cell (Corrosion Cell Kit, model K0047, volume 1 L, EG&G) at 25°C. The working electrode was embedded in a Teflon® holder (model K0105 Flat Specimen Holder Kit, EG&G), leaving an area of 0.950 cm2 exposed to the solution. A saturated calomel electrode (SCE) placed in a Luggin capillary was used as the reference electrode. Carbon rods served as the counterelectrode. The measurements were made using an Autolab PGSTAT 12 (Metrohm Autolab, Utrecht, Netherlands) potentiostat/galvanostat controlled by Nova 1.8 software.

Prior to taking any measurements, the samples were allowed to stabilize under open circuit conditions for approximately 1 hour. During that time, the open circuit potential, Eocp, was measured as a function of time. The stable, quasi-steady state potential reached at the end of the stabilization period is denoted as the corrosion potential, EC0IT.

Following stabilization, the electrochemical measurements were carried out. The linear polarization measurements were performed in a potential range of ± 10 mV vs. ?Corr at a 0.1 mV/s potential scan rate. The values of polarization resistance, Rp, were deduced from the slope of fitted current density vs. potential line using the Nova 1.8 software. Potentiodynamic measurements were performed at a 1 mV/s potential scan rate starting at 250 mV negative to icorr- The potential was then increased in the anodic direction. Corrosion parameters, corrosion potential, and corrosion density, corr, were determined using the Tafel analysis, while the value of the pitting potential, Epitt, was determined as the potential value within the passive range at which the current density starts to increase suddenly due to the process of localized pitting corrosion. For each sample, measurements were performed at least in triplicate.

The results are shown in Fig. 1. The curve labeled (a) represents the uncoated aluminum alloy substrate and the curve labeled (b) represents the coated substrate. The results demonstrate that the coating exhibits excellent barrier anti-corrosion properties. No breakdown was observed up to 7 V.

Example 3

Sol A was prepared as described in Example 1. A second sol (sol D) was prepared separately as follows. A mixture of 8.98 g ZTP in 1-propanol and 3.34 g MAA was prepared in a beaker. The molar ratio of ZTP to MAA was 1:2. As in Example 1, an excess amount of MAA was available to react with MAPTMS. Both sols were stirred for half an hour, after which sol D was added slowly to sol A with vigorous stirring. The molar ratio of MAPTMS to ZTP was 1:0.96. Relative to Examples 1 and 2, the condensation reaction was faster. As a result, ageing was complete after 1 hour.

A coated substrate was prepared as described in Example 1. The coated substrate was dried at room temperature under sunlight for 1 hour to form the final cured coating. It was found that the higher molar ratio of ZTP had a positive impact on the contact angle of the coating, which increased from 45° for the uncoated substrate to 83° for the coated substrate, as measured using an Easydrop contact angle measurement instrument.

Example 4

Sol A was prepared as described in Example 1. A second sol (sol E) was prepared separately as follows. A mixture of 1.12 g ZTP in 1-propanol and 0.21 g MAA was prepared in a beaker. The molar ratio of ZTP to MAA was 1: 1. As in Example 1, MAA forms a chelate with ZTP and is freed after the first and second sols are combined, rendering it free to react with MAPTMS and/or itself. Both sols were stirred for half an hour, after which sol E was added slowly to sol A with vigorous stirring. The molar ratio of MAPTMS to ZTP was 1 :0.12. The sol mixture was aged, applied to a substrate (magnesium alloy AZ31), and cured by exposure to sunlight following the procedure described in Example 1.

The electrochemical corrosion properties of the coated AZ31 substrate were determined using potentiodynamic polarization measurements as described in Example 2 for both the coated and an uncoated sample during immersion in Hanks balanced solution having the following composition: 8 g/1 NaCl, 0.4 g/1 KC1, 0.25 g/1 NaH2P04 x 6H20, 0.06 g/1 MgS04 x 7H20, and 1 g/1 glucose (pH = 7.5), rather than 0.1M NaOH. The results are shown in Fig. 2. The curve labeled (a) represents the uncoated magnesium alloy substrate and the curve labeled (b) represents the coated substrate. The results demonstrate that the coating exhibits excellent barrier anti- corrosion properties. No breakdown was observed up to 1.0 V more positive than the open circuit potential (OCP), which represents excellent anodic protection even in this highly corrosive medium for a magnesium alloy.

Example 5

The process described in Example 1 was followed to prepare samples in which the sol-gel coating was deposited on an aluminum alloy substrate (AA 2024-T3). The coated substrates were then subjected to the salt spray test set forth in International Standard Organization (ISO) Standard No. 9227-2006 entitled "Corrosion Tests in Artificial Atmosphere." The test was carried out in a salt spray chamber having a capacity of 0.17 m3 (ASCOTT, Staffs, Great Britain). The concentration of sodium chloride solution was 50 g/L. The pH of the NaCl solution was set between 6.0 and 6.5 to obtain a pH of between 6.5 and 7.2 after heating the solution to 35°C. The pH value was adjusted with 0.1 M NaOH or HC1 solutions.

The device for spraying the salt solution included a supply of clean air, controlled pressure and humidity, reservoir to contain the salt solution, and one atomizer. The compressed air supplied to the atomizer passed through a filter to remove all traces of oil or solid matter. The temperature of the hot water in the saturation tower was 46°C and the overpressure was 85 kPa. The temperature in the salt spray chamber was 35°C ± 2°C.

Samples were taken from the chamber and photographed in order to follow the progress of corrosion with time. The results are shown in FIG. 3. The top row of photographs represents the uncoated substrate while the bottom represents the coated substrates. The results are shown for different exposure periods: 0 hours (FIG. 3(a)); 12 hours (FIG. 3(b)); 24 hours (FIG. 3(c)); and 21 days (FIG. 3(d)). The results demonstrate that the sol-gel composition provided corrosion resistance.

A number of embodiments of the invention have been described.

Nevertheless, it will be understood that various modifications may be made without departing from the spirit and scope of the invention. Accordingly, other embodiments are within the scope of the following claims.

Claims

WHAT IS CLAIMED IS:
1 1. A curable hybrid sol-gel composition comprising the combination of:
2 (a) a first sol comprising the combination of (i) a hydrolysable silicon alkoxide
3 and (ii) a silicon alkoxide having at least one non-hydrolysable substituent bonded
4 to the silicon atom; and
5 (b) a second sol comprising the combination of (i) a hydrolysable metal oxide in
6 which the central metal atom is selected from the group consisting of Ti, Zr, Al, B,
7 Sn, and V, and (ii) a (meth)acrylic acid-functional component.
8
9 2. A curable hybrid sol-gel composition according to claim 1 wherein the
I o hydrolysable silicon alkoxide has the formula: Si(OR1)(OR2)(OR3)(OR4) wherein
I I each R1, R2, R3, and R4, independently is a substituted or unsubstituted C1-C14 12 alkyl, aryl, alkenyl, or alkynyl group.
1 3
14 3. A curable hybrid sol-gel composition according to claim 2 wherein each R1, R2, R3,
1 5 and R4, independently is a substituted or unsubstituted C1-C14 alkyl group.
16
1 7 4. A curable hybrid sol-gel composition according to claim 2 wherein each R1, R2, R3,
1 8 and R4, independently is an unsubstituted C1-C6 alkyl group.
1 9
20 5. A curable hybrid sol-gel composition according to claim 1 wherein the
21 hydrolysable silicon alkoxide is tetraethyl orthosilicate.
22
23 6. A curable hybrid sol-gel composition according to claim 1 wherein the silicon
24 alkoxide having a least one non-hydrolysable substituent bonded to the silicon
25 atom has the formula: R8-(CH2)m-Si(OR5)(OR6)(OR7) where each R5, R6, and R7,
26 independently is a substituted or unsubstituted C1-C14 alkyl, aryl, alkenyl, or
27 alkynyl group; m is 0-20; and R8 is a (meth)acrylate, amino, glycidyl, or
28 isocyanato group.
29
30 7. A curable hybrid sol-gel composition according to claim 6 wherein each R5, R6,
31 and R7, independently, is an unsubstituted C1-C6 alkyl group.
8. A curable hybrid sol-gel composition according to claim 6 wherein m is 1-6.
9. A curable hybrid sol-gel composition according to claim 6 wherein R8 is a
(meth)acrylate group.
10. A curable hybrid sol-gel composition according to claim 1 wherein the silicon alkoxide having a least one non-hydrolysable substituent bonded to the silicon atom is 3-methacryloxypropyltrimethoxy silane.
11. A curable hybrid sol-gel composition according to claim 1 wherein the second sol comprises the combination of (i) a hydrolysable metal oxide in which the central metal atom is Zr and (ii) a (meth)acrylic acid-functional component.
12. A curable hybrid sol-gel composition according to claim 11 wherein the
hydrolysable metal oxide in which the central metal atom is Zr has the formula: Zr(OR9)(OR10)(ORn)(OR12) wherein each R9, R10, R11, and R12, independently, is a substituted or unsubstituted C1-C14 alkyl, aryl, alkenyl, or alkynyl group.
13. A curable hybrid sol-gel composition according to claim 12 wherein each R9, R10, R11, and R12, independently is a substituted or unsubstituted C1-C14 alkyl group.
14. A curable hybrid sol-gel composition according to claim 12 wherein each R9, R10, R11, and R12, independently is an unsubstituted C1-C6 alkyl group.
15. A curable hybrid sol-gel composition according to claim 1 wherein the second sol comprises the combination of (i) zirconium tetrapropoxide and (ii) a (meth)acrylic acid-functional component.
16. A curable hybrid sol-gel composition according to claim 1 wherein the
(meth)acrylic acid-functional component is (meth)acrylic acid.
17. A curable hybrid sol-gel composition comprising the combination of:
(a) a first sol comprising the combination of tetraethyl orthosilicate and 3- methacryloxypropyltrimethoxysilane; and
(b) a second sol comprising the combination of zirconium tetrapropoxide and
(meth)acrylic acid.
18. An article comprising a substrate and an anti-corrosion coating on a surface of the substrate, wherein the anti-corrosion coating comprises the cured product of the hybrid sol-gel composition of claim 1 or claim 17.
19. An article according to claim 18 wherein the substrate comprises a metal or metal alloy substrate.
20. An article according to claim 18 wherein the substrate comprises aluminum or an aluminum alloy.
21. A method of making a curable hybrid sol-gel composition comprising:
(A) combining (a) a first sol comprising the combination of (i) a hydrolysable silicon alkoxide and (ii) a silicon alkoxide having a least one non-hydrolysable substituent bonded to the silicon atom; and (b) a second sol comprising the combination of (i) a hydrolysable metal oxide in which the central metal atom is selected from the group consisting of Ti, Zr, Al, B, Sn, and V, and (ii) a
(meth)acrylic acid-functional component; and
(B) ageing the combined sols for a period of at least 1 minute.
22. A method according to claim 21 comprising ageing the combined sols for a period ranging from about 30 minutes to about 5 days.
23. A method according to claim 21 comprising ageing the combined sols for a period of at least 30 days.
98 24. A method of improving the corrosion resistance of a substrate comprising:
99 (A) applying the hybrid sol-gel composition of claim 1 or claim 17 to a surface of
100 the substrate to form a coated surface; and
101 (B) exposing the coated surface to ultraviolet radiation to cure the coating.
102
103 25. A method according to claim 24 wherein the substrate comprises a metal or metal
104 alloy substrate.
105
106 26. A method according to claim 24 wherein exposing the coated surface to
107 ultraviolet radiation comprises exposing the coated surface to daylight.
PCT/IB2014/062687 2013-07-02 2014-06-27 Hybrid sol-gel compositions and corrosion-resistant coatings based upon same WO2015001461A1 (en)

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US61/842,025 2013-07-02

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WO2018073186A1 (en) * 2016-10-17 2018-04-26 Fundacion Tecnalia Research & Innovation A hybrid sol-gel corrosion-resistant coating composition

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