# Patent

## Title
Pigmented organometallic sol

## Abstract

A surface treatment, especially for titanium and aluminum alloys, forms a pigmented sol-gel film covalently bonded on the metal surface to produce desired color, gloss, reflectivity, electrical conductivity, emissivity, or a combination thereof usable over a wide temperature range. The coating retains its characteristics and impact resistance following exposures to temperatures at least in the range from −321° F. to 750° F. An aqueous sol containing an organometallic alkoxide containing either Ti or Al and an organosilane with an organic acid catalyst and stabilizer is applied to etched or grit blasted substrates by dipping, spraying, or drenching, to produce bonds in a single application comparable in strength and performance to standard anodize controls. The sol-gel coating may be graded in its ceramic character by adjusting the organosilane component between TEOS and silanes that have more distinctive organic character by virtue of organic ligands attached to the silicon.

## Background
REFERENCE TO RELATED APPLICATIONS
The present application is a continuation application based upon U.S. patent application Ser. No. 10/384,908 filed Mar. 7, 2003, now U.S. Pat. No. 7,001,666 which was a divisional application based upon U.S. patent application Ser. No. 09/169,280, filed Oct. 8, 1998, now U.S. Pat. No. 6,605,365, which was a continuation-in-part application based upon any of the following applications: Ser. No. 08/742,168 (now U.S. Pat. No. 5,849,110); Ser. No. 08/742,171 (now U.S. Pat. No. 5,958,578); Ser. No. 08/740,884 (now U.S. Pat. No. 5,869,141); or Ser. No. 08/742,170, now abandoned each of which was filed on Nov. 4, 1996. It also claims the benefit of U.S. Provisional Patent Application 60/068,715, filed Dec. 23, 1997.


TECHNICAL FIELD
A sol-gel surface coating containing pigment is applied to a substrate, especially to a metal, through a waterborne reactive sol to provide a stable oxide surface that results in corrosion resistance and desired color, gloss, reflectivity, electrical conductivity, emissivity, or a combination thereof over a wide range of temperatures.
BACKGROUND OF THE INVENTION
Conversion coatings for titanium, aluminum, or other metals are electrolytic or chemical films that promote adhesion between the metal and an organic adhesive resin, especially for adhesive bonding. Anodizing is a conventional process for making electrolytic films by immersing titanium or its alloys in chromic acid or an alkaline earth hydroxide or aluminum in chromic, sulfuric, or phosphoric acid. Anodizing produces a porous, microrough surface into which primer (a dilute solution of adhesive) can penetrate. Adhesion results primarily from mechanical interlocking between the rough surface and the primer. Chemical films include either a phosphate-fluoride conversion coating or films made with alkaline peroxide or other alkaline etchants for titanium substrates and Alodine films (i.e., a chromate conversion coating) for aluminum substrates.
Because they use strong acids or strong bases and toxic materials (especially heavy metals such as chromates), these surface treatment processes are disadvantageous from an environmental viewpoint. They require significant amounts of water to rinse excess process solutions from the treated parts. The rinse water and spent process solutions must be treated to remove dissolved metals prior to their discharge or reuse. Removing the metals generates additional hazardous wastes that are challenging to cleanup and dispose. Controlling exposure of workers to the hazardous process solutions during either tank or manual application requires special control and exposure monitoring equipment that increases the process cost. They greatly increase the cost of using the conventional wet-chemical processes. A process that will produce adhesive bonds with equivalent strength and environmental durability to these standard processes without generating significant hazardous wastes while eliminating the use of hazardous or toxic materials would greatly enhance the state-of-the-art. The present invention is one such process. In addition, the process of the present invention can be applied by spraying rather than by immersion. Therefore, it is more readily used for field repair and maintenance.
Surface anodizing chemically modifies the surface of a metal to provide a controlled oxide surface morphology favorable to receive additional protective coatings, such as primers and finish paints. The surface oxides function as adhesion coupling agents for holding the paint lacquer, an organic adhesive, or an organic matrix resin, depending on the application. Anodizing improves adhesion between bonded metals. It also improves adhesion between the metal and a fiber-reinforced composite in hybrid laminates, like those described in U.S. Pat. Nos 4,489,123 or 5,866,272. We incorporate these patents by reference. Structural hybrid laminates have strengths comparable to monolithic metal, and have better overall properties than the metal because of the composite layers. At higher temperatures (like those anticipated for extended supersonic flight), conventional anodized treatments have inadequate performance in addition to being environmentally unfriendly. The thick oxide layers that anodizing produces become unstable at elevated temperatures. The oxide layer dissolves into the base metal to produce surface suboxides and an unstable interfacial layer.
Obtaining the proper interface for the organic resin at the surface of the metal is an area of concern that has been the focus of considerable research. For example, cobalt-based surface treatments for aluminum are described in U.S. Pat. Nos. 5,298,092; 5,378,293; 5,411,606; 5,415,687; 5,468,307; 5,472,524; 5,487,949; and 5,551,994. U.S. Pat. No. 4,894,127 describes boric acid—sulfuric acid anodizing of aluminum.
Bonding sites on surfaces for binders include covalent bonds, hydrogen bonds, or van der Waals forces. Conventional approaches (anodizing and chromate conversion coating) promote adhesion by producing a high surface area coating which has both mechanical and physical (Lewis acid-base, dispersion, hydrogen bonding, etc.) interactions with the adhesion primer. An aerospace coupling agent can be used to create strong covalent bonds between the metal substrate and the organic primer. The present invention improves adhesion by crating a sol-gel-based coating containing a coupling agent on the metal surface. A metal-to-resin gradient occurs through a monolayer of organometallic coupling agents. Generally we use a mixture of coupling agents. The organometallic compounds preferably have zirconium or silicon active moieties to interact with, react with, or bond to the metal surface. Some mechanical interaction may result from the surface porosity and microstructure. The organic portion of the organometallic compounds usually has a reactive functional group appropriate for covalently bonding with the adhesive or matrix resin. A preferred sol-gel film is made from a sol having a mixture of organometallic coupling agents. One component (usually containing zirconium) bonds covalently with the metal while a second component bonds with the resin. Thus, the sol-gel process orients the sol coating having a metal-to-resin gradient on the surface.
The standard anodizing processes, conversion coatings, or oxide surface preparations, especially for titanium, are inappropriate to use with new polyimide adhesives that are promising as adhesives for vehicles that will experience extended exposure to hot/wet conditions. At high temperatures, the solubility of oxygen in titanium is high and the oxide layer simply dissolves with the oxygen migrating into the base metal. The result is interfacial failure at the metal-adhesive interface. To alleviate this type of bond failure, the surface oxygen needs to be tied up in a stronger bond that will not dissociate in bonding or during operation of the system. A zirconate-silicate sol coating of the present invention is useful at these extended hot/wet conditions because the Zr—O bond that forms between the coating and the metal surface is more durable than a Ti—O bond. The free energy of formation for the metal oxides is such that a Zr—O bond is more stable at high temperatures than a Ti—O or Si—O bond. The higher bond strength of the Zr—O bond prevents dissolution of the oxide layer, so the Zr component in our sol coating functions as an oxygen diffusion barrier. We can use yttrium, cerium, or lanthanum in addition to or as a replacement for the Zr, because these elements also produce high strength oxide bonds that function as an oxygen diffusion barrier. The high cost of these compounds, however, dictates that they be used sparingly. Therefore, we developed a mixed metal coating having Zr and Si to produce the desired metal-to-resin gradient needed for good adhesion in structural adhesive bonds, hybrid laminates, or paint adhesion applications. Our coating integrates the oxygen diffusion barrier function of the Zr (or its alternatives) with an organosilicate network desirable for superior bonding performance.
The present invention combines pigments with the sol-gel corrosion inhibitor thin film, to overcome many of the shortcomings of paint. Paints are commonly used to protect a surface and to provide color, gloss, reflectivity, or the like on a substrate. Paints generally disperse metal or ceramic pigments and a binder in a water or organic vehicle to form a film when dried on a surface. Typically, the binder is an organic resin. Paints generally have application only at relatively low temperatures. They can be difficult to apply uniformly. They are relatively heavy and are expensive to repair. Extreme environments, such as high temperatures or space environments with high ultraviolet, atomic oxygen, and particle exposure, degrade typical organic resins. The present invention combines pigments with sol-gel binder thin films to give greater performance and durability under extreme conditions.
SUMMARY OF THE INVENTION
The present invention is a sol for coating metal surfaces and composite substrates, especially aluminum or titanium alloys, to produce a sol-gel film, generally containing pigment, as a surface coating having suitable appearance and substrate protection qualities, including color, gloss, reflectivity, electrical conductivity, emissivity, or a combination thereof. The sol-gel film or sol coating also provides corrosion resistance to a limited degree and can promote adhesion through a hybrid organometallic coupling agent at the metal surface. Our preferred sol provides high temperature surface stability.
We use a sol to produce the sol-gel film on the surface. The sol is preferably a dilute solution of an organometallic compound, such as tetra-i-propoxyzirconium, tetra-n-propoxyzirconium, an aluminum alkoxide, a titanium alkoxide, or a combination thereof, and an organosilane coupling agent, such as 3-glycidoxypropyltrimethoxysilane for epoxy or polyurethane systems or a corresponding primary amine for polyimide systems, with an acetic acid catalyst and Zr hydrolysis rate stabilizer for aqueous formulations.
The sol usually is filled with pigments to provide desired, color, gloss, reflectivity, electrical conductivity, emissivity, or the like. The sol-gel film is usually applied by spraying or drenching the metal in or with the sol without rinsing. For metal surfaces, the sol-gel film produces a gradient changing from the characteristics of metal to those of organic resins. Good adhesion results from clean, active metal surfaces with sol coatings that contain the organometallic coupling agents in the proper orientation. After application, the sol coating is dried at ambient temperature or, more commonly, heated to a temperature between ambient and 250° F. to complete the sol-gel film formation.
Ideally, covalent bonding occurs between the metal surface and a zirconium compound in the sol. Successful bonding requires a clean and chemically active metal surface. The strength and durability of the sol coating depends upon chemical and micro-mechanical interactions at the surface involving, for example, the metal's porosity and microstructure and on the susceptibility of the sol coating to rehydrate. The methods used to prepare the surface for the sol-gel coating are part of the coating sequence of the present invention.
The sol-gel is normally applied in several coats to form the final coating. It may be beneficial to vary the chemistry of the sol-gel slightly between coats. For example, the initial coats might use TEOS (tetra-ethyl-orthosilicate) as the organosilane to produce a more ceramic-like layer while the later coats might use an aminosilane with an active functional group to enhance bonding with overcoats, adhesives, or the like.



BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a block diagram of the typical steps in the surface treatment process of the present invention.
FIG. 2 is a graph showing wedge crack extension for a sol-coated titanium alloy of the present invention compared with a chromic acid anodize standard.
FIG. 3 is a graph showing wedge crack extension for a sol-coated aluminum alloy of the present invention compared with a phosphoric acid anodized standard.
FIG. 4 is a chart showing lap shear ultimate stress test results for several coupons of titanium-6Al-4V alloy adhered with Cytec FM-5 polyimide adhesive.
FIG. 5 is a chart showing floating roller peel resistance test results for sol-coated 2024 and 7075 aluminum alloys compared with phosphoric acid anodize standards.
FIG. 6 is a graph showing cumulative crack growth of alcohol-based and water-based sol coatings on a titanium alloy as a function of the duration of exposure to hot/wet conditions.
FIG. 7 is a graph showing the effect of surface cleaning and pretreatment by plotting cumulative crack growth against the duration of exposure to hot/wet conditions for samples with differing surface treatments.
FIG. 8 is a graph showing the effect of drying time at 230° F. on the time to failure of wedge crack extension test samples.
FIG. 9 is a graph showing the effect of spraying versus dipping (immersing) to apply the coating, plotting cumulative crack growth against the duration of exposure to hot/wet conditions.
FIG. 10 is a graph showing cumulative crack growth as a function of extended exposure to hot/wet conditions comparing sol-coated metals with chromic acid anodized standards.
FIG. 11 is an isometric view of a typical hybrid laminate.
FIG. 12 is an isometric view of a sandwich panel having hybrid laminate skins and a honeycomb core as typically used in an aerospace skin panel.
FIG. 13 is a sectional view showing the typical layers in a sol coated metal product, here illustrated as a lap joint having an adhesive bond.
FIG. 14 is a schematic sectional view of the sol coating.
FIG. 15 is another schematic sectional view of the sol coating for paint adhesion showing the interfaces at the metal and resin interfaces and the peptizing (i.e. crosslinking between the metals) within the sol coating between the Zr and Si.



DETAILED DESCRIPTION OF THE INVENTION
First, we will discuss some generally applicable aspects of the sol and of the sol coating. Then, we will discuss the pigmented sol that is the focus of the present invention.
1. The Sol Coating
Sol coating of metals achieves resin-to-substrate bonding via chemical linkages (covalent bonds, hydrogen bonds, or van der Waals forces) while minimizing environmental impacts otherwise caused by the traditional use of highly diluted hazardous metals. A preferred sol for making the sol coating (also called a sol-gel film) on a metal substrate includes an organozirconium compound (such as tetra-n-propoxyzirconium) to bond covalently to the metal through Zr and an organosilane (such as 3-glycidoxypropyltrimethoxysilane) to bond covalently to the organic primer, adhesive, or resin (with an acetic acid catalyst in water-based formulations as a catalyst for the silane and as a hydrolysis rate stabilizer for the zirconate).
In a successful surface treatment, the typical failure mode for adhesively bonded specimens in a hot/wet environment is cohesive failure in the organic adhesive layer. In such cases, the sol-gel film is stronger than the bulk adhesive, so the adhesive bond is as strong as possible.
We use sol-gel chemistry to develop binder coatings about 20-500 nm thick that produce a gradient from the metallic surface through a hybrid organometallic sol-gel film to the adhesive. Polishing the surface may improve our control of the coating thickness. If the film is too thick, it becomes glassy. Bond strength and durability in our preferred sol coating is increased by including organosilanes and organozirconium compounds. The organosilanes covalently bond to or otherwise associate with the organic adhesive resin or primer. Ideally, covalent bonding also occurs at the interface between the sol-gel and metal surface. Mechanical interactions may also play a role depending on the design (i.e., porosity, microstructure) of the substrate or the sol coating. Durability of the sol-gel film in humid conditions depends on whether the film rehydrates.
The term “sol-gel,” a contraction of solution-gelation, refers to a series of reactions where a soluble metal species (typically a metal alkoxide or metal salt) hydrolyzes to form a metal hydroxide. The soluble metal species usually contain organic ligands tailored to correspond with the resin in the bonded structure. The metal hydroxides condense (peptize) in solution to form a hybrid organic/inorganic polymer. Depending on reaction conditions, the metal polymers may condense to colloidal particles or they may grow to form a network gel. The ratio of organics to inorganics in the polymer matrix is controlled to maximize performance for a particular application.
Many metals are known to undergo sol-gel reactions. Silicon and aluminum sol-gel systems have been studied extensively. Representative sol-gel hydrolysis and condensation reactions, using silicon as an example, are shown in equations (1) and (2).

Si(OEt)4+2H2OSi(OH)4+4 EtOH  hydrolysis (1)

Si(OH)4SiO2+2 H2O  condensation (2)

wherein Et is ethyl (CH3CH2—). The hydrolysis and condensation reactions can be complete, resulting in complete conversion into the metal oxide or a hydrous metal hydroxide. They can also be partial, leaving more of the alkoxide functionalities in the finished gel. Depending upon the reaction conditions, reactions (1) and (2) can produce discrete oxide particulates, as demonstrated in the synthesis of nanoscale particles, or they can form a network gel, which can be exploited in film formation. The solubility of the resulting gel in a solvent will depend upon the size of the particles and degree of network formation.

Surface preparation is important, if not critical, to produce strong, durable bonds. We prefer a clean and chemically active metal surface to bond a sol-gel film from the sol by spraying, immersing, or drenching. Cleaning is a key factor toward obtaining good adhesion. If the surface is dirty, bonding is blocked by the dirt or occurs between the sol and the dirt rather than between the sol and the surface. Obtaining a chemically active surface is not trivial. Titanium produces a passive oxide surface. A bare, pure titanium surface will immediately oxidize in air or dry oxygen to form a barrier titanium oxide film which has a thickness of 2-4 nm (20-40 Å). Titanium surface oxides do not hydrolyze as readily as aluminum surface oxides to form active metal hydroxides. Water will, however, chemisorb onto the surface of the titanium oxide. Aluminum oxidizes as quickly, or more quickly in air.
HNO3—HF etching of titanium alloys removes TiO2 alpha case, but creates a smooth surface which is difficult to bond to. Traditional alkaline etches like TURCO 5578 or OAKITE 160, produce a roughened surface better suited for adhesive bonding, but produce a tenacious smut layer. The smut causes adhesion to be reduced dramatically. Extended soaking in hot HNO3 after the alkaline etch still leaves some smut. In our preferred process, we clean and rinse the surface, etch with HNO3—HF, rinse again, and alkaline etch. Again after another rinse, we desmut the surface with BOECLENE once or in multiple stages to produce a clean and active surface best suited for adhesive bonding through the sol coating of the present invention.
Our model of the formation of a sol-gel film on titanium involves Lewis acid/base interaction of a hydrolyzed zirconium alkoxide, an organosilane, or both in the sol with the titanium oxide surface. This interaction is possibly assisted by chemisorbed water to cause the formation of a coupled Zr—O—Ti or Si—O—Ti linkage and a new Ti—OH bond on the surface. A similar reaction occurs on aluminum. The ability of the metal alkoxides to covalently bond with the metal surface most likely requires more energy in the case of titanium than aluminum. Complete coupling and formation of covalent bonds with titanium alloys may not occur until the part reaches higher temperatures, such as they usually experience during adhesive curing.
Sol-gel chemistry is quite versatile. Reaction conditions (for example, concentration of reagents and catalyst type) control the relative rates of the hydrolysis and condensation reactions. Sol-gel solutions can be prepared which readily form thin films or which condense to fine colloidal particles. Starting materials and reaction conditions can produce films with morphology similar to surface coatings achieved with anodize and etch processes. Density, porosity, and microstructure can be tailored by controlling the chemistry of the sol.
Sol-gel condensation reactions are affected by the acid-base character of the metal/oxide surface. The isoelectronic point (IEP, a measure of surface pH) for titanium is more acidic (IEP=6.0) than an aluminum surface (IEP=9.2), which changes the surface chemistry of the metal with the sol.
2. Screening Studies on Sol Coatings
We conducted screening studies to define the sol formulation on test panels-of titanium-6Al-4V (Ti-6-4) alloy sized 6′′×6′′×0.50′′ initially prepared by degreasing the surface with an aqueous detergent (11, FIG. 1). The panels were then either grit blasted with #180 grit alumina (13) followed by a final aqueous detergent cleaning to minimize the presence of loosely adhered grit or acid etched in a HNO3—HF immersion tank (not shown in FIG. 1). Our preferred sol for these tests consisted of a dilute aqueous mixture of 3-glycidoxypropyltrimethoxysilane (GTMS) and tetra-n-propoxyzirconium (TPOZ) with an acetic acid catalyst. Typically, the panels were dip-coated with a 10 minute immersion time (15), held under ambient conditions for 15 to 30 minutes (17), and dried in a 230° F. oven for 15-30 minutes (19). With the sol coating complete the specimens were ready for accepting primer (21) and then an epoxy adhesive (23). We also tested corresponding formulations using alcohol as the carrier or solvent. These epoxy sols typically have a pH around 4-5.
Our test specimens were primed with BMS 5-89 chromated adhesive primer (American Cyanamid BR127). Two sol coated panels were then bonded together to form an adhesive lap joint in an autoclave using BMS 5-101 Type II Grade (Dexter-Hysol EA 9628) 250° F. cure epoxy adhesive.
Screening level testing used the ASTM D 3762 Wedge Test with exposure at 140° F. and greater than 95% relative humidity to test the bond strength. The bonded panels were cut into five 1′′×6′′ strip specimens and wedges were driven into the bondline. Progress of the crack along the bondline was measured after the initial driving of the wedge, and after exposure to 140° F. and greater than 95% relative humidity for one hour, 24 hours, one week, and longer. Samples were monitored in the humidity chamber for over 2500 hours total exposure time. Typical test results compared with conventional chromic acid anodizing (CAA) are shown in FIG. 2. Test data for comparable aluminum specimens with 7075 or 2024 aluminum alloys are shown in FIG. 3. Here, the standard surface treatment for comparison was phosphoric acid anodizing (PAA).
FIG. 4 reports test results of the ultimate strength of Ti-6-4/FM-5 polyimide adhesive lap joints. FIG. 5 reports the average roller peel resistance of aluminum/epoxy specimens similar to those made for the crack growth tests reported in FIG. 3.
Additionally, lap shear testing showed good wedge crack screening characteristics. Finger panels were primed and lap bonded with the 5-101 adhesive. Measurements were taken at −65° F., room temperature, and 165° F.
A water-based system alleviates many of the flammability, safety, toxicity, and environmental concerns associated with the process when the sol is alcohol-based. We chose a glycidoxysilane (an epoxy) because of its stability in solution and its ability to crosslink with common, aerospace epoxy, urethane, or cyanate ester adhesives. The silane is acid-base neutral (pH=7.0) so its presence in the sol mixture does not increase the relative hydrolysis and condensation rates of the alkoxides. Sols including the organosilanes are relatively easy to prepare and to apply with reproducible results.
The choice of the organosilane coupling agent was a significant factor in improving hot/wet stability of the BMS epoxy bonding system. The GTMS has an active epoxy group which can react with the bond primer. GTMS did not form strong Lewis acid-base interactions with the hydrated titanium oxide substrate. The titanium oxide surface was more accessible to the zirconium organometallic when GTMS was used, allowing the desired stratification of the sol-gel film in essentially a monolayer with the epoxy groups of the silane coupling agents oriented toward the primer. We believe this orientation allowed strong covalent bonding to develop between the titanium substrate and zirconia and silica (i.e. M-O-M bonds), as well as maximizing bonding between the epoxy moiety of the GTMS to the epoxy adhesive. The ideal concentration will depend upon the mode of application. A higher concentration may be preferred for drench or spray applications.
For polyimides (including bismaleimides), we usually replace GTMS with an aminoalkylsilane or an aminoarylsilane to match the silane coupling chemistry with the resin system. In these sols which operate best at a pH 8-9, we add ammonium hydroxide in small amounts to adjust the pH and to disrupt the Zr-acetate complex that otherwise forms.
Physical size of the silane coupling agent also has an effect on adhesion. Aluminum studies revealed that both the initial adhesion and hydrolytic stability decreased when epoxycyclohexylpropyltrimethoxysilane was used instead of GTMS as the coupling agent. We attribute the difference in performance to a difference in size of the organic functionality. This size effect is most likely the result of physical interference of both hydrolysis and condensation reactions by the bulky alkyl group attached directly to the silicon. Hydrolysis was incomplete and the silicon hydroxide could not effectively condense with the aluminum surface. These results suggest that the most effective coupling agents for a spray or drench coating application will be smaller so as not to sterically hinder hydrolysis and condensation reactions.
The concentrations of the reactants in the sol were generally determined as volume percentages. In the screening tests, a 2 vol % of GTMS and 1 vol % of TPOZ was used. This concentration corresponds to a molar ratio of silicon to zirconium of 3.7:1. More organosilane is generally used in polyimide formulations than for the epoxy formulations that use GTMS. Related studies suggest that a slightly higher concentration of reactants, namely a total of (Si+Zr)=4.4 volume % may yield better results, so the ratio of GTMS to TPOZ might need further adjustment to obtain the optimal performance (strongest surface adherence). We believe that a higher adhesion will occur with a mixed (Zr+Si) sol because of the more chemically active Zr. The sol might also include cerium, yttrium, titanium, or lanthanum organometallics, such as yttrium acetate trihydrate or other hydrates, yttrium 2-ethylhexanoate, i-proproxyyttrium, methoxyethoxyyttrium, yttrium nitrate, cerium acetate hydrate, cerium acetylacetonate hydrate, cerium 2-ethylhexanolate, i-propoxycerium, cerium stearate, cerium nitrate, lanthanum nitrate hexahydrate, lanthanum acetate hydrate, or lanthanum acetylacetonate, or an aluminum alkoxide, together with the Zr or in its place.
The organozirconium compound reduces or minimizes the diffusion of oxygen to the surface and to stabilize the metal-resin interface. As a variation to the sol coating process, a stabilizer might be applied to the surface to form a barrier film prior to applying the hybrid organometallic sol to form the sol-gel film.
Preliminary screening tests were also conducted with and without conductive pigments on various substrates. For the purpose of this initial study, a 10% pigment loading level (with respect to sol-gel binder weight) was used to examine coating uniformity and sprayability. In these tests, we used aluminum and nickel metallic fillers. While we do not expect these fillers to be in the optimized formulations, they were a low cost way of testing compositional changes and loading levels for the conductive systems.
Table 1 describes sample configuration and initial results from these screening studies. Within a series of specimens, four different substrates were tested (aluminum 7075-T6, cyanate ester-carbon fiber composite, mylar, and glass) at three coating thicknesses. Samples series #2 consisted of the unpigmented silicon-zirconium sol-gel binder having GTMS and TPOZ at a concentration of 10 vol %. This series was carried out to get control information about the coating system. The pigmented sols used 10 vol % GTMS/TPOZ sol as the vehicle. Sample series #3 added an aluminum leafing pigment to the GTMS/TPOZ sol while series #4 and #6 used an aluminum non-leafing pigment at 10% and 20% by volume, respectively. Aluminum proved to be a poor pigment with which to achieve a conductive coating. Sample series #5 and #12 added a nickel flake pigment at different concentrations. Sample series #8, #10, #13, #14, #17, and #18 used carbon black at several concentrations in the GTMS/TPOZ sol. While conductivity could be obtained at higher concentrations, the adhesion of the sol-gel was reduced. Sample series #15, #16, #19, and #20 used different concentrations of tin oxide, and achieved conductive coatings at concentrations of 30 vol % pigment. Sample series #21, #22, and #26 added different concentrations of silvered spheres, but failed to provide acceptable, conductive, sol-gel coatings. Sample series #24 added indium tin oxide, but obtained no response at a concentration of 20 vol %. Finally, sample series #23 and #27 added different mixtures of nickel flake and carbon black to achieve conductive sol-gel coatings on glass.







TABLE 1







Conductive Pigment Screening Tests with Sol-Gel Coating


(GTMS/TPOZ 10 vol %)

















Coating
Surface



Sample

Pigment

Thickness
Resistivity


#
Conductive filler
Vol %
Substrate
(mils)
(ohms/sq)
Comments
















2-1
none
0
Al 7075 T6
0

did not wet


2-2
none
0
C fib/cyan est


out on Mylar


2-3
none
0
Mylar
0.1
no response


2-4
none
0
glass
0
no response


2-5
none
0
Al 7075 T6
0.1


2-6
none
0
C fib/cyan est


2-7
none
0
Mylar
0.1
no response


2-8
none
0
glass
0.2
no response


2-9
none
0
Al 7075 T6
0.2


2-10
none
0
C fib/cyan est


2-11
none
0
Mylar
0.2
no response


2-12
none
0
glass
0.2
no response


3-1
Al 13 um leaf
10
Al 7075 T6
0.4

Al leaf did


3-2
Al 13 um leaf
10
C fib/cyan est


not disperse


3-3
Al 13 um leaf
10
Mylar
0.3
no response


3-4
Al 13 um leaf
10
glass
0.2
no response


3-5
Al 13 um leaf
10
Al 7075 T6
0.4


3-6
Al 13 um leaf
10
C fib/cyan est


3-7
Al 13 um leaf
10
Mylar
0.5
no response


3-8
Al 13 um leaf
10
glass
0.4
no response


3-9
Al 13 um leaf
10
Al 7075 T6
0.6


3-10
Al 13 um leaf
10
C fib/cyan est


3-11
Al 13 um leaf
10
Mylar
0.4
no response


3-12
Al 13 um leaf
10
glass
0.4
no response


4-1
Al 17 um nleaf
10
Al 7075 T6
0.4

Coated nicely


4-2
Al 17 um nleaf
10
C fib/cyan est


4-3
Al 17 um nleaf
10
Mylar
0.3
no response


4-4
Al 17 um nleaf
10
glass
0.2
no response


4-5
Al 17 um nleaf
10
Al 7075 T6
0.6


4-6
Al 17 um nleaf
10
C fib/cyan est


4-7
Al 17 um nleaf
10
Mylar
0.5
no response


4-8
Al 17 um nleaf
10
glass
0.5
no response


4-9
Al 17 um nleaf
10
Al 7075 T6
0.6


4-10
Al 17 um nleaf
10
C fib/cyan est


4-11
Al 17 um nleaf
10
Mylar
0.6
no response


4-12
Al 17 um nleaf
10
glass
0.6
no response


5-1
Ni flake
10
Al 7075 T6
0.3

Ni settled out


5-2
Ni flake
10
C fib/cyan est


must agitate


5-3
Ni flake
10
Mylar
0.4
no response
briskly


5-4
Ni flake
10
glass
0.2
no response


5-5
Ni flake
10
Al 7075 T6
0.5


5-6
Ni flake
10
C fib/cyan est


5-7
Ni flake
10
Mylar
0.5
no response


5-8
Ni flake
10
glass
0.6
.51 E7


5-9
Ni flake
10
Al 7075 T6
0.4


5-10
Ni flake
10
C fib/cyan est


5-11
Ni flake
10
Mylar
0.5
.33 E5


5-12
Ni flake
10
glass
0.6
.24 E5


6-1
Al 17 um nleaf
20
Al 7075 T6
0.5

sprayed well


6-2
Al 17 um nleaf
20
C fib/cyan est
0.4

opaque


6-3
Al 17 um nleaf
20
glass
0.6
no response


6-4
Al 17 um nleaf
20
Al 7075 T6
0.7


6-5
Al 17 um nleaf
20
C fib/cyan est
0.6


6-6
Al 17 um nleaf
20
glass
0.8
no response


8-1
Carbon black
4
Al 7075 T6
0.5

splotchy


8-2
Carbon black
4
C fib/cyan est
0.4

appearance,


8-3
Carbon black
4
glass
0.5
no response
poor pigment


8-4
Carbon black
4
Al 7075 T6
0.7

dispersion


8-5
Carbon black
4
C fib/cyan est
0.6


8-6
Carbon black
4
glass
0.7
no response


10-1
Carbon black
5
Al 7075 T6
0.3

surfactant


10-2
Carbon black
5
C fib/cyan est
0.1

added,


10-3
Carbon black
5
glass
0.3
.68 E6
did not


10-4
Carbon black
5
Al 7075 T6
0.5

spray


10-5
Carbon black
5
C fib/cyan est
0.3

well


10-6
Carbon black
5
glass
0.3
.94 E5


12-1
Ni flake
20
Al 7075 T6
0.8

coating is rough


12-2
Ni flake
20
C fib/cyan est
0.6


12-3
Ni flake
20
glass
0.6
.98 E2


12-4
Ni flake
20
Al 7075 T6
1.1


12-5
Ni flake
20
C fib/cyan est
0.5


12-6
Ni flake
20
glass
1.1
.54 E2


13-1
Carbon black
5
Al 7075 T6
0.3

different


13-2
Carbon black
5
C fib/cyan est
0.2

surfactant,


13-3
Carbon black
5
glass
0.3
no response
sprayed OK


13-4
Carbon black
5
Al 7075 T6
0.3


13-5
Carbon black
5
C fib/cyan est
0.3


13-6
Carbon black
5
glass
0.1
.47 E6


14-1
Carbon black
20
Al 7075 T6
na

milled longer


14-2
Carbon black
20
C fib/cyan est
na

with surfactant,


14-3
Carbon black
20
glass
na
.21 E4
sprayed OK


14-4
Carbon black
20
Al 7075 T6
0.9

but cracks


14-5
Carbon black
20
C fib/cyan est
0.9

appeared


14-6
Carbon black
20
glass
0.7
.20 E4


15-1
Tin oxide - 1
10
Al 7075 T6
0.3

Coating had fish


15-2
Tin oxide - 1
10
C fib/cyan est
0.5

eyes and didn't


15-3
Tin oxide - 1
10
glass
0.3
no response
cover well


15-4
Tin oxide - 1
10
Al 7075 T6
0.5


15-5
Tin oxide - 1
10
C fib/cyan est
0.4


15-6
Tin oxide - 1
10
glass
0.7
no response


16-1
Tin oxide - 1
20
Al 7075 T6
0.4

not very opaque,


16-2
Tin oxide - 1
20
C fib/cyan est
0.6

poor coverage


16-3
Tin oxide - 1
20
glass
0.4
no response


16-4
Tin oxide - 1
20
Al 7075 T6
0.5


16-5
Tin oxide - 1
20
C fib/cyan est
0.4


16-6
Tin oxide - 1
20
glass
0.5
no response


17-1
Carbon black
15
Al 7075 T6
0.3

sprayed well


17-2
Carbon black
15
C fib/cyan est
0.3

initially but after


17-3
Carbon black
15
glass
0.2
.12 E4
6 passes cracks


17-4
Carbon black
15
Al 7075 T6
0.5

formed


17-5
Carbon black
15
C fib/cyan est
0.5


17-6
Carbon black
15
glass
0.8
.24 E4


18-1
Carbon black
25
Al 7075 T6
0.4

cracked after 4


18-2
Carbon black
25
C fib/cyan est
0.3

passes,


18-3
Carbon black
25
glass
0.3
.15 E4
poor adhesion


18-4
Carbon black
25
Al 7075 T6
1.3


18-5
Carbon black
25
C fib/cyan est
1


18-6
Carbon black
25
glass
1.4
.40 E4


19-1
Tin oxide - 1
30
Al 7075 T6
0.6

sprayed well


19-2
Tin oxide - 1
30
C fib/cyan est
0.2


19-3
Tin oxide - 1
30
glass
0.4
.18 E7


19-4
Tin oxide - 1
30
Al 7075 T6
0.7


19-5
Tin oxide - 1
30
C fib/cyan est
0.8


19-6
Tin oxide - 1
30
glass
0.6
.37 E6


20-1
Tin oxide - 2
30
Al 7075 T6
0.3

sprayed well


20-2
Tin oxide - 2
30
C fib/cyan est
0.3


20-3
Tin oxide - 2
30
glass
0.3
.36 E6


20-4
Tin oxide - 2
30
Al 7075 T6
0.5


20-5
Tin oxide - 2
30
C fib/cyan est
0.5


20-6
Tin oxide - 2
30
glass
0.4
.17 E6


21-1
Silvered sphere
10
Al 7075 T6
1.5

very low coverage


21-2
Silvered sphere
10
C fib/cyan est
1.3


21-3
Silvered sphere
10
glass
1.7
no response


21-4
Silvered sphere
10
Al 7075 T6
1.8


21-5
Silvered sphere
10
C fib/cyan est
1.2


21-6
Silvered sphere
10
glass
1.9
no response


22-1
Silvered sphere
20
Al 7075 T6
1.8

low coverage


22-2
Silvered sphere
20
C fib/cyan est
1.6

nearly transparent


22-3
Silvered sphere
20
glass
1.6
no response
after 8 passes


22-4
Silvered sphere
20
Al 7075 T6
2


22-5
Silvered sphere
20
C fib/cyan est
1.7


22-6
Silvered sphere
20
glass
1.9
no response


23-1
Ni/Carbon bl
15/5
Al 7075 T6
0.7

sprayed well


23-2
Ni/Carbon bl
15/5
C fib/cyan est
0.5


23-3
Ni/Carbon bl
15/5
glass
0.5
.15 E3


23-4
Ni/Carbon bl
15/5
Al 7075 T6
1.2


23-5
Ni/Carbon bl
15/5
C fib/cyan est
1.2


23-6
Ni/Carbon bl
15/5
glass
1.1
.26 E2


24-1
In/Sn oxide
20
Al 7075 T6
0.7

not very uniform


24-2
In/Sn oxide
20
C fib/cyan est
0.4

settled while


24-3
In/Sn oxide
20
glass
0.5
no response
spraying


24-4
In/Sn oxide
20
Al 7075 T6
0.8


24-5
In/Sn oxide
20
C fib/cyan est
0.6


24-6
In/Sn oxide
20
glass
0.7
no response


25-1
Tin oxide - 1
40
Al 7075 T6
0.6

coating very


25-2
Tin oxide - 1
40
C fib/cyan est
0.4

opaque and


25-3
Tin oxide - 1
40
glass

.17 E7
uniform


25-4
Tin oxide - 1
40
Al 7075 T6
1.1


25-5
Tin oxide - 1
40
C fib/cyan est
1.2


25-6
Tin oxide - 1
40
glass

.61 E6


26-1
Silvered sphere
30
Al 7075 T6
1.8

did not spray


26-2
Silvered sphere
30
C fib/cyan est
1.6

well,


26-3
Silvered sphere
30
glass

no response
non-uniform lay


26-4
Silvered sphere
30
Al 7075 T6
2.1

down of spheres,


26-5
Silvered sphere
30
C fib/cyan est
1.9

tend to migrate


26-6
Silvered sphere
30
glass

no response


27-1
Ni/Carbon bl
10/2.5
Al 7075 T6
0.6

sprayed well


27-2
Ni/Carbon bl
10/2.5
C fib/cyan est
0.4


27-3
Ni/Carbon bl
10/2.5
glass

1.47 E3


27-4
Ni/Carbon bl
10/2.5
Al 7075 T6
0.9


27-5
Ni/Carbon bl
10/2.5
C fib/cyan est
1.1


27-6
Ni/Carbon bl
10/2.5
glass

1.09 E2









Surface conductivity measurements were conducted using a four-point probe under ambient conditions. Most of the specimens in this series showed no electrical response down to the detection limits (approximately 1×108 ohm/sq) of the probe. The sol-gel binder alone (series #2) was not expected to be conductive. Pigmentation at a 10% loading level was not high enough to produce conductivity in these aluminum specimens. The 0.5 mil-thick sol-gel coating doped with nickel flake was slightly conductive, showing values of approximately 3×104 ohms/sq.
Mechanical evaluation of the coatings in Table 1 consisted of tape adhesion tests and some impact testing. The adhesion testing shows the original binder (series #2) has excellent adhesion on both metal and composite substrates. The adhesion test results varied with addition of fillers, with some loss of adhesion occurring in certain pigment loaded specimens. At this point, this loss of adhesion is not of great concern. No special care or surface treatments on the substrates were used in these screening studies. The substrate surfaces were simply degreased and slightly roughed using a Scotchbrite pad. After a coating with acceptable conductivity has been formulated, we will go back and optimize the adhesion aspects of the formulation and interface.
The sol can be applied in several coats and may have a gradient from ceramic character to more organic character in depth from adjacent the metal surface to the interface with a paint, resin composite, or adhesive. Ceramic character can be enhanced by minimizing the organic side chains (ligands) on the Si in the sol. For example, we might use tetra-ethyl-orthosilicate (TEOS) as the organosilane for the first coat of sol. Then, we may apply a layer having equal amounts of TEOS and GTMS. Dissolve the TEOS in alcohol to hydrolyze it before adding the mixture to water. The last coat in this example might use only GTMS as the organosilane. We believe that a more ceramic character adjacent the metal might create a more effective barrier to block water or other corrosive agents. Similar adjustments might be made with the organozirconium to produce stronger ceramic character. Of course, additional or fewer layers might be applied. Commonly we apply 3-6 layers or coats of the sol even if we do not tailor the sol-gel by adjusting the organometallic ingredients in the sol. In all cases, however, we maintain the ratio of the Zr:Si in each layer.
Alcohol-based sols allow us to precisely control the amount of hydrolysis. Optimization of the water-based system, however, actually yielded better hot/wet durability results than the alcohol-based system, as demonstrated by comparing similar alcohol and water-based coatings (FIG. 6). These results, however, may vary if the alcohol-based sol includes hydrolysis control for the zirconium.
Aging of the sol which we call the “induction time” is another important factor in using our sols. Complete hydrolysis and condensation of the organometallic in the sol-gel film is important to develop a hydrolytically stable metal oxide film in the metal. The presence of hydrolyzable alkoxides in the sol-gel film will have two adverse effects. First, every residual alkoxide represents an incomplete condensation site between the metal and the coupling agents. Incomplete condensation, therefore, decreases the ultimate bond strength of the sol-gel film. Second, in a humid environment, these alkoxide residues can hydrolyze. The structural changes accompanying hydrolysis cause stress in the sol-gel film which, we believe, promotes failure to occur within the sol-gel film or at one of the interfaces (metal/film or film/primer or adhesive).
Aging is a function of the rates of the hydrolysis reaction of the zirconium alkoxides and the organosilane. Tetra-n-propoxyzirconium reacts more rapidly with water or other active hydrogens than the silane. The zirconate hydrolyzes rapidly using ambient moisture and condenses with itself or with absorbed water on the titanium surface. If not properly controlled, this zirconate hydrolysis self-condensation reaction can produce insoluble zirconium oxyhydroxides which will precipitate and become nonreactive.
If, however, the sol is applied too short a time after being made, the organosilane may not be fully hydrolyzed. As the sol ages, the hydrolyzed silicon and zirconium components may condense among themselves, forming oligomers and networks. These networks will eventually become visible to the naked eye and become insoluble. The ideal solution age is at the point that the zirconium and silicon are hydrolyzed sufficiently that zirconium and silicon react with the metal surface. At this point, generally some metal polymers and networks have formed in the sol and they will give the sol-gel film some structure.
We made the zirconium and silicon components hydrolyze on a similar time scale by mixing the zirconium alkoxide with glacial acetic acid to stabilize the fast reacting four-coordinate zirconate center and to enable a water-based system. This mixing effectively changed the geometric and electronic nature of the zirconium component. Other organic acids, like citric acid, can be substituted for the acetic acid. We can also use glycols, ethoxyethanol, H2N—CH2—CH2—OH, or the like.
The relative rates of the hydrolysis and condensation reactions involved in the sol coating process are controlled by the type of catalyst (either acid or base), the concentrations of the reagents in the reactions, the metal alkoxide selected, and the water available for hydrolysis. An acidic catalyst promotes the hydrolysis reaction over condensation while a basic catalyst does the opposite. We examined the effects of various acidic catalysts, such as acetic acid and nitric acid, and basic catalysts, such as ammonium hydroxide and triethylamine. For these formulations, the basic catalysts promoted the condensation reactions too vigorously, which shortened the pot-life of the solution. Colloidal zirconate-silicate particles precipitated too soon after the sol was mixed. The nitric acid was effective as a catalyst, but did not stabilize the zirconate via a coordinating ligand like the acetate ion in acetic acid, so aging of the sol produced differing, unpredictable results. Thus, acetic acid was chosen as the preferred catalyst. We make the sols dilute to control the self-condensation reactions, thereby extending the pot life. Still, the sols must be used soon after they are prepared.
Acetic acid functions as a catalyst for the hydrolysis of the organosilane and as a hydrolysis rate stabilizer for the zirconium complex. The acetic acid helps to make both ingredients ready for bonding at comparable rates. In general throughout our screening tests, we added 0.13 moles of glacial acetic acid to 0.091 moles of the organozirconium before combining the organosilane with the organozirconium. We have not optimized the amount of glacial acetic acid, however, in our initial screening tests.
In our tests, we cleaned the metal surface using abrasive blasting or acid etching with HNO3—HF in both liquid and paste form. Since the sol reacts directly with chemical moieties on the substrate surface, adhesion is sensitive to surface precleaning. Residues or smut resulting from the cleaning processes can drastically effect the adhesive bond performance, because residues and smut are relatively loosely adhered to the surface.
FIG. 7 shows the wedge crack test results for Ti-6Al-4V panels given a variety of surface pretreatments and then coated with the same sol. Our results indicate that degreasing with an aqueous detergent with a gentle scrubbing action or agitation was sufficient for removing most soils and grease from the metal surface. Subsequent grit blasting was generally better than acid etching for pretreatment of the surface. We believe that grit blasting enhanced mechanical interaction by producing a macrorough surface. The grit blasted surface may hold the sol on the surface longer during the ambient temperature flash, allowing a longer reaction time between the sol and surface, but the time difference is rather short. Prehydrolysis of the surface using steamy or hot water may activate the metal by populating the surface with chemisorbed water. The water on the surface can react with the activated surface to produce surface hydroxyls which are available for condensation with the sol. Surface hydroxyls are especially important for titanium alloys.
The two best performing sets of samples in our pigment-free sol were both grit blasted with #180 alumina and had the roughest surfaces. Of these two grit blasted samples, the set which was cleaned with Alconox detergent following grit blasting had better performance than one wiped only with methyl ethyl ketone (MEK). Solvent wiping of the rough surfaces of grit blasted panels with lint free cloth frequently left small shreds or fiber residues on the substrates. Cloth residues increased with higher pressure exerted on the wiping cloth. Test results for panels etched for one minute in HNO3—HF did not perform as well as the grit blasted panels. The poorest wedge crack test performance was obtained from panels abraded by hand with #80 and #150 grit silicon carbide sandpaper. The sandpaper produced a relatively non-uniform surface that typically was contaminated with silicon carbide. Detergent washing did not remove the contamination. Sanding does not produce the same mechanical surface as grit blasting.
A paste etch process was considered as an alternative to the HNO3—HF acid etch bath for field repair. The paste mixed the nitric and hydrofluoric acid in an emulsifier. It was applied with a brush on the surface of the titanium panels. Four 6′′×5′′ titanium panels were solvent wiped and prepared for the process. Hydrogen bubbles were produced on the surface of the metal during the process by the reaction of the acid and the metal surface. These bubbles became encapsulated in the paste. A continuous brushing motion over the surface of the panel was necessary to keep the etchant in contact with the titanium. Without brushing, the etching was uneven.
TURCO 5578 alkaline etch produces a mat finish, similar to an anodize, resulting from the formation of a microrough surface. This pretreatment shows superior hot/wet durability.
The use of conventional dry grit blasting as a surface preparation pretreatment prior to sol coating has both advantages and disadvantages depending on the type of metal surface to be treated and the environment in which the process is being carried out. Grit blasting produced the highest strength and most durable adhesive bonds of the tested surface treatments over the course of this program. Grit blasting should work well in practice on thicker panels or parts requiring limited amounts of blasting. Care must be taken not to warp the panel as the result of stresses introduced during the blasting.
Grit blasting cannot be used on titanium foil or-honeycomb core without serious risk of damage to the substrate or on fatigue critical parts. Blasting produces holes in the metal in these cases. Complex parts might be difficult to access to produce a uniform finish. Although the equipment and materials required for grit blasting are not exotic, they may not be available at sites where sol coatings could otherwise easily be applied. We do not use it when applying pigmented sols.
In other tests, we blasted titanium panels with different grit sizes of alumina #46 grit, #180 grit, and a very fine polishing alumina with an average size of 50 micrometers. All of the grit sizes evenly abraded the surface and yielded a uniform matte finish. Surface roughness was measured using a surface profilometer, using a half inch traverse and a 0.03 cutoff. The average roughness (Ra) was 144 microinches for the #46 grit panel, 30 for the #180 grit panel, and 22 for the panel blasted with the fine grit. Surface contaminants, like heavy greases or oils, were not easily removed during grit blasting using the fine alumina powders. The grit was simply imbedded into the contaminant and lost all velocity. The finest alumina grit was too friable and broke down quickly during the blasting process. After a certain time period, the very fine particles were no longer effective at abrading the surface. The dust was hard to contain within the sandblasting apparatus.
We used scanning Auger microscopy to analyze the panels after blasting. The effective oxide thickness of the non-blasted area was measured at approximately 200 Å, while the total structured surface was about 2000 Å for that of the blasted area. Bright particles were observed imbedded into the surface and were verified to contain primarily aluminum and oxygen, most likely as Al2O3. Acid etching removed the embedded alumina particles from the titanium surface only after the titanium had been etched away and removed from around the particles. Unfortunately, post-blasting etching also removed the roughened texture of the surface. We do not know the role alumina particles play, if any, in adhesion to the grit blasted surface.
No single surface pretreatment appears to provide optimum results over the full range of substrates. Various combinations of acid etch and alkaline etch treatments apparently work well on certain alloys, but questions remain as to whether they introduce hydrogen embrittlement problems for Ti foil or honeycomb core substrates. Our preferred cleaning and activation processes are prewetting, steam cleaning, alkaline etching to activate the surface, and BOECLENE or other acid etching (i.e. H2SO4—HNO3-ammonium bifluoride) to desmut titanium alloys.
The drying cycle for the sol coating is another significant processing parameter to controlling adhesive bond performance. The drying cycle includes: (1) ambient air flash time after application of the sol; (2) oven dry time at temperature; and (3) storage time in air thereafter prior to application of the primer. As shown in FIG. 8, shorter drying times at 230° F. tended to yield better results. An oven drying time of 15-30 minutes at 140-230° F. in air lead to better hot/wet durability.
FIG. 9 shows a difference we observed in performance arising from applying the sol by spraying or dipping. In this experiment, the sol was sprayed onto the substrates using a high velocity, low pressure (HVLP) spray gun. A coat consisted of light, but complete, coverage of the surface. The coating was allowed to flash dry between coats. In all cases, the sprayed coatings did not perform as well as the dipped coatings. Specimens sprayed with an even number of coats did not perform as well as specimens sprayed with an odd number of coats, this effect may be an artifact of how the gradient coating layered onto the surface. In applying an even number of coats, the GTMS may couple with the next layer's glycidoxy end of the GTMS in the next layer, the silica oriented away from the metal surface where it-cannot bond with the metal and where it interferes with the sol-gel film/primer interfacial chemistry. Consequently, there would be fewer organic functionalities-available for bonding to the resin. With an odd number of coats, a glycidoxy edge would occur at the outer surface if this intermediate reaction occurs. Hence, we suspect, we achieve better performance. This gradient effect has been seen in multilayers of phospholipids and in other biochemical systems.
We also examined a drench method for applying the sol, which combines elements of both the dip and spray processes. In this application technique, the surface of the part is wetted with a continuous stream of solution for a given period of time. The solution surface is wet with the solution for longer than in the spray process, but not as long as the dip process. One of the advantages of this technique is that it does not require the precise skills of an expert sprayer. It also uses significantly less solution than the dip (immersion) process. The coating thicknesses are controlled by the coating formulation itself and length of time that the surface is wet.
Our testing on epoxy systems was primarily conducted using solvent-based, chromated primer Cytec BR127. We conducted tests with the nonchromated water-based Cytec XBR 6757 primer. The water-based primer with a preferred sol-gel formulation yielded comparable results to the solvent-based primer.
Titanium samples (Table 2) were aqueous degreased, then grit blasted using 180 grit alumina abrasive powder, and treated with sol using a dip coating.







TABLE 2







Titanium Specimens Prepared For Epoxy Adhesion Performance Testing












Sample
Sample Size
# of

Surface



ID
(inches)
Panels
Test
Treatment
Primer















GAB01
6 × 6 × 0.125
4
Wedge Crack
GTMS/TPOZ
BR 127





Extension


GAB02
6 × 6 × 0.125
4
Wedge Crack
GTMS/TPOZ
Cytec 6757





Extension


GAB03
6 × 6 × 0.050
2
Wedge Crack
GTMS/TPOZ
BR 127





Extension


GAB04
6 × 6 × 0.050
2
Wedge Crack
GTMS/TPOZ
Cytec 6757





Extension


GAB05
4 × 7 × 0.063
12
Lap Shear,
GTMS/TPOZ
BR 127





Various Conditions


GAB06
4 × 7 × 0.063
8
Lap Shear,
GTMS/TPOZ
Cytec 6757





Various Conditions


GAB07
finger panels
6
Lap Shear,
GTMS/TPOZ
BR 127





Various Conditions


GAB08
finger panels
6
Lap Shear,
GTMS/TPOZ
Cytec 6757





Various Conditions


GAB010
6 × 6 × 0.125
4
Wedge Crack
CAA/5V
BR 127





Extension


GAB011
6 × 6 × 0.125
12
Lap Shear,
CAA/5V
BR 127





Various Conditions









The chromic acid anodize (CAA) specimens displayed 100% cohesive failure. The failure modes of the sol-gel panels varied. Panels primed with the solvent-based BR127 tended to show between 10-50% cohesive failure and the remainder adhesive failure at the adherent-sol interface, while the panels primed with the water-based XBR 6757 exhibited from 80-100% cohesive failure.
The results of crack growth tests during long term exposure to 140° F. condensing humidity are shown in FIG. 10. H133-2 is a sol that had been aged for 1.9 hrs, while H133-3 had aged for 0.2 hrs prior to application. These solutions produced coatings having crack growth comparable with the chromic acid anodize standards even after 2000 hours hot/wet exposure. The crack growth rate had leveled off at approximately 0.1 inches crack extension. Abrupt jumps in the data are due to the difficulty in visually measuring minute changes in the crack extension. Ideally, a smooth curve could be drawn into the raw data representing the growth rate over time. These results show that the hot/wet durability of these water-based sol coatings compares well with the CAA-controls.
Lap shear data were collected on an Instron Series IX Automated Materials Testing System 6.04. The sample rate was 9.1 pts/sec with a crosshead speed of 0.05 in/min. Lap shear data is listed in Table 3. Results are an average of five finger test specimens per data point.







TABLE 3







Lap Shear Data











CAA Control
Boeing SG
Boeing SG



with Cytec BR 127
with Cytec BR 127
with Cytec XBR 6757














Ultimate Stress
Failure Mode
Ultimate Stress
Failure Mode
Ultimate Stress
Failure Mode



(psi)
(% coh)
(psi)
(% coh)
(psi)
(% coh)

















−65° F.
7988
80
7900
100
8822
100


Lap Shear


RT
5935
100
6278
100
6015
100


Lap Shear


180° F.
3722
100
4123
100
3586
100


Lap Shear









The lap shear failure mode is predominantly cohesive within the adhesive layer in all of the specimens at all of the temperatures. The data for the CAA control and the sol-gel surface preparations with both primers was essentially the same within experimental error.
Lap shear coupons produced with a sol that had been aged for 150 hrs or one that had been aged for 338 hrs had essentially the same ultimate stress values. Exposure of the lap shear specimens made with sol in a hot/wet environment resulted in a 14% decrease in ultimate stress after 168 hrs and 27% after 500 hrs. A 500 hour hot/wet exposure of the CAA control specimens resulted in a 7% degradation.
Electronic Spectroscopy for Chemical Analysis (ESCA) studies conducted on an ethanol-based formulation revealed the mode of failure-during hot/wet exposure. The bonding surfaces of two previously tested wedge crack sample coupons were examined using ESCA analysis techniques. The first sample, H83KAK-1, was a grit blasted Ti-6-4 panel which had been coated with an isopropanol solution of 2% GTMS, 1% TPOZ and 1% 80%-acetic acid. It was tested at 120° F. and 95% relative humidity for 864 hours and had an average increase in the initial crack length of 0.45 inches by the end of the test.
The sample was split in half and the smaller mating surface section from adhesively failed areas of the coupon were examined. The bare titanium surface of the adhesively failed sample section had high carbon, low titanium, and small amounts of silicon and zirconium. As this surface was sputter-etched, the percentages of silicon, zirconium, and chromium increased and reached a maximum before dropping off with continued sputtering. After 300 Å of sputter etching, the carbon content had reached a minimum and the titanium, aluminum, and vanadium content had reached a maximum. At this depth, the zirconium content was about 20% below its maximum value and the silicon content was more that 50% below its maximum value. Table 4 shows the sputtering data for this system.







TABLE 4







ESCA Sputter Data for Failed Surfaces














adhesive


metal



atom
(sputter)
metal
metal
sputter

















O
40.97
28.23
36.88
31.52



Ti


2.62
22.74



C
36.89
59.61
44.36
19.06



Al
4.05
2.99
6.12
14.16



Si
11.9
4.45
3.42
5.38



Zr
2.81
0.51
0.63
2.34



Ar



2.2



N
1.1
0.91
0.95
1.45



V



1.15



Cr
2.29
1.43
1.82










Aging studies with ESCA suggest that aging the solution does not alter the surface characteristics significantly.

Roughness of the etched titanium surface prevented accurate determination of the thickness of the sol coating. ESCA measures an area of the surface approximately 600 μm in diameter. Table 4 shows the surface composition following various sputter times on the coated sample. The etched titanium surfaces have “craters” approximately 15 μm in diameter and 2-5 μm deep. Therefore, the ESCA experiment will measure about 20 “craters” and associated ridges. The sol coating is likely to be thinner on the ridges than in the craters, perhaps thin enough for the substrate material to have a measurable signal even without sputtering.
The ESCA data for both samples in Table 5 show a small amount of titanium at the surface indicating that some areas of the substrate are not coated or that sol coating on the ridges is thinner than about 130 Å. Argon plasma sputtering the surface gradually removes the sol coating, as indicated by the decrease in Si and Zr, but there is not a sharp change in surface composition. The data are consistent with a surface having roughness greater than the coating thickness.







TABLE 5







ESCA Data for Unexposed Water-based Sol-Gel Specimens










24 hr old solution
1 hr old solution
















345 Å
430 Å

430 Å




Light
Sput-
Sput-

Sput-


Atomic %
Surface
Sputter
tered
tered
Surface
tered
















Carbon
44.8
19.0
5.2
5.5
57.5
23.0


Oxygen
40.6
52.8
23.0
23.5
32.1
31.4


Titanium
3.1
9.2
51.0
54.0
2.4
31.3


Aluminum
0.6
2.4
9.8
8.3
0.6
5.8


Vanadium
—
—
2.8
2.4
—
1.7


Zirconium
2.0
3.0
0.7
1.0
0.8
0.5


Niobium
0.5
1.0
0.3
—
0.3
—


Molybdemun
0.2
0.5
0.2
—
0.2
—


Fluorine
—
0.8
—
—
—
—


Silicon
8.1
10.8
—
—
3.5
—


Nitrogen
—
—
3.3
1.8
1.1
2.4


Copper
—
—
—
—
0.3
0.3


Calcium
—
—
—
—
1.2
1.2


Argon
—
0.4
3.7
3.4
—
2.4









The theoretical composition of the fully hydrolyzed sol-gel film is 4 parts SiO1.5Gly and 1 parts ZrO2 where Gly is the glycidoxy group attached to the silicon. The (silicon+zirconium):carbon:oxygen ratio for a homogeneous coating formed from this sol is 1:4:4:3.2. The experimental value for the surface of the 24 hr old formulation specimen shows the (silicon+zirconium):carbon:oxygen ratio to be approximately 1:4:5:4.0, close to the theoretical value. The ratio of (Si+Zr):C:O ratio becomes 1:1.2:3.8. Continued sputtering further reduces the carbon signal to near background levels and the oxygen signal decreases as well. We interpret the data to indicate that the deposited film is not homogeneous. The glycidoxysilane is located primarily on the surface with the coating composition changing to zirconia and titania and finally the metallic substrate. This measured gradient is consistent with our model of formation of films from our sols and observations of increasing water aversion of substrates as coatings are deposited. The thickness of the sol coating is not accurately determined by this measurement but it appears to be a minimum of 100-300 Å. Considering the escape depth of ESCA being about 100 Å, the glycidoxy-rich surface layer is no more than about 75-150 Å thick as indicated by the decrease in the carbon level.
The low carbon level in the coating after 450 Å etch indicates that hydrolysis of the sol is essentially complete within 24 hours. Data for coatings deposited from the same sol aged for only 1 hour show significantly greater amounts of carbon both at the surface and at the 450 Å level. Incomplete hydrolysis will leave alkoxy groups attached to both silicon and zirconium. In addition, acetate groups from the incomplete hydrolysis of the stabilized zirconate will also be incorporated throughout the coating. The ESCA data do not differentiate between acetate, glycidoxy, and alcohol carbon and oxygen.
We also conducted experiments using aluminum substrates (alloys 7075 and 2024). FIG. 3 shows the cumulative crack growth or extension as a function of time for an epoxy adhesive. Crack growth was the smallest for a sol coated 7075 alloy. The hot/wet durability of the sol coated specimens was comparable with the phosphoric acid anodized (PAA) controls for 1000 hrs of testing. The sol coated specimens were acceptable as measured by BAC 5555 PAA requirements, so the sol coating is an alternative and improvement to PAA for at least these aluminum alloys.
We collected lap shear data as well for the sol coated 7075 and 2024 alloys. Room temperature (RT) results surpass the minimum threshold specified in BAC 5555. Our tests indicate that specimens primed with a waterbased nonchromated primer (Cytec XBR 6757) performed as well as or better than specimens primed with the conventional chromated, solvent-based primer (Cytec BR 127). Again, 7075 alloys had better performance than 2024 alloys. Floating roller peel test data (reported as the average of five individual specimens) showed that sol coated aluminum specimens compared favorably with the bond strengths achieved with conventional PAA controls.
Drenching v. dipping for aluminum substances has little effect on the bond strength. This fact makes the sol coating desirable for field repair and depot maintenance because specialized equipment likely is not required to obtain the benefits of sol coating. Also, the data we collected suggests that the coating process is robust rather than a “craft.” We also found little effect from drenching versus mist spraying.
Parameters such as concentration, acid catalyst, aging, hydrolysis/concentration, and the ratio of the reactants will need to be optimized for large scale and spray operation. We anticipate that these will be different than those optimized for dipping. The use of surfactants and thixotropic agents in the solution may improve the spray characteristics of the solution, but may adversely affect the bonding performance. These agents may help to provide a more uniform sprayed coating and improve the manufacturability of the process.
There are fundamental differences in the manner of film formation between spraying and dipping. With dipping or immersion coating, the thermodynamically favored products of slower reactions can dominate. With the part immersed in the solution, reactant can reach to the metal surface through mechanical, thermal, and mass transport mechanisms. Reaction products can diffuse away from the surface. The most thermodynamically stable coating will develop. In the case of spraying, only a thin film of the sol contacts the surface. Depletion of reactants can and likely does occur as the sol flows down the surface. Consequently, reaction products build up and may influence the chemistry that occurs. In addition, reaction products remain on the surface when the film dries. The sol-gel film developed with spraying is dominated by kinetically accessible products. Advantages of spraying include coating thickness control and uniformity.
The preferred zirconium compounds for making the sol are of the general formula (R—O)4 Zr wherein R is lower aliphatic having 2-5 carbon atoms, especially normal aliphatic (alkyl) groups, and, preferably, tetra-n-propoxyzirconium, because of its being readily available commercially. We believe that branched aliphatic, alicyclic, or aryl groups would also perform satisfactorily. For applications involving extended exposure to hot/wet conditions, we want the organo moiety on the zirconium to have thermo-oxidative stability. Corresponding organometallics, especially a titanium alkoxide or an aluminum alkoxide, might be used together with or in place of the zirconium compound.
The preferred organosilane compounds (available from Petrarch or Read) for making the sol are:
3-aminopropyltriethoxysilane,
3-glycidoxypropyltrimethoxysilane,
p-aminophenyltrimethoxysilane,
m-aminophenyltrimethoxysilane,
allyltrimethoxysilane
n-(2-aminoethyl)-3-aminopropyltrimethoxysilane
3-aminopropyltrimethoxysilane
3-glycidoxypropyldiisopropylethoxysilane
(3-glycidoxypropyl)methyldiethoxysilane
3-glycidoxypropyltrimethoxysilane
3-mercaptopropyltrimethoxysilane
3-mercaptopropyltriethoxysilane
3-methacryloxypropylmethyldiethoxysilane
3-methacryloxypropylmethyldimethoxysilane
3-methacryloxypropyltrimethoxysilane
n-phenylaminopropyltrimethoxysilane
vinylmethyldiethoxysilane
vinyltriethoxysilane or
vinyltrimethoxysilane.
In these organometallics, the organo moiety preferably is aliphatic or alicyclic, and generally is a lower n-alkoxy moiety having 2-5 carbon atoms. The organosilane includes typically an epoxy group (for bonding to epoxy or urethane resins or adhesives) or a primary amine (for bonding to polyimide resins or adhesives).
If the sols are alcohol-based, the preferred alcohols are ethanol, isopropanol, or another lower aliphatic alcohol.
The sols can be used to make sol-gel films on the following aluminum and titanium alloys: Al 2024; Al 7075; Ti-6-4; Ti-15-3-3-3; Ti-6-2-2-2-2; and Ti-3-2.5. The sol coating method can also be used with copper or ferrous substrates, including stainless steel or an Inconel alloy.
3. Hybrid Laminates
Sol coated metals are useful in hybrid laminates like those described in U.S. Pat. No. 4,489,123. These hybrid laminates are candidates for use as aircraft skin panels and other structural applications in subsonic or, especially, supersonic aircraft. The utility of these hybrid laminates hinges on a sound, strong adhesive bond between the metal and resin. The sol coating of the present invention provides a high strength adhesion interface at relatively low cost compared with conventional alternatives in a reasonably simple manufacturing process.
Hybrid laminates should have a high modulus (absolute strength) and be fatigue resistant so that they have long life. They should exhibit thermomechanical and thermo-oxidative stability, especially in hot/wet conditions. They should have a high strength-to-weight ratio while having a relatively low density as compared to a solid (monolithic) metal. They should be damage resistant and damage tolerant, but they should dent like metal to visibly show damaged areas long before the damage results in actual failure of the part. They should be resistant to jet fuel and aerospace solvents. Finally, they should be resistant to crack growth, preferably slower than monolithic titanium.
The hybrid laminates generally have alternating layers of titanium alloy foil 110 and a fiber-reinforced organic matrix composite 120 (FIG. 11). The foil typically is sol coated in accordance with the method of the present invention to enhance adhesion between the foil and the matrix resin of the composite (and any intervening primers or adhesives). The sol coating may also provide corrosion resistance to the titanium. The foil typically is about 0.01-0.003 inches thick (3-10 mils) of β-annealed titanium alloy having a yield strain of greater than about 1%. The composite typically is a polyimide reinforced with high strength carbon fibers. The polyimide is an advanced thermoplastic or thermosetting resin capable of extended exposure to elevated temperatures in excess of 350° F., such as BMI, PETI-5, PIXA, KIIIB, or a Lubowitz and Sheppard polyimide. The composite is one or more plies to provide a thickness between the adjacent foils of about 0.005-0.03 inches (5-30 mils). Other configurations of the hybrid laminates, like metal reinforced resin composites, might be used.
The preferred composite is formed from a prepreg in the form of a tow, tape, or woven fabric of continuous, reinforcing fibers coated with a resin to form a continuous strip. Typically, we use a unidirectional tape. The fibers make up from about 50 to 70 volume percent of the resin and fibers when the fiber is carbon, and from about 40 to about 60 volume percent when the fiber is boron. When a mixture of carbon and boron fibers is used, total fiber volume is in the range 75 to 80 volume percent. The plies may be oriented to adjust the properties of the resulting composite, such as 0°/90° or 0°/−45°/+45°/0°, or the like.
Hybrid laminates of this type exhibit high open-hole tensile strength and high compressive strength, thereby facilitating mechanical joining of adjacent parts in the aircraft structure through fasteners. The laminates might also include Z-pin reinforcement in the composite layers or through the entire thickness of the laminate. Z-pinning techniques are described in U.S. Pat. Nos. 5,736,222; 6,027,798; 5,980,665; 5,862,975; or 5,869,165.
The hybrid laminates can be used in skin panels on fuselage sections, wing sections, strakes, vertical and horizontal stabilizers, and the like. The laminates are generally bonded as the skins 100 of sandwich panels that preferably are symmetrical and include a central core 130 of titanium alloy honeycomb, phenolic honeycomb, paper honeycomb, or the like (FIG. 12), depending on the desired application of sandwich panel. Sandwich panels are a low density (light weight), high strength, high modulus, tailorable structure that has exceptional fatigue resistance and excellent thermal-mechanical endurance properties.
The hybrid laminates are also resistant to zone 1 lightning strikes because of the outer titanium foil.
Outer metal layers protect the underlying composite from the most severe hot/wet conditions and the cleaning solvents that will be experienced during the service life of the product, especially if it is used on supersonic aircraft.
To prepare the hybrid laminates, generally we pretreat cleaned, β-annealed Ti-6Al-4V alloy foils in various concentrations (i.e. 20%, 60%, or 80%) of TURCO 5578 alkaline etchant (supplied by Atochem, Inc. of Westminster, Calif.). After water rinsing the foils are immersed in 35 vol % HNO3—HF etchant at 140° F. to desmut the foil, they are rinsed again, and, then, are sol coated.
For the strongest interaction between the sol-gel film and the composite, we prefer that the organic moiety of the silane correspond with the characteristics of the resin. For example, PETI-5 is a PMR-type or preimidized, relatively low molecular weight resin prepreg having terminal or pendant phenylethynyl groups to promote crosslinking and chain extension during resin cure. Therefore, the silane coupling group might include a reactive functionality, such as an active primary amine; an anhydride, carboxylic acid, or an equivalent; or even a phenylethynyl group, to promote covalent bonding between the sol coating and the resin. The organic moiety might simply be an aliphatic lower alkyl moiety to provide a resin-philic surface to which the resin will wet or have affinity for to provide adhesion without producing covalent bonds between the organosilane coupling agent and the resin. The aliphatic moiety, however, would still provide hydrogen atoms for hydrogen bonding with the numerous heteroatoms (oxygen) in the cured PETI-5 imide. If the resin includes a nadic or maleic crosslinking functionality, as Lubowitz and Sheppard suggest or as occurs in bismaleimides, then the organosilane coupling agent might include the same nadic or maleic crosslinking functionality or an amine, —OH, or —SH terminal group for covalent bonding through capping extension or the Michael's addition across the active unsaturated carbon-carbon bond in the resin's cap. For higher temperature applications, we recommend using an aromatic organometallics since these compounds should have higher thermo-oxidative stability.
Greater covalent interaction between the resin and sol-gel film is likely to occur if the resin is a PMR formulation at the time of layup onto the foil rather than a fully imidized resin of relatively high formula weight, such as Lubowitz and Sheppard propose. Of course, PMR formulations have their processing limitations. Knowing which resin approach will provide the best overall performance in the hybrid laminates remains for further testing, as does selection of the absolute type of resin and its formulation. Ideally, the resin is easy to process because it has few adverse aging consequences from extended exposure to ambient conditions common during fiber placement. The resin prepregs should also have long shelf lives. Alternately, the resin should be suitable for in situ consolidation while being placed on the foil.
Tows of mixed carbon and boron fibers suitable for these hybrid laminates are sold under the tradename HYBOR by Textron Specialty Materials of Lowell, Mass. Boron fibers provide high compressive strength, while carbon fibers provide high tensile strength. The preferred boron fiber has the smallest diameter (typically 4-7 mils) and the highest tensile elongation.
Hybrid laminates can have open-hole tensile strengths of about 150-350 ksi and an ultimate tensile strength in excess of 2×106 psi/lb/in3.
4. Paint Adhesion
A sol coating is particularly useful as an adherent for surface coatings (paints), especially urethane coatings, that are common in aerospace applications. Essentially the same aspects that make the sol coatings advantageous for hybrid laminates make them advantageous for paint adhesion. They convert the metal surface into a surface with high affinity for the paint binder. They preferably include components that covalently bond to the metal substrate as well as to the paint binder. In this application, rather than applying an adhesive 33 (FIG. 13) over the primer 39, we apply the exterior surface coating or paint 55 (FIG. 15) typically pigments carried in a urethane binder. The sol coating provides long lasting durability for adherence of the primer and finish coating to the metal.
The sol coating of the present invention promises to improve paint adhesion and to simplify field repair and maintenance of painted metal surfaces, especially titanium or aluminum structure painted with epoxy or urethane paints. Because the sol has essentially a neutral pH, it can be easily used in the field for touch up without the precautions or special equipment necessary for andozing. Through the sol coating 45, the paint 55 is essentially covalently bonded to the metal 65 as shown in FIG. 15 and adhesion is significantly enhanced. We obtain improved adhesion even for parts that have had acid surface etching several weeks prior to priming and painting.
The preferred sol coating process for paint adhesion improvement involves:
(a) cleaning the surface with an aqueous detergent or another cleaning solvent.
(b) wetting the surface for at least five (5) min prior to applying the sol;
(c) applying the sol by spraying or another suitable means while continuing to keep the surface wet for 1-2 min;
(d) drying the sol to form a sol coating at ambient conditions for 15-60 min;
(e) heating the sol coating to a temperature in the range from 160-250° F. (preferably, 230±20° F.) for 15-45 min to complete the drying; and
(f) applying primer or paint, as appropriate, between 2-72 hours after completing drying steps (a) & (e).
The sol has a pot life of up to about ten hours. Of course, there is an induction time following mixing that reduces the period of time in which the sol can be applied. We achieve the most consistent results using deionized water as the carrier or solvent. The deionized water should have a minimum resistivity of about 0.2 M. The sol might also be used as a coupling agent in polyimide resin composite bonds (especially BMI or KIIIB composites) to other resin composite parts or to metals.
The sol coating can be applied to advantage on sheet, plate, foil, or honeycomb. While described primarily with reference to Ti, the sol coating is also useful on Al; Cu, or Fe pure metals or alloys. One application for copper includes coating a susceptor mesh or foil used in thermoplastically welded composite structures. Another application for coated copper includes protecting the metallic interlayers in multichip modules or multilayer chip module packaging. Suitable ferrous alloys are mild steel, cold rolled steel, stainless steel, or high temperature alloys, such as the nickel-iron alloys in the INCONEL family.
To prepare the sol according to the mixing procedure outlined in Table 6. The absolute volume mixed can vary as needed. Once mixed the sol may age for 4-6 hours to reach equilibrium.







TABLE 6







Sol Preparation for Amino-based Silanes







STEP











Stir 500 ml deionized (DI) water in 1000 ml
Flask 1 (1000 ml)


flask


Add 4 Drops NH4OH


Verify pH around 7-8 (add more if appropriate)


Add 7.3 ml glacial acetic acid (GAA) to 50 ml
Flask 2 (50 ml)


flask


Add 10 ml TPOZ into 50 ml flask with GAA


Shake mixture


Add 34 ml organosilane to 1000 ml flask, avoid
Flask 1 (1000 ml)


drops on sides of flask


Cover flask


Stir for 20 to 30 minutes


Add about 300 ml DI to 500 ml flask
Flask 3 (500 ml)


Add about 200 ml DI to 200 ml flask
Flask 4 (200 ml)


Dilute contents of 50 ml flask with equivalent
Flask 2 (50 ml)


volume of DI water


Add entire contents of 50 ml flask to 500 ml
Flask 2 (50 ml) +


flask (should be clear)
Flask 3 (500 ml)


Add 3 ml of NH4OH, squirt in while, agitating


violently; pH should be about 5 (milky white)


Add contents of 500 ml flask to 1000 ml flask
Flask 3 (500 ml) +



Flask 1 (1000 ml)


rinse 500 and 50 ml flasks with DI water from
Flask 1 (1000 ml),


200 ml flask (pH between 8-9) into 1000 ml
Flask 2 (50 ml)


flask
Flask 3 (500 ml),



Flask 4 (200 ml)


Allow solution to age for up to 4-6 hours under


constant agitation prior to application









A presently preferred surface pretreatment for the metal (albeit one different from that schematically illustrated in FIG. 1) includes the steps outlined in Table 7.







TABLE 7







Surface Treatments









Pretreatment Process Steps
Temp
Time













Aqueous Degrease with Super
150 ± 5 F.
20 to 30
minutes


Bee per BAC 5763 (optional)


Water immersion rinse
 100 ± 15 F.
3 to 5
minutes


(optional)


Alkaline Clean Brulin 815 GD
140 ± 5 F.
20 to 40
minutes


per BAC 5749


Water immersion rinse
 100 ± 15 F.
3 to 5
minutes









Water Spray Rinse
Ambient
NA










Turco 5578 Alkaline Etch
190 ± 5 F.
15 to 20
minutes


(80% concentration)


DI Water Immersion Rinse
Ambient
3 to 5
minutes


HNO3 Desmut (35%
150 ± 5 F.
3 to 4
minutes


concentration)


DI Water Immersion Rinse with
Ambient
3 to 5
minutes


Agitation









DI Water Spray Rinse
Ambient
NA










Verify parts are water break





free for greater than 60


seconds









BOECLENE desmutting can replace HNO3. The composition and use of BOECLENE is described in U.S. Pat. No. 4,614,607, which we incorporate by reference. Acid etching might use other etchants than HNO3—HF1, but we prefer that etchant.

5. Pigmented Sols

While our preferred sol has GTMS and TPOZ in concentrations of about 3-30 vol % (0.03-0.3M), we might also include aminopropyltrimethoxysilane to tailor the coating for adhesion to polyimide overcoats or to help disperse the organic, metallic, metal sulfide, or metal oxide pigments that we add to obtain a desired gloss, color,-reflectivity, conductivity, emissivity, or combination thereof. We might also add a titanium alkoxide-or an aluminum alkoxide, like titanium isopropoxide or aluminum butoxide, in combination with the TPOZ or in place of the TPOZ to provide desired characteristics for the coating.
Generally the molar (or volumetric) ratio of GTMS:TPOZ is about 3.7:1, but the optimum ratio depends on the application for the coating.
The coating thickness increases as the concentration of the organometallics (or reagents) of the sol increases. In addition, the ease of application and the rate of build up of the coating increases as the organometallics concentration increases. At dilute concentrations, many coats might be required. Runs and drips are difficult to control because of the low concentration of organometallics. Concentrated sols, however, may exhibit poor adhesion to the substrate, especially when the coating is sprayed on. For spraying, we prefer to limit the organometallics concentration to about 15-30 vol % (0.15-0.30M). Our goal is to provide a sol-gel replacement for paint that will have high impact resistance and be usable over a wide range of temperatures.
To minimize the proportion of organics in the coating, we can substitute tetra-ethyl-orthosilicate (TEOS) for all or part of the GTMS or other organosilane, first hydrolyzing it in alcohol. We can make graded sol-gels by adjusting the ceramic character as we previously described.
The concentration of pigments we can add to the sol is also directly proportional to the organometallics concentration. Also, because the coating is very thin (on the order of nanometers), the pigments should have comparable or smaller characteristic dimensions. The molar ratio of pigments to organometallics should be in the range from about 1-3 parts pigment to 1 part organometallics. The concentration of pigments also depends on the size and physical and chemical characteristics of the pigments. Their total wetted surface area appears to be an important consideration. The sols might also include carbon or graphite particles or fibers.
Generally the pigments are metal flakes, metal oxide particles, or organometallic particles. Suitable aluminum flake pigments include the Aquasil BP series of pigments available from Siberline Manufacturing Co. The pigments might be glass, mica, metals (like nickel, cobalt, copper, bronze, and the like available from Novamet) or glass flake, silver coated glass flake, mica flake, or the like available from Potters Industries, Inc. These flakes typically are about 17-55 μm for their characteristic dimension. In some applications, ceramic pigments may be appropriate. Of course, the pigments can be mixed to provide the desired characteristics for the coating.
We have had success spraying with a Binks Mach 1 HVLP spray gun pigmented sols that included Titanox 2020 titanium oxide pigment (available from NL Industries), copper oxide or iron oxide pigments (available from Fischer Scientific), or NANOTEK titania, zinc oxide, or copper oxide pigments (available from Nanophase Technologies Corporation). These pigments are generally spherical with diameters in the range form about 30 nm (for the NANOTEK pigments) to micron sizes.
Our pigmented sol coatings pass wet and dry tape adhesion tests and the GE 80 in-lb impact test on 2024 aluminum, as required for enamel coatings per Boeing Material Specification (BMS) 10-60K “Protective Enamel.” The coatings pass the impact test even at liquid nitrogen temperatures (about −196° C. (−321° F.)) and after thermal cycling (or extended exposure) to about 750° F. in air. In fact, in one impact test, the substrate failed rather than the coating after we heated the sample for one hour at 1000° F. Coatings using powder pigments are better in impact tests than those that use flakes. The differences in impact test results may arise from the high aspect ratios (length/width) characteristic of flakes, but may also reflect our failure to optimize the sol formulations and spray gun settings for the sols we have tested to date.
The pigmented coatings should also satisfy Boeing Material Specification BMS 14-4H “Protective Coating, Inorganic, Heat, Weather and Oil Resistant,” if the coated products are targeted for use in aerospace applications. Unlike the traditional coatings qualifying to BMS 14-4H, the pigmented sol coatings of the present invention are significantly thinner and, thereby, do not impose as significant a weight penalty on the final product.
Other suitable pigments include those described in U.S. patent application Ser. No. 08/770,606 entitled “High Efficiency Metal Pigments” or U.S. Provisional Patent Application 60/089,328 filed Jun. 15, 1998, entitled “Method for Making Particulates of Controlled Dimensions.” Other potential pigments are described in the CRC HANDBOOK OF CHEMISTRY AND PHYSICS, 51st ed., F-60 through F-62 (1970).
Our method to prepare the sol alters the reaction kinetics from traditional sols and results in sol-gel coatings. We achieve a relatively long effective pot life for the sol as opposed to processes like Yoldas uses in U.S. Pat. No. 4,754,012. In fact, the pot life of our sol is comparable to conventional aerospace catalyzed paints (4-8 hours) rather than 0.5-1.0 hour. Typically our pot lives are from 0.5-6 hours, but we have successfully applied sols as old as 24 hours. We believe that the sol-gel's adhesion degrades if the pot life is excessive. We have yet to measure the adhesion for the sol-gel formed with a 24 hour old sol.
Alcohol-based sols present fire hazards. They are regulated today and are likely to be prohibited at some in the future. Our water-based sols can be applied wherever it is convenient, because they are low volatile-omitting formulations. Alcohol-based sols require special health and safety equipment. The waterborne sols do not require a specialized paint spray booth.
Conductive coatings have promise for space vehicles to prevent electrostatic discharges grounding, and electromagnetic interference (EMI) problems. In a space environment, the preferred sol-gel coating provides resistance to atomic oxygen, ultraviolet radiation, and/or high energy particles that comnmonly erode unprotected substrates, especially composites, in low earth orbit (LEO). Such a coating might be the pigment Zr—Si sol or a graded sol using TEOS in one or more layers.
While we have described preferred embodiments, those skilled in the art will readily recognize alterations, variations, and modifications which might be made without departing from the inventive concept. Therefore, interpret the claims liberally with the support of the full range of equivalents known to those of ordinary skill based upon this description. The examples illustrate the invention and are not intended to limit it. Accordingly, define the invention with the claims and limit the claims only as necessary in view of the pertinent prior art.

## Claims

1. A graded mixed metal Zr:Si sol-gel, comprising:
(a) a first layer made by mixing in a suitable carrier an effective amount of an organozirconium with tetraethyl orthosilicate (TEOS) to form a sol-gel network;
(b) a second layer made by mixing in a suitable carrier an effective amount of the organozirconium and an organosilane selected from the group consisting of:
3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane,
p-aminophenyltrimethoxysilane, m-aminophenyltrimethoxysilane,
allyltritnethoxysilane, n-(2-aminoethyl)-3-aminopropyltrimeethoxysilane,
3-arninopropyltrimethoxysilane, 3-glycidoxypropyldiisopropylethoxysilane,
(3-glycidoxypropyl)methyldiethoxysilane 3-glycidoxypropyltrimethoxysilane-,
3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane,
3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropylmethyldimethoxysilane,
3-methacryloxypropyltrimethoxysilane, n-phenylaminopropyltrimethoxysilane, vinylmethyldiethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, and mixtures thereof to form a sol-gel network, and
(c) an organometallic alkoxide having Ti or Al in at least one of the first layer and the second layer; and wherein the first layer has a stronger ceramic character than the second layer.